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Influences on the Distribution and Occurrence of Nitrate-Nitrogen and Total Phosphorus in the Water Resources of the Suw...

Permanent Link: http://ufdc.ufl.edu/UFE0021039/00001

Material Information

Title: Influences on the Distribution and Occurrence of Nitrate-Nitrogen and Total Phosphorus in the Water Resources of the Suwannee River Water Management District
Physical Description: 1 online resource (262 p.)
Language: english
Creator: Hornsby, H David
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: aquifer, domains, floridan, groundwater, hydrochemical, loads, nitrate, phosphorus, surfacewater, suwannee
Soil and Water Science -- Dissertations, Academic -- UF
Genre: Soil and Water Science thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: In Florida, the Suwannee River is highly influenced by the interconnection with groundwater. This relationship affects the quality and quantity of water in the river. An increasing temporal trend in nitrate-nitrogen (NO3-N) concentration and a declining temporal trend for total phosphorus (TP) concentrations has been identified in the river. Loadings of NO3-N were consistently highest in the Middle Suwannee River Basin (MSRB) and the Lower Santa Fe River Basin (LSFRB). The research objectives were to indentify changes in riverine TP and NO3-N concentrations and relate to anthropogenic influences, characterize groundwater/surfacewater interaction in the MSRB and LSFRB and locate segment(s) with the greatest NO3-N load entering the river, delineate groundwater domains in the Suwannee River Water Management District (SRWMD) using potentiometric surface maps and hydrochemical facies analysis, and determine relationships of groundwater domain TP and NO3-N concentrations to domain landuse/landcover. The increasing temporal trend in NO3-N concentrations and declining temporal trend in TP concentrations are still present in the river. The declining trend in TP is related to management of a phosphate mining discharge. The NO3-N concentration observed in the Suwannee River at Branford is likely related to fertilizer sales/use in Suwannee and Lafayette counties. The increase in NO3-N loading in the MSRB and LSFRB occurred over small segments of each river. The NO3-N load increases in the MSRB and LSFRB appear to be due to groundwater inputs based on riverine chemical signature and river discharge. Eight groundwater domains were delineated from the SRWMD potentiometric surface maps and were refined to nine domains using hydrochemical facies analysis. Groundwater domain landuse/landcover was related to observed groundwater domain TP and NO3-N concentrations. When crop and pasture land was greater than 12 % of the land area of the groundwater domain elevated groundwater NO3-N concentrations were observed. These landuses receive much of the fertilizer used in the basins. Groundwater domains with elevated NO3-N concentrations are adjacent to the MSRB and LSFRB. Groundwater domains with elevated NO3-N concentrations are affecting the surfacewater quality that receives discharge from these groundwater domains and the most likely source of the NO3-N is fertilizer use in the groundwater domains.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by H David Hornsby.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Graetz, Donald A.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021039:00001

Permanent Link: http://ufdc.ufl.edu/UFE0021039/00001

Material Information

Title: Influences on the Distribution and Occurrence of Nitrate-Nitrogen and Total Phosphorus in the Water Resources of the Suwannee River Water Management District
Physical Description: 1 online resource (262 p.)
Language: english
Creator: Hornsby, H David
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007

Subjects

Subjects / Keywords: aquifer, domains, floridan, groundwater, hydrochemical, loads, nitrate, phosphorus, surfacewater, suwannee
Soil and Water Science -- Dissertations, Academic -- UF
Genre: Soil and Water Science thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: In Florida, the Suwannee River is highly influenced by the interconnection with groundwater. This relationship affects the quality and quantity of water in the river. An increasing temporal trend in nitrate-nitrogen (NO3-N) concentration and a declining temporal trend for total phosphorus (TP) concentrations has been identified in the river. Loadings of NO3-N were consistently highest in the Middle Suwannee River Basin (MSRB) and the Lower Santa Fe River Basin (LSFRB). The research objectives were to indentify changes in riverine TP and NO3-N concentrations and relate to anthropogenic influences, characterize groundwater/surfacewater interaction in the MSRB and LSFRB and locate segment(s) with the greatest NO3-N load entering the river, delineate groundwater domains in the Suwannee River Water Management District (SRWMD) using potentiometric surface maps and hydrochemical facies analysis, and determine relationships of groundwater domain TP and NO3-N concentrations to domain landuse/landcover. The increasing temporal trend in NO3-N concentrations and declining temporal trend in TP concentrations are still present in the river. The declining trend in TP is related to management of a phosphate mining discharge. The NO3-N concentration observed in the Suwannee River at Branford is likely related to fertilizer sales/use in Suwannee and Lafayette counties. The increase in NO3-N loading in the MSRB and LSFRB occurred over small segments of each river. The NO3-N load increases in the MSRB and LSFRB appear to be due to groundwater inputs based on riverine chemical signature and river discharge. Eight groundwater domains were delineated from the SRWMD potentiometric surface maps and were refined to nine domains using hydrochemical facies analysis. Groundwater domain landuse/landcover was related to observed groundwater domain TP and NO3-N concentrations. When crop and pasture land was greater than 12 % of the land area of the groundwater domain elevated groundwater NO3-N concentrations were observed. These landuses receive much of the fertilizer used in the basins. Groundwater domains with elevated NO3-N concentrations are adjacent to the MSRB and LSFRB. Groundwater domains with elevated NO3-N concentrations are affecting the surfacewater quality that receives discharge from these groundwater domains and the most likely source of the NO3-N is fertilizer use in the groundwater domains.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by H David Hornsby.
Thesis: Thesis (Ph.D.)--University of Florida, 2007.
Local: Adviser: Graetz, Donald A.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2007
System ID: UFE0021039:00001


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INFLUENCES ON THE DISTRIBUTION AND OCCURRENCE OF NITRATE-NITROGEN
AND TOTAL PHOSPHORUS INT THE WATER RESOURCES OF THE SUWANNEE RIVER
WATER MANAGEMENT DISTRICT





















By

H. DAVID HORNSBY


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY
OF FLORIDA INT PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE
OF DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

2007






























O 2007 H. David Hornsby































To my wife, Jennifer, my children Lauren, Jenna, and Kyra, and the Suwannee River









ACKNOWLEDGMENTS

I thank my advisor, Dr. Donald Graetz, for his guidance, assistance and encouragement

through out this study. I thank my committee members, Dr. Thomas Obreza, Dr. Wendy

Graham, Dr. Vimala Nair and Dr. Sam Upchurch, for their valuable suggestions and guidance.

I thank the Florida Geological Survey and Florida Department of Environmental

Protection for providing personnel and equipment for field sampling. I especially thank Rick

Copeland, Tom Greenhalgh and Harley Means of the Florida Geological Survey and Rick Hicks

of the Department of Environmental Protection for their assistance with this study.

I thank the Suwannee River Water Management District for providing me the opportunity

to work on one of the most unique and wonderful systems in the world.

I thank my wife for her support and encouragement during this journey.












TABLE OF CONTENTS
Pac

ACKNOWLEDGMENTS .............. ...............4.....


LIST OF TABLES ........._.. ..... ._ __ ...............7....


LIST OF FIGURES .............. ...............12....


LI ST OF AB BREVIAT IONS ........._.._ ......___ ............... 19....


AB S TRAC T ..... ._ ................. ............_........2


CHAPTER

1 INTRODUCTION .............. ...............24....


2 LITERATURE REVIEW .............. ...............27....

Overview of the Suwannee River Basin ................ .............. ......... .....27
Location .............. ...............27....

Hydrology .............. ...............27....
Phy si ography ................. ...............29........... ....
S oil s............... ...............3 0.

Hydro geology .............. ...............33....
Land Use Overview .............. ...............34....
Water Quality Characteristics ....... ................ .. ..... ..._ ........3
Nutri ents ................. ...............37.................

Phosphorus ........._.. ..... ._ ...............37.....
Phosphorus cycle ............... .............. ..........3
Occurrence of phosphorus in groundwater ........._._. ..... .._._............39
Concerns with phosphorus ....__ ......_____ .......___ ............3
Water quality standards for phosphorus .............. ...............40....
N itrogen .............. ...............40....
Nitrogen cycle ................. ...............41.......__.....
Occurrence of nitrate-nitrogen ................. ........___ ......... 42.... ....
Concerns with nitrate-nitrogen .............. ...............43....
Water quality standards for nitrate-nitrogen ......___............. ...... .........44
W ater Quality Assessments .............. ...............45....
Groundwater Domain Delineation ...._. ......_._._ .......__. ............4

3 COMPARISONS OF PRE AND POST OUTSTANDING FLORIDA
WATER CONCENTRATIONS, TRENDS AND RECENT
OCCURRENCES OF TOTAL PHOSPHORUS AND NITRATE-
NITROGEN CONCENTRATIONS ................. ...............63.................


Introduction ................. ...............63.................
Materials and Methods............... ...............65












Long Term Trend Analysis............... .. .... .. ................6
Recent Distribution and Occurrences of Total Phosphorus and
Nitrate-Nitrogen ......__................. .......__ .........65
Results and Discussion .............. ...............66....
Long Term Trend .................. ......... ......... .........._._ ............6
Comparison of Pre and Post OFW Water Quality ................. .....................67
Anthropogenic Factors ................. .. ............ .... .. ..................... 6
Recent Distribution and Occurrences of Total Phosphorus and
Nitrate-Nitrogen ................. ......_ ..... ...............71..
Upper Floridan aquifer water quality .....__.___ ..... ....__ ..........._.....71
Spring water quality ........._... .....__ ...............73...
Surface water quality .............. ...............74....
Summary and Conclusions .............. ...............76....

4 NITRATE-NITROGEN LOADING FROM GROUND WATER TO
SELECTED REACHES OF THE SUWANNEE AND SANTA FE RIVERS ..107


Introduction ............ ..... .._ ...............107...
M materials and M ethods ............ ..... .._ ...............109..
Results and Discussion ............ _...... ._ ...............111...
Middle Suwannee River Basin. ....__ ......_____ .......___ ...........11
Lower Santa Fe River Basin ....__ ......_____ .......___ ..........15
Summary and Conclusions ............ .....__ ...............119..


5 GROUNDWATER DOMAIN DELINEATION AND LANDUSE
INFLUENCES ON GROUNDWATER QUALITY ............__ ..........___.....146


Introduction ............ ..... ._ ...............146...
M materials and M ethods ............ ..... ._ ...............151...
Results and Discussion .............. ...............152....
Summary and Conclusions .............. ...............158....


6 SY NT HESIS ............ ..... ._ .............. 18 5...


APPENDIX


A HISTORICAL TOTAL PHOSPHORUS AND NITRATE-NITROGEN ...........189


B WATER QUALITY SUMMARY ............__......__ ....___ ...........19


C SELECTED MIDDLE SUWANNEE SPRINGS .............. ....................23


D WATER QUALITY SUMMARY BY GROUNDWATER DOMAINS ............236


REFERENCE LIST .............. ...............253....


BIOGRAPHICAL SKETCH ................. ...............262......... ......










LIST OF TABLES


Table Pn

2-1 Reaches of the Suwannee River ................. .............. ......... .....52

2-2 National NO3-N concentrations in 383 U.S. Rivers. .............. ...............52

2-3 Tidal-freshwater water quality indices based on NO3-N
concentration. ............. ...............52.....

3-1 Comparison of pre and post OFW concentrations of TP and NO3-N
to OFW baseline concentrations of TP and NO3-N for the Suwannee
River at Branford. ............. ...............78.....

3-2 Comparison of baseline annual NO3-N load to water years 1998 to
2005 annual NO3-N load ................. ...............78................

3-3 Cross correlation of N fertilizer sales and annual median riverine
NO3-N concentration for the Suwannee River at Branford. ....................79

3-4 Summary of NO3-N and TP concentrations in the upper Floridan
aquifer for the Suwannee River Water Management District
(2001 to 2006). ............. ...............79.....

3-5 Summary ofNO3-N and TP concentrations for the Springs by
River Basin in the Suwannee River Water Management District
(1989 to 2006). ............. ...............80.....

3-6 Summary of NO3-N and TP concentrations for each River
Basin (1989 to 2006). ............. ...............8 1....

3-7 TP and NO3-N Loadings by Watersheds/Reach in the Suwannee
River for water year 2005. ............ ...............82.....

4-1 Suwannee River and Santa Fe River segments used in this study along
with sampling dates and other pertinent information. ............ ................121

4-2 Middle Suwannee River Basin spring comparison 2000 to 2006
of discharge, NO3-N concentration, NO3-N Load and contribution
of the total NO3-N load increase in the study reach.. ............ ...... .......... 122

4-3 Middle Suwannee River Basin NO3-N change profile 2000 and 2006. ..123

4-4 Lower Santa Fe River Basin NO3-N change profile 2001 and 2006.......123











Table Page

4-5 Lower Santa Fe River Basin refined NO3-N change profile for 2006.....123

4-6 Lower Santa Fe River Basin spring comparison 2000 to 2006 of
discharge, NO3-N concentration, NO3-N Load and contribution of
the total NO3-N load increase in the study reach ................. .................1 24

4-7 Discharge, NO3-N concentration, NO3-N Load and contribution of
the total NO3-N load increase in the study reach for Lower Santa
Fe River Basin springs in refined segments (October 10, 2006). ...........125

5-1 Principal component analysis showing significant components ..............159

5-2 Statistical summary for NO3-N and TP by groundwater domain. ..........160

5-3 1995 level 2 Florida Landuse Code for the Alapaha
groundwater domain. ............ ...............161.....

5-4 1995 level 2 Florida Landuse Code for the Aucilla
groundwater domain. ............ ...............162.....

5-5 1995 level 2 Florida Landuse Code for the Coastal
groundwater domain. ............ ...............163.....

5-6 1995 level 2 Florida Landuse Code for the Dixie
groundwater domain. ............ ...............164.....

5-7 1995 level 2 Florida Landuse Code for the Ichetucknee
groundwater domain. ............ ...............165.....

5-8 1995 level 2 Florida Landuse Code for the Santa Fe
groundwater domain. ............ ...............166.....

5-9 1995 level 2 Florida Landuse Code for the Steinhatchee
groundwater domain. ............ ...............167.....

5-10 1995 level 2 Florida Landuse Code for the Suwannee
groundwater domain. ............ ...............168.....

5-11 1995 level 2 Florida Landuse Code for the Waccasassa
groundwater domain. ............ ...............169.....

B-1 Summary of upper Floridan groundwater quality for the Suwannee
River Water Management District (2001 to 2006). ............ .................192










Table Pay~

B-2 Summary of water quality parameters for the Springs of Aucilla
River Basin (1989 to 2006) ................. ...............193..............

B-3 Summary of water quality parameters for the Springs of Coastal
Rivers Basin (1989 to 2006). ............. ...............194....

B-4 Summary of water quality parameters for the Springs of Lower
Suwannee River Basin (1989 to 2006). ............. ....................19

B-5 Summary of water quality parameters for the Springs of Santa Fe
River Basin (1989 to 2006) ................. ...............196..............

B-6 Summary of water quality parameters for the Springs of Upper
Suwannee River Basin (1989 to 2006). ............. ....................19

B-7 Summary of water quality parameters for the Springs of Waccasassa
River Basin (1989 to 2006) ................. ...............198..............

B-8 Summary of water quality parameters for the Springs of
Withlacoochee River Basin (1989 to 2006) ................. .....................199

B-9 Summary of surfacewater quality parameters for the Alapaha
River Basin (1989 to 2006) ................. ...............200..............

B-10 Summary of surfacewater quality parameters for the Aucilla
River Basin (1989 to 2006) ................. ...............201..............

B-11 Summary of surfacewater quality parameters for the Coastal Rivers
Basin (1989 to 2006) ................. ...............202..............

B-12 Summary of surfacewater quality parameters for the Lower
Suwannee River Basin (1989 to 2006). ............. ....................20

B-13 Summary of surfacewater quality parameters for the Santa Fe River
Basin (1989 to 2006) ................. ...............204..............

B-14 Summary of surfacewater quality parameters for the Upper
Suwannee River Basin (1989 to 2006). ............. ....................20

B-15 Summary of surfacewater quality parameters for the Waccasassa
River Basin (1989 to 2006) ................. ...............206..............

B-16 Summary of surfacewater quality parameters for the Withlacoochee
River Basin (1989 to 2006) ................. ...............207..............












Table


B-17A TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 1998. ............. ...............208....

B-17B TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 1999. ................ ......... ...............208 ....

B-17C TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 2000. ............. ...............209....

B-17D TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 2001 ................ ...............209........... ...

B-17E TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 2002. ............. ...............210....

B-17F TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 2003 ................ ...................... ..................210

B-17G TP and NO3-N loadings by watersheds/reach in the Suwannee River
for water year 2004. ................ ...............211...............

D-1 Groundwater quality statistical summary by groundwater domain.........236

D-2A. The Kruskal-Wallis Test for the groundwater domains differences
using nine domains. ............. ...............244....

D-2B. The Kruskal-Wallis Test for the groundwater domains differences
using eight domains. ............. ...............244....

D-2C. The Kruskal-Wallis Test for the groundwater domains differences
using seven domains. ............. ...............245....

D-2D. The Kruskal-Wallis Test for the groundwater domains differences
using six domains............... ...............245

D-2E. The Kruskal-Wallis Test for the groundwater domains differences
using five domains. ............. ...............246....

D-2F. The Kruskal-Wallis Test for the groundwater domains differences
using four domains............... ...............246

D-2G. The Kruskal-Wallis Test for the groundwater domains differences
using three domains. ............. ...............247....










Table


D-2H. The Kruskal-Wallis Test for the groundwater domains differences
using two domains. ............. ...............247....










LIST OF FIGURES


Finure Page

1-1 Basins of the Suwannee River System. ........... ...............26......

2-1 Physiography regions of the Suwannee River Water Management District. ...53

2-2 High leaching soils in the Suwannee River Water Management District.........54

2-3 Generalized geologic cross section of the region. ............ .....................5

2-4 Confined and unconfined regions of the Floridan aquifer system. .........__......56

2-5 Map showing the reaches of the Suwannee River in Florida. ........................57

2-6 Plot of mean alkalinity (mg L1 as CaCO3) in the five reaches of the
Suwannee River in Florida. ............. ...............58.....

2-7 Plot of mean color (PCU) in the five reaches of the Suwannee River
in Florida. ............. ...............58.....

2-8 P cycle in soils. ............ ...............59.....

2-9 N cycle in soils. ............. ...............60.....

2-10 Nutrient loadings by watershed/reach in the Suwannee River System
for water year 1998. ............ ...............61.....

2-11 Estimated N inputs for Suwannee County. ............ ...............62.....

2-12 Estimated N inputs for Lafayette County. ............ ...............62.....

3-1 Suwannee River Water Management District surfacewater quality
monitoring network. ............. ...............83.....

3-2 Suwannee River Water Management District groundwater quality
monitoring network. ............. ...............84.....

3-3 Median TP for the Suwannee River at Branford with linear trend lines. ........85

3-4 TP concentration by water year for Suwannee River at Branford. Box
represents 25th percentile, median, 75th percentile and whiskers represents
the upper and lower observed value............... ...............86.

3-5 Median N03-N for the Suwannee River at Branford with linear trend line. ...87











Figure Page

3-6 NO3-N concentration by water year for Suwannee River at Branford. Box
represents 25th percentile, median, 75th percentile and whiskers represents
the upper and lower observed value............... ...............88.

3-7 Population for Lafayette and Suwannee counties, 1950 through 2004. ..........89

3-8 Median NO3-N concentration for the Suwannee River at
Branford and population for Lafayette and Suwannee counties. .....................90

3-9 Median TP concentration for the Suwannee River at
Branford and population for Lafayette and Suwannee counties. .....................91

3-10 Fertilizer sales data for Suwannee and Lafayette counties. ............ ................92

3-11 Median TP concentration for the Suwannee River at Branford and N
fertilizer sale for Suwannee and Lafayette counties. ............ .....................93

3-12 Median NO3-N concentration for the Suwannee River at Branford and
N fertilizer sales for Suwannee and Lafayette counties. ............. ..................94

3-13 Median NO3-N concentration for the Suwannee River at
Branford and N fertilizer sales and total crop acres for
Suwannee and Lafayette counties. ............. ...............95.....

3-14 Median K concentration for the Suwannee River at Branford with
linear trend line. ............ ...............96.....

3-15 Median K and median NO3-N concentrations for the Suwannee
River at Branford. ............ ...............97.....

3-16 Median K concentration for the Suwannee River at Branford
and K fertilizer sale for Suwannee and Lafayette counties. ............. ................98

3-17 Mean upper Floridan aquifer TP concentration contour map for
water year 2006. ............. ...............99.....

3-18 Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2006. ............. ...............100....

3-19 Mean upper Floridan aquifer K concentration contour map for
water year 2006. ................. ...............101....... .....

3-20 TP Loads for the Suwannee River to the Gulf of Mexico for water
years 1990 to 2005. ............ ...............102.....










Figure Page

3-21 NO3-N Loads for the Suwannee River to the Gulf of Mexico for water
years 1990 to 2005. ............ ...............103.....

3 -22 Annual TP loads and rainfall by water year for the Suwannee River. .............104

3-23 Annual NO3-N loads and rainfall by water year for the Suwannee River. ......105

3 -24 Suwannee River Basin loading by watershed/reach for
water year 2005. ............. ...............106....

4-1 Suwannee River Water Management District stations on the
Suwannee River with aerial photography. ............ ...... ............... 12

4-2 Suwannee River Water Management District stations on the
Santa Fe River with aerial photography. ............. ...............127....

4-3 Mean NO3-N and TP for Suwannee River Water Management District
Suwannee River stations (1989 to 2006). ............ ...... ............... 12

4-4 Mean NO3-N and TP for SRWMD Santa Fe River stations
(1989 to 2006). ............. ...............129....

4-5 Middle Suwannee River Basin sampling points (July 21, 2000) for
NO3-N profile............... ...............130

4-6 Middle Suwannee River Basin (Dowling Park to Branford) NO3-N
profie on July 21, 2000. ............. ...............131....

4-7 NO3-N profie of the Middle Suwannee River Basin (October 2000). ............132

4-8 NO3-N profie of Middle Suwannee River Basin (October 2000 and
September 2006). ............ ...............133.....

4-9 The relationship of discharge and NO3-N concentration for the Suwannee
River at Branford (1989 to 2006). ............. ...............134....

4-10 The relationship of specific conductance and discharge for the Suwannee
River at Branford (1989 to 2006)............... ...............135.

4-11 The relationship of specific conductance and NO3-N concentration for the
Suwannee River at Branford (1989 to 2006). ............. ....................13

4-12 Middle Suwannee River Basin sampling points and discharge cross-sections
(October 2000 and September 2006). ............ ...............137.....










Figure Page

4-13 Comparison of segment NO3-N load change per m of river in the Middle
Suwannee River Basin (July 2000 and September 2006). ............. ................138

4-14 Lower Santa Fe River Basin sampling points (June 7, 2000) for
N O3-N profie. ............. ...............139....

4-15 NO3-N profie of the Lower Santa Fe River Basin on June 7, 2000. ...............140

4-16 NO3-N profie of the Lower Santa Fe River Basin (September 2001
and October 2006). ............. ...............141....

4-17 Lower Santa Fe River Basin segments for September 2001 NO3-N profie. ...142

4-18 Refined Lower Santa Fe River Basin segments for October 2006
N O3-N profie. ............. ...............143....

4-19 Comparison of segment NO3-N load change per m of river in the Lower
Santa Fe River Basin (September 2001 to October 2006). ............. ...... ........._144

4-20 Refined segments NO3-N load change per m of river in the Lower Santa Fe
River Basin in October 2006. ............. ...............145....

5-1 Groundwater domains based on 1985 potentiometric surface. ........................170

5-2 Groundwater domains based on 1990 potentiometric surface. ........................171

5-3 Groundwater domains based on 1995 potentiometric surface .........................172

5-4 Groundwater domains based on 2002 potentiometric surface. ........................173

5-5 Groundwater domains based on 2005 potentiometric surface. ........................174

5-6 Principal component 1 contours for hydrochemical facies analysis.................175

5-7 Principal component 2 contours for hydrochemical facies analysis.................176

5-8 Refined groundwater domains based on composite potentiometric surfaces
and hydrochemical facies analysis. ............. ...............177....

5-9 Median groundwater TP concentration by groundwater domains. ..................178

5-10 Median groundwater NO3-N concentration by groundwater domains. ...........179











Figure Page

5-11 1995 level 2 Florida Landuse Code landuse/landcover for the Suwannee
River W ater Management District. ............. ...............180....

5-12 Median groundwater NO3-N concentration versus percentage of
groundwater domains in crop and pasture lands. ............. ....................18

5-13 Median groundwater TP concentration versus percentage of groundwater
basins in crop and pasture lands. ............. ...............182....

5-14 Median groundwater NO3-N concentration and percentage of groundwater
basins in crop and pasture lands. ............. ...............183....

5-15 Landuses within crop and pasture lands code for the groundwater domains
with elevated median NO3-N. ............. ...............184....

A-1 Median TP concentration for the Suwannee River at Branford. ................... ....189

A-2 Median NO3-N concentration for the Suwannee River at Branford. ................190

A-3 Median K concentration for the Suwannee River at Branford. .......................191


B-1A Mean upper Floridan aquifer TP concentration contour map for
water year 2001 ........... ..... ._ ...............212..

B-1B Mean upper Floridan aquifer TP concentration contour map for
water year 2002. ........... ..... ._ ...............213..

B-1C Mean upper Floridan aquifer TP concentration contour map for
water year 2003 ........... ..... ._ ...............214..

B-1D Mean upper Floridan aquifer TP concentration contour map for
water year 2004. ........... ..... ._ ...............215..

B-1E Mean upper Floridan aquifer TP concentration contour map for
water year 2005 ........... ..... .._ ...............216..

B-2A Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2001 ................ ...............217...............

B-2B Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2002 ................. ...............218................

B-2C Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2003 ................ ...............219................










Figure Page

B-2D Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2004 ................. ...............220................

B-2E Mean upper Floridan aquifer NO3-N concentration contour map for
water year 2005 ................. ...............221................

B-3A Mean upper Floridan aquifer K concentration contour map for
water year 2001 ................ ...............222...............

B-3B Mean upper Floridan aquifer K concentration contour map for
water year 2002 ................. ...............223................

B-3C Mean upper Floridan aquifer K concentration contour map for
water year 2003 ................ ...............224................

B-3D Mean upper Floridan aquifer K concentration contour map for
water year 2004 ................. ...............225................

B-3E Mean upper Floridan aquifer K concentration contour map for
water year 2005 ................. ...............226................

B-4A Suwannee River Basin loading by watershed/reach for water year 1998.........227

B-4B Suwannee River Basin loading by watershed/reach for water year 1999.........228

B-4C Suwannee River Basin loading by watershed/reach for water year 2000.........229

B-4D Suwannee River Basin loading by watershed/reach for water year 2001.........230

B-4E Suwannee River Basin loadings by watershed/reach for water year 2002.......231

B-4F Suwannee River Basin loading by watershed/reach for water year 2003.........232

B-4G Suwannee River Basin loading by watershed/reach for water year 2004.........233

C-1 Plot of NO3-N versus K concentrations for spring SUW718971. ................... .234

C-2 Plot of NO3-N versus K concentrations for spring SUW725971. ................... .23 5

D-1 1985 potentiometric surface map for the Suwannee River Water
Management District ................. ...............248....._._. ....

D-2 1990 potentiometric surface map for the Suwannee River Water
Management District. ...._.._................. ........_ _. ........24










Fioure


D-3 1995 potentiometric surface map for the Suwannee River Water
Management District ................. ...............250...............

D-4 2002 potentiometric surface map for the Suwannee River Water
M management District ................. ...............251...............

D-5 2005 potentiometric surface map for the Suwannee River Water
Management District ................. ...............252...............









LIST OF ABBREVIATIONS

ADCP Acoustic Doppler Current Profiler

BMP best management practice

C carbon

oC degrees Celsius

CAFO confined animal feeding operation

CFC chloroflurocarbons

efs cubic feet per second

d day

DAC S Florida Department of Agriculture and Consumer Services

DO dissolved oxygen

DOC dissolved organic carbon

EPA United States Environmental Protection Agency

F.A.C. Florida Administrative Code

FDEP Florida Department of Environmental Protection

FDER Florida Department of Environmental Regulation

FLUC Florida Land Use Code

GPS global positioning system

HRS Department of Health and Rehabilitative Services

IFAS Institute of Food and Agricultural Sciences

K potassium

kg kilogram

km kilometer









L liter

L s^l liter per second

LSRB Lower Suwannee River Basin

LSFRB Lower Santa Fe River Basin

m meter

Clg gl micrograms per gram

mg L1 milligram per liter

Cpg L1 micrograms per liter

MLRA Maj or Land Resource Area

ms1 mean sea level

MSRB Middle Suwannee River Basin

N nitrogen

NAWQA National Water Quality Assessment

NH4' ammonium

NO2~ nitrite

NO3~ nitrate

NO3-N nitrate-nitrogen

NOx-N nitrate plus nitrite nitrogen

NRCS Natural Resource Conservation Service

OFW Outstanding Florida Water

OM organic matter

P phosphorus

PCA principal component analysis










platinum cobalt unit

phosphate

Suwannee River Basin

Suwannee River Basin Nutrient Management Working Group

Suwannee River Water Management District

total dissolved soilds

total Kj eldahl nitrogen

Total Maximum Daily Load

Total organic carbon

total phosphorus

United States

United States Department of Agriculture

United States Geological Survey

Water Assessment Regional Network

year


PCU

PO43-

SRB

SRBNMWG

SRWMD

TDS

TKN

TMDL

TOC

TP

U.S.

USDA

USGS

WARN

y









Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

INFLUENCES ON THE DISTRIBUTION AND OCCURRENCE OF NITRATE-NITROGEN
AND TOTAL PHOSPHORUS INT THE WATER RESOURCES OF THE SUWANNEE RIVER
WATER MANAGEMENT DISTRICT

By

H. David Hornsby

December 2007

Chair: Donald Graetz
Major: Soil and Water Science

In Florida, the Suwannee River is highly influenced by the interconnection with

groundwater. This relationship affects the quality and quantity of water in the river. An

increasing temporal trend in nitrate-nitrogen (NO3-N) concentration and a declining temporal

trend for total phosphorus (TP) concentrations has been identified in the river. Loadings ofNO3-

N were consistently highest in the Middle Suwannee River Basin (MSRB) and the Lower Santa

Fe River Basin (LSFRB).

The research obj ectives were to identify changes in riverine TP and NO3-N

concentrate on s and relate to anthrop ogeni c i influence s, character ze groundwater/surfac water

interaction in the MSRB and LSFRB and locate segments) with the greatest NO3-N load

entering the river, delineate groundwater domains in the Suwannee River Water Management

District (SRWMD) using potentiometric surface maps and hydrochemical facies analysis, and

determine relationships of groundwater domain TP and NO3-N concentrations to domain

landuse/landcover.

The increasing temporal trend in NO3-N concentrations and declining temporal trend in

TP concentrations are still present in the river. The declining trend in TP is related to










management of a phosphate mining discharge. The NO3-N concentration observed in the

Suwannee River at Branford is likely related to fertilizer sales/use in Suwannee and Lafayette

counties. The increase in NO3-N loading in the MSRB and LSFRB occurred over small

segments of each river. The NO3-N load increases in the MSRB and LSFRB appear to be due to

groundwater inputs based on riverine chemical signature and river discharge. Eight groundwater

domains were delineated from the SRWMD potentiometric surface maps and were refined to

nine domains using hydrochemical facies analysis. Groundwater domain landuse/landcover was

related to observed groundwater domain TP and NO3-N concentrations. When crop and pasture

land was greater than 12 % of the land area of the groundwater domain elevated groundwater

NO3-N concentrations were observed. These landuses receive much of the fertilizer used in the

basins. Groundwater domains with elevated NO3-N concentrations are adj acent to the MSRB

and LSFRB. Groundwater domains with elevated NO3-N concentrations are affecting the

surfacewater quality that receives discharge from these groundwater domains and the most likely

source of the NO3-N is fertilizer use in the groundwater domains.









CHAPTER 1
INTTRODUCTION

The Suwannee River Basin (SRB) is shared by two states: Georgia and Florida (Figure 1-

1). The SRB covers 9,950 square miles [25,770 km2] Of land drained by the Suwannee, Alapaha,

Withlacoochee, and Santa Fe rivers in Florida and Georgia. The SRB in Florida covers 4,230

square miles [10,955 km2] (Katz and DeHan, 1996). The Suwannee River is the State River of

Florida. The Florida Legislature in 1979 designated the Suwannee River in Florida an

Outstanding Florida Water which means the river has significant cultural and ecological value to

the State of Florida. Also, the Suwannee River is one of the last rivers in the United States that

flows unimpeded by dams, dikes, or levees and is the second largest discharging river in Florida

(FDEP, 2001). The SRB consists of three maj or tributaries: the Withlacoochee River (and its

tributary Little River), Alapaha River, and Santa Fe River (Berndt, 1996) as shown in Figure 1-1.

The SRB has been farmed since the 1700's, and the present road patterns reflect historic

travel routes. River and stream corridors and larger wetland areas have, for the most part,

remained relatively undeveloped and provide excellent wildlife habitat (Fernald and Purdum,

1998). National Wildlife Refuges managed by the United States Fish and Wildlife Service

occupy both the headwaters and delta of the Suwannee River.

Agriculture constitutes most of the developed land uses within the SRB in Florida,

including pine plantations, row crops, and pastures. Irrigated acreage has increased considerably

in the SRB over the last several decades as technologies have improved and market conditions

have changed (Marella, 2004). The primary water source is ground water from the Floridan

aquifer system in Florida (Fernald and Purdum, 1998). Trends over the last decade indicate a

general shift towards more intensive production of food and forage crops as well as animal

husbandry. Agricultural crops and products from the SRB include dairy and poultry, fruits and










vegetables, grains, pasture, hay, and forestry products. Forestry, primarily pine plantations,

covers large areas of the SRB and provides timber and fiber for mills within and outside the

SRB.

In recent years, water quality data have indicated an increasing temporal trend for nitrate-

nitrogen (NO3-N) in the Suwannee River. The rate of increase is 0.02 mg N L^1 y^l (Ham and

Hatzell, 1996). Possible sources of the NO3-N in the SRB are atmospheric deposition, septic

tanks, fertilizer, and animal waste (Andrews, 1994). Data have shown that NO3-N loadings are

consistently highest in the Middle Suwannee River and the Lower Santa Fe River basins.

This Dissertation contributes the following:

1. An understanding of the changes in concentrations of total phosphorus (TP) and NO3-N
in the Suwannee River due to possible anthropogenic influences.

2. Summary of recent ground and surface water quality data in the Suwannee River Water
Management District (SRWMD).

3. Characterization of groundwater/surfacewater interactions in the Middle Suwannee River
Basin (MSRB) and the Lower Santa Fe River Basin (LSFRB). This characterization
located the segment (s) of the river where the greatest NO3-N load enters the river system
from ground water.

4. Determination of the groundwater domains within the SRWMD using potentiometric
surface maps and principal component analysis of groundwater quality. Groundwater
domain TP and NO3-N concentrations were statistically evaluated to ensure that each
groundwater domain was statistically different from each other and a summary of
groundwater quality by groundwater domain was generated.

5. Landcover/Landuse was clipped to each groundwater domain and correlations will be run
to determine relationship to groundwater domain TP and NO3-N concentrations and level
2 Florida Land Use Codes (FLUC) landuses.

























































irla ill


Legend
Suwannee River Basin
SAlapaha River Basin
SLittle River Basin
SLower Suwannee River Basin
SSanta Fe River Basin
SUpper Suwannee River Basin
SWithiacoochee River Basin
Florida/Georgia Hydrography


GEORGIA
FLORIDA


r


z


0 10 20


40 Miles









CHAPTER 2
LITERATURE REVIEW

Overview of the Suwannee River Basin

Location

The Suwannee River Basin (SRB) is located within the Coastal Plain physiographic

region of the southeastern U. S., extending from near Cordele, Georgia, to Cedar Key, Florida, in

the Gulf of Mexico (Fernald and Purdum, 1998). The Okefenokee Swamp contains the

headwaters of both the Suwannee and St. Marys Rivers (Femald and Purdum, 1998). The SRB

covers part of South Georgia and North Florida (Figure 1-1), and has at least 60 units of

government with jurisdiction (Homnsby and Raulston, 2000). Valdosta, Georgia is the largest

city within the SRB, followed by Lake City, Florida. Interstate 75 traverses the length of the

SRB; Interstate 10 crosses the southern third.

Hydrology

The SRB hydrology is highly varied in terms of flows, water quality, aquatic habitat, and

related values. The SRB includes freshwater swamp, small surfacewater streams, large rivers,

extensive tidal salt marshes, and interior-drained karst areas with extensive spring discharge.

The character of the Suwannee River changes dramatically as it progresses down stream,

reflecting the geology, physiography, and land cover of the region it drains (Femald and Purdum,

1998).

Surface drainage characteristics dominate the upper two-thirds of the SRB. The dendritic

pattern of the stream drainage is also evidenced by the forested stream corridors. Surface

drainage exists where soils contain more clays and fine sediments that are more resistant to

infiltration. Streams, lakes, and wetlands are more abundant in the upper Suwannee River, and

in the upper Santa Fe River basins. Water quality conditions in these areas reflect the dominant









influence of surfacewater systems which contain low dissolved minerals and generally acidic

conditions due to low buffering (FDEP, 2001).

In the southern third of the SRB, a relatively thin layer of highly porous sand overlies the

Floridan aquifer system, and the Suwannee River takes on more groundwater quality

characteristics (Hornsby and Ceryak, 1999). Rainfall in these areas percolates directly to the

aquifer. The relative absence of surfacewater features such as streams, lakes, and wetlands

indicates areas where recharge to the aquifer is direct. The transition between these areas

includes many stream-to-sink sub-basins, where surface stream flow is abruptly captured by

sinkholes and is directed to the aquifer. This transition zone lies along a feature in Florida

known as the Cody Escarpment or Cody Scarp (Fernald and Purdum, 1998). These areas, as

well as the numerous springs along the lower river reaches, act as points of interaction between

surface water and ground water (Scott et al., 2004).

Water quality conditions in the Suwannee and its tributaries reflect the physical setting of

the SRB. Areas dominated by surface drainage typically have more acidic water, higher levels

of sediment and particulate matter, and higher variability in flow regime. Downstream of White

Springs, Florida, the Suwannee River receives inflow from over 200 known springs (Scott et al.,

2004; Hornsby and Ceryak, 1998). The influx of ground water from the upper Floridan aquifer

system buffers the acidity and darker color of the surface water with relatively constant flow of

clear, mineral-rich ground water which provides base flow to the Suwannee River (Hornsby and

Ceryak, 1999). Base flow in a river system is a natural condition of ground water discharge to

the river and is the primary source of flow in the system during low flow (Pittman et al., 1997).

Ground water influence on water quality in the river is more pronounced during low flow and in

the river reaches having the greatest number of springs and the least tributary inflow (Hull et al.,









1981). The upper Floridan aquifer will receive recharge from the Suwannee River when the

surface water levels are above the adj acent aquifer potentiometric level. This results in the

spring to estevelle, which is the cessation of discharge due to the surfacewater head overcoming

the groundwater head. This results in reverse flow of springs or surfacewater entering the

aquifer.

Physiography

Hydrogeology within the SRB is directly related to the physiography. The SRB can be

divided into three general physiographic regions: Northern Highlands, Gulf Coastal Lowlands,

and River Valley Lowlands as shown in Figure 2-1 (White, 1970).

The Northern Highlands region is mainly characterized by altitude and thick, clayey

strata that overlie the Floridan aquifer system. The land surface throughout the area is greater

than 100 feet (30.5 m) above mean sea level (msl) and reaches heights up to 230 feet (70. 1 m)

ms1 (White, 1970; Homnsby and Ceryak, 1999; Fernald and Purdum, 1998).

The area to the west and southwest is the Gulf Coastal Lowlands. The land surface of

this area is less than 100 feet (30.5 m) ms1 and the maj ority of the clayey sediments have been

eroded away (White, 1970; Homnsby and Ceryak, 1999; Fernald and Purdum, 1998). Limestone

is at or near land surface throughout the Gulf Coastal Lowlands.

The most persistent topographic feature in the State of Florida is the Cody Scarp, which

is the boundary between the Highlands and Lowlands (Puri and Vemnon, 1964; Homnsby and

Ceryak, 1999; Fernald and Purdum, 1998). It is a very significant feature as it pertains to

hydrogeology of the SRB. Every river or stream (except the Suwannee River) that originates in

the Highlands disappears underground as it crosses the Cody Scarp (White, 1970; Homnsby and

Ceryak, 1999; Fernald and Purdum, 1998). The few streams that exist in the Gulf Coastal









Lowlands have eroded downward into the upper Floridan aquifer system and have intersected the

unconfined upper Floridan aquifer. Base flow to Gulf Coastal Lowland streams is supplied by

artesian spring flow from the upper Floridan aquifer system (Scott et al., 2002; Scott et al., 2004;

Pittman et al., 1997).

The third physiographic region is the River Valley Lowlands. River Valley Lowlands are

erosional/depositional features formed by the rivers that originate in the Highlands and pass

through the River Valley Lowlands to the Gulf of Mexico (White, 1970; Hornsby and Ceryak,

1999).

Soils

The Natural Resource Conservation Service (NRCS) formerly known as the Soil

Conservation Service (SCS), a branch of the United States Department of Agriculture (USDA),

has defined three maj or land resource areas (MLRAs) within the SRB in the Suwannee River

Water Management District (SRWMD). The three MLRAs are Southern Coastal Plain, North-

Central Florida Ridge, and Eastern Gulf Coast Flatwoods (Soil Survey Staff, 1997). The

Southern Coastal Plain's soils are predominantly Udults. These soils are characterized as deep

and have a thermic temperature regime, an udic moisture regime, a loamy or sandy surface layer.

The North-Central Florida Ridge's soils are predominantly Udults and Psamments. These soils

are characterized by having a thermic temperature regime and an udic moisture regime. The

soils range from well drained to poorly drained and generally sandy. The predominant Eastern

Coast Flatwood' s soils are Aquults, Aquepts, and Aquods. These soils are characterized by

having a thermic temperature regime and an aquic moisture regime. The soils are generally

sandy and poorly drained or very poorly drained (Soil Survey Staff, 1997). Nair et al. (2004)

noted the sandy soils of the SRB in Florida have little ability to absorb phosphorus (P) and that









many animal husbandry operations were applying P-rich lagoon effluent to permanent

sprayfields. This application of P-rich lagoon effluent increased the P loading to the sites and

may result in P loss via surfacewater runoff or leaching to ground water. Furthermore, Obreza

and Means (2006) noted that the sandy soils of the SRB were vulnerable to nutrient and

agrichemical leaching, especially under excessive rainfall or irrigation conditions.

The Middle Suwannee River Basin (MSRB) is a sub-basin of the SRB which is located in

Suwannee and Lafayette counties in Florida. Generally, soils in the MSRB are sandy well

drained to excessively drained. For agricultural production, these soils present issues with

irrigation and leaching of nutrients from the root zone (USDA, 1993). Furthermore, these soils

have medium to high potential for nitrogen (N) leaching to ground water. Most agricultural

production in the MSRB occurs primarily on Entisols and Ultisols (Obreza and Means, 2006).

Entisols are soils that do not display evidence of pedogenic horizon development (Brady and

Weil, 2000). Entisols are able to support any vegetation and occur in any climate. Entisols form

in inert parent materials such as quartz sand or slowly soluble rock such as limestone (Carlisle et

al., 1985). The properties unique to Florida Entisols are a dominance of mineral soil and an

absence of distinct pedogenic horizons except for an ochric epipedon, an albic horizon, and a

spodic or argillic diagnostic subsurface horizon that is below 80 inches[203 cm] (Collins, 2003).

Ultisols occur in humid regions and formation is from weathering and leaching that results in

subsurface horizons of illuvial accumulations, such as, quartz, kaolinite, and iron oxides (Brady

and Weil, 2000; Soil Survey Staff, 2007). Generally, Ultisols are acidic with nutrients

concentrated within a few centimeter of the land surface and have a relatively low capacity to

retain fertilizers (Soil Survey Staff, 2007).









Soil orders with high leaching potential in the SRWMD are shown in Figure 2-2. These

soil orders include Ultisols, Spodosols, Inceptisols and Entisols with Entisols being the maj ority

of the high leaching soils. High leaching Ultisols in the SRWMD are Apopka (loamy, siliceous,

subactive, hyperthermic Grossarenic Paleudults) and Valdosta (siliceous, thermic Psammentic

Paleudults) [Houston et al., 1965; Carlisle, 1985 and Soil Survey Staff, 2007]. High leaching

Spodosols are Cassia (sandy, siliceous, hyperthermic Oxyaquic Alorthods), Hurricane (sandy,

siliceous, thermic Oxyaquic Alorthods), Mandarin (sandy, siliceous, thermic Oxyaquic

Alorthods), and Ridgeland (sandy, siliceous, thermic Oxyaquic Alorthods) [Soil Survey Staff,

2007]. High leaching Inceptisol are Fort Meade (siliceous, hyperthermic humic Psammentic

Dystrudepts), Orlando (siliceous, hyperthermic humic Psammentic Dystrudepts), Pickney

(sandy, siliceous, thermic Cumulic Humaquepts) and Placid (sandy, siliceous, hyperthermic typic

Humaquepts). The high leaching Entisols are Adamsville (hyperthermic, uncoated aquic

Quartzipsamments), Alaga (thermic, coated typic Quartzipsamments), Alpin (thermic, coated

Lamellic Quartzipsamments), Astatula (hyperthermic, uncoated typic Quartzipsamments),

Bigbee (thermic, coated typic Quartzipsamments), Candler (hyperthermic, uncoated Lamellic

Quartzipsamments), Chipley (thermic, coated aquic Quartzipsamments), Clara (siliceous,

thermic spodic Psammaquents), Foxworth (thermic, coated typic Quartzipsamments),

Gainesville (hyperthermic, coated typic Quartzipsamments), Kershaw (thermic, uncoated typic

Quartzipsamments), Lake (hyperthermic, coated typic Quartzipsamments), Lakeland (thermic,

coated typic Quartzipsamments), Orsino (hyperthermic, uncoated spodic Quartzipsamments),

Ortega (thermic, uncoated typic Quartzipsamments), Osier (siliceous, thermic typic

Psammaquents), Ousley (thermic, uncoated aquic Quartzipsamments), Paola (hyperthermic,

uncoated spodic Quartzipsamments), Penney (thermic, uncoated Lamellic Quartzipsamments),









Pompano (siliceous, hyperthermic typic Psammaquents), Resota (thermic, coated spodic

Quartzipsamments), Ridgewood (thermic, uncoated aquic Quartzipsamments), and Tavares

(hyperthermic, uncoated typic Quartzipsamments) [Houston et al., 1965; Carlisle, 1985 and Soil

Survey Staff, 2007].

The dominant Entisols soils in the MSRB are Alpin and Penney (Figure 2-2). The Alpin

series consists of very deep, excessively drained, moderately rapidly permeable soils on uplands

and river terraces of the Coastal Plain. The soils formed in thick beds of sandy eolian or marine

deposits. (Soil Survey Staff, 2007). The Penney series consists of very deep, excessively

drained, rapidly permeable soils on uplands. The soils formed in thick beds of sandy eolian or

marine deposits (Soil Survey Staff, 2007). These soils have leaching potential.

Sabasan (2004) identified NO3-N concentrations in various landuse on Entisols, Ultisols,

and Spodosols in the Santa Fe River Watershed. For landuse pine plantations, the NO3-N

concentrations for Entisols, Ultisols, and Spodosols were 0.05, 0.33 and 0.28 Clg N g- of soil,

respectively. For landuse improved pasture, the NO3-N concentrations for Entisols, Ultisols, and

Spodosols were 0.51, 1.80 and 1.65 Clg N g- of soil, respectively. For landuse crops, the NO3-N

concentrations for Entisols, Ultisols, and Spodosols were 2.70, 2.60 and 0.56 Clg N g- of soil,

respectively.

Hydrogeology

A highly productive regional aquifer exists within the SRB that is capable of producing

thousands of gallons of water per minute to wells. This aquifer is referred to as the Floridan

Aquifer system (Miller, 1997). The upper Floridan aquifer system is the primary source of

drinking water and base flow in the SRB (FDEP, 2001). The Floridan aquifer system is made up

of limestone and dolostone. Carbonate rock (limestone and/or dolostone) as much as 5,000 feet










(1,524 m) thick exists in the subsurface of the SRB. These strata, which are primarily Tertiary in

age, make up the Florida Platform. The Floridan aquifer system is found within these strata in

the Florida Platform (Figure 2-3) and in similar strata in the Carolinas and portions of Alabama.

The permeable portion of this carbonate-rock platform ranges from about 600 feet (182.9 m) to

1,700 feet (518.2 m) in thickness (Miller, 1982).

Water that recharges the Floridan aquifer system comes from rainfall and focused

recharge through leaky sediments at the base of the upper aquifers, at the edge of the upper

aquifers where the clayey base becomes discontinuous, or through sinkholes that penetrate into

the aquifer system (Ceryak et al., 1983; Hornsby and Ceryak, 1999). There are two distinct

regions of the upper Floridan aquifer within the SRB in Florida: a confined region and an

unconfined region (Figure 2-4). The confined regions are where there is a layer of clay over

limestone, thus reducing/retarding the recharge of rainwater and fostering surface water runoff.

The unconfined regions are where limestone is at or near land surface and are recharged directly

from percolating rainfall, since the only sediment overlying the aquifer is porous sand (Hornsby

and Ceryak, 1999). These unconfined regions allow for direct recharge of the upper Floridan

aquifer and allows for the contamination of the upper Floridan aquifer by water-soluble

contaminants such as nitrates (NO37).

Land Use Overview

The land use patterns that have evolved within the SRB reflect the opportunities and

constraints of the land. Most of the developed land uses in the SRB historically have been

located on the upland, better-drained regions. The SRB has been farmed since the 1700's and

the present road patterns reflect historic travel routes. River and stream corridors and larger

wetland areas have, for the most part, remained relatively undeveloped and provide excellent









wildlife habitat (Fernald and Purdum, 1998). National Wildlife Refuges managed by the United

States Fish and Wildlife Service bracket both the headwaters and delta of the Suwannee River.

Growth and development within the Florida side of the SRB has been steady since the

1960s, but at a relatively slower rate than other areas in Florida (Fernald and Purdum, 1998).

Most of the urban development has occurred near the Interstate 75 corridor, and in proximity to

cities and towns. The estimated population in 2006 in the SRB within Florida is 350,000 (K.

Webster, 2007, Personal Communication). Growth projections for the SRB indicate a 13 to 15

% increase in the population over the coming decade (Fernald and Purdum, 1998).

Agriculture defines most of the developed land uses within the SRB in Florida, including

pine plantations, row crops, and pastures. Irrigated acreage has increased considerably in the

SRB over the last several decades as technologies have improved and market conditions have

changed (Marella, 2004). Drinking water source is primarily ground water from the Floridan

aquifer system in Florida (Fernald and Purdum, 1998). Agriculture acreages within the SRB

over the last decade indicate a declining trend, which indicates a general shift towards more

intensive production of food, forage crops and animal husbandry on less acreage. Agricultural

crops and products from the SRB include dairy and poultry, fruits and vegetables, grains,

pasture, hay, and forestry products. Forestry, primarily pine plantations, covers large areas of the

SRB and provides timber and fiber for mills within and outside the SRB.

Water Quality Characteristics

The Suwannee River system's hydrology and water chemistry is influenced by

physiographic characteristics (FDER, 1985). The geologic and physiographic changes that the

Suwannee River undergoes as it traverses through north central Florida results in dramatic

longitudinal changes in water chemistry (Ceryak et al., 1983; FDER, 1985). The changes in









these characteristics may best be described by recognizing six reaches of the Suwannee River in

Florida, as shown in Figure 2-5 (Hornsby et al., 2000). A description of the reaches is given in

Table 2-1.

Water chemistry in the Suwannee River changes in a unique way from upstream to

downstream (Bass and Cox, 1985). Hornsby and Mattson (1998) used water chemistry and

stream structure to define six distinct reaches of the Suwannee River; the upper river (Reaches 1

and 2) is a soft, acidic, blackwater stream, with waters of low mineral content and high color

(Figures 2-6 and 2-7). As the river progresses downstream (Reaches 3, 4, 5 and 6), it receives

increasing amounts of water from the upper Floridan aquifer, which changes river water quality

to a clear, slightly colored, alkaline stream (Figures 2-6 and 2-7). These natural chemical

gradients influence the ecology of the river in many ways. In terms of overall biological

production, the upper river tends to be more oligotrophic, while the lower river is more

productive .

Total organic carbon (TOC) concentrations are higher in the upper reaches of the river

(Hornsby et al., 2000), largely due to the dissolved organic carbon (C) associated with the high

water color. Nutrient concentrations (dissolved N and P) are low in the uppermost reach (Reach

1), generally near detection limits of less than 0.05 mg N L^1 and 0.04 mg P L^1 (Hornsby et al.,

2000). The low levels of nutrients in the upper reach contribute to its low biological

productivity. Dissolved N and P concentrations both generally increase going downstream.

Peak P levels are seen in Reach 2, partly due to the geology, as the river crosses the exposed

Hawthorn Group that contains high levels of phosphate in the form of carbonate-fluorapatite

(Maddox et al., 1992), and partly due to discharges from phosphate mining and processing.

Highest NO3-N levels are seen in the middle and lower reaches (Reaches 3,4,5 and 6), and a









historical trend of increasing NO3-N has been identified in the middle and Lower Suwannee and

Lower Santa Fe rivers (Ham and Hatzell, 1996). Much of NO3-N increase comes from

groundwater discharges via springs along the river corridor (Katz et al., 1999; Pittman et al.,

1997). Areas of elevated NO3-N have been identified in the upper Floridan aquifer in these

regions (Hornsby et al., 2005B). Sources of this N are diverse and include agricultural

operations, sewage spray fields, areas with dense concentrations of septic tank drain fields, and

stormwater runoff to sinkholes.

The 2004 State Water Quality Assessment 305(b) Report prepared by the Florida

Department of Environmental Protection (FDEP) indicates generally "good" water quality in the

SRB. Portions of the lower river and most of the estuary are designated as "impaired" and are

candidates for Total Maximum Daily Load (TMDL) establishment. Portions of the upper

Suwannee and Santa Fe sub-basins are indicated to be "potentially impaired". These

assessments appear to be based largely on low dissolved oxygen (which is partly natural due to

groundwater discharge), nutrients, and/or elevated fecal coliform levels.

Nutrients

For water quality concerns, the two nutrients that receive the most attention in water are P

and N. The most common forms of P and N that plants uptake are H2PO4- and HPO42- for P and

NO3- and NH4' for N (Brady and Weil, 2000).

Phosphorus

Phosphorus is second only to N in its importance in the production of healthy plants and

profitable yields (Brady and Weil, 2000). Phosphorus is needed for the production of adenosine

triphosphate (ATP) that is the energy source for most biochemical process, a component of

deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Native soils are generally low in









available P thus soil amendments have been used to promote crop yields (Havlin et al., 1999).

Unfortunately, more P is often added to the soil than is removed by plant uptake (Brady and

Weil, 2000). This results in excess P in the soil and allows for the movement of the P via erosion

or leaching.

Phosphorus cycle

Phosphorus is a macronutrient for primary producers. The availability of P for biological

uptake has little to no relationship to the total P (TP) content in soils (Havlin et al., 1999).

Factors which control H2PO4- and HPO42- in the soil solution are pH, adsorption, desorption,

mineralization and immobilization, precipitation, dissolution, fertilization, soil organic matter,

leaching and plant uptake.

The sources for P in the environment are fertilizer, soil organic matter, primary minerals

and secondary minerals. Secondary minerals are formed when P complexes with cations and

precipitates out of the soil solution. Primary and secondary minerals can dissolve to supply the

soil solution P. Soil organic matter is both a source and a sink of P. Soil organic matter can

complex with P or the P can be incorporated in to the soil microbial mass. This is

immobilization of P. The release of P into the soil solution by the soil organic matter is

mineralized. Fertilization with P results in the increase of soil solution P by increasing the

amount of P in the soil, which saturates the possible adsorption sites in the soil.

The pH of the soil solution determines the form(s) of P available. At low pH, between 2

and 6, H2PO4~ is the dominant form while at higher pH, 8 to 12, HPO42- is the dominant form. At

pH 7.2 there are equal amounts of H2PO4- and HPO42- in Solution (Havlin et al., 1999).

Adsorption of P is a process in which P in soil solution is removed and accumulated at

the interface of the soil (minerals and clays) and solution. The adsorption of P reduces the









availability of the P for plant uptake. The reverse process, desorption, is the release of adsorbed

P into the solution.

The P cycle in soils is shown in Figure 2-8. However, the P cycle can be reduced to the

following relationship (Havlin et al., 1999):

Soil solution Po labile P t nonlabile P

Soil solution P is the P which is dissolved in soil pore water. Labile P is the P that is readily

available to the soil solution to replace P, which is removed by biological uptake. Nonlabile P is

the P in the soil, which is not available to the soil solution due to chemical or biological

immobilization (Havlin et al., 1999; Brady and Weil, 2000).

Occurrence of phosphorus in groundwater

Maddox et al. (1992) defined the background concentration of ortho-phosphate (H2PO4 ,

HPO42- and PO43-) in the upper Floridan aquifer to be less than 0.10 mg P L^1 while surface water

within the SRWMD ranges in concentration of TP and ortho-phosphate from 0.001 to 26.6 mg P

L^ and 0.001 to 26.2 mg P L^1, respectively (Hornsby and Mattson, 1998). The P concentrations

in the Suwannee River vary as the river traverses from the headwaters to the Gulf of Mexico.

The high concentrations of P in the Suwannee River is observed in the upper river where the

river comes in contact with the Hawthorne Group, a P bearing unit, and also, receives discharge

from a phosphate mining operation. From the upper Suwannee River to Gulf of Mexico, the P

concentrations decline in the river (Hornsby and Mattson, 1998).

Concerns with phosphorus

The primary concern with P is eutrophication of surface water bodies. The input of P into

these surface waters results in increased bio-activity, favoring organisms able to adapt to the

environmental changes in the water. Thus, the bio-diversity will be reduced. Also, harmful algae









such as blue green can produce toxins that can cause fish kills and prevent the water from being

suitable for human consumption (Brady and Weil, 2000).

Water quality standards for phosphorus

Currently, there is no groundwater standard for P (in any form) and no numeric

surfacewater standard for P (in any form) for the State of Florida. Florida Administrative Code

(F.A.C.) 62-302.530 for surface water has a narrative standard for nutrients, which states, "that

nutrients shall not cause an imbalance to flora or fauna". The only surfacewater body with a

numeric standard for P is the Everglades which has a standard of 10 Clg P L^1 per Florida

Administrative Code (F.A.C.) 62-302.540.

The FDEP uses a screening concentration for total N and TP of 0.45 and 0. 1 mg L^1,

respectively (T. Greenhalgh, 2005, Personal Communication). The screening concentrations are

based on total N and TP concentrations in surfacewater bodies that will support a chlorophyll a

concentration of 20 Clg L^1 (J. Hand, 2005, Personal Communication). These screening

concentrations for total N and TP are used to determine impaired water bodies by nutrients.

These impaired water bodies are reported biannually to the United States Environmental

Protection Agency (EPA) and are placed on the State's TMDL list for development of TMDLs

for nutrients.

Nitrogen

Nitrogen is the most commonly deficient nutrient in crop production (Havlin et al., 1999).

Therefore, most crops require the addition of N for optimum yield. Nitrogen is needed by

organisms for the production of protein. The most mobile form of N in the environment is nitrate

(NO3-). Nitrate is completely soluble in water. The movement of nitrates in the environment can

pose risks to humans and animal health as well as impact the quality of the environment.









Nitrogen cycle

Nitrogen is a macronutrient for primary producers. The N cycle is shown in Figure 2-9.

The four general steps in this cycle are 1) N fixation, 2) ammonification, 3) nitrification, and 4)

denitrification (Havlin et al., 1999):

Nitrogen fixation can be a biological or chemical process. The biological process

converts atmospheric nitrogen gas [N2(g)] to organic nitrogen (N) matter while chemical fixation

can occur naturally by lighting in the atmosphere converting N2(g) to nitric acid (HNO3) Or by

man converting N2(g) to NH3, N2-, NO3~ USed in synthetic fertilizers.

Ammonification is the decomposition of soil organic matter by soil organisms to release

ammonium ion (NH4 ) fTOm organic matter. The released NH4' can then be used by nitrifying

organisms in a process called nitrification if conditions are suitable or immobilized by soil

organisms or available for plant uptake. Also, in high pH in soils and waters, the NH4' can

volatize to NH3(g) Or become fixed in a biologically unavailable form in some clay mineral

lattices.

Nitrification is the conversion ofNH4+ to NO3- by a biological mediated reaction that

oxidizes the N. The process in the conversion NH4' to NO3~ is a two step reaction. The first step

is the conversion of NH4+ to NO2-. Bacteria called nitrosomona~s mediate this reaction. The

second step is the conversion of NO2- to NO3-. Bacteria called nitrobacter mediate this reaction.

The rate limiting step is the conversion of NH4+ to NO2 -

Denitrification is the conversion of NO3~ to gaseous forms of nitrogen (N2(g), N20(,)).

The process occurs under anaerobic conditions. Denitrifying bacteria (Pseudomona~s, Baccillus

and Paracoccus)PP~~PP~~~PP~~PP in anaerobic conditions have the ability to use NO3~ aS the terminal electron









acceptor in place of 02(g) for respiration. Through the biological mediated reactions, N (in NO3~

goes from an oxidation state of +5 to 0.

The amount of decomposable organic matter (OM) strongly influences denitrification.

The NO3~ is used in place of 02(g) in the respiration process by the denitrifying bacteria. Thus,

OM is the food source and the amount of C available defines the amount of denitrification that

will occur to produce energy for the denitrifying bacteria.

Soil water content determines the amount of denitrification by impeding 02(g) diffusion

into the soil by the soil pore spaces being filled with water. Thus, water fills pore spaces and

promotes anaerobic conditions by creating regions in the soil where the concentration 02(g) is

reduced or 02(g) is removed from the system

The process of denitrification will only occur when the concentration of 02(g) is too low

to meet biological requirements for aerobic respiration. However, in well aerated soils,

denitrification can occur due to development of anaerobic microsites.

Occurrence of nitrate-nitrogen

Nitrate is a widespread contaminant of shallow ground water and the levels of

contamination are increasing (Spalding and Exner, 1993). Nationally, Spalding and Exner (1993)

conducted an evaluation of the occurrence of NO3-N in groundwater. The percentage of wells

sampled with NO3-N concentrations higher than the 10 mg N L found in the following states were:

18 % in Iowa, 27 % in Kansas, 17 % in Nebraska, 3 % in North Carolina, Ohio, and Arkansas, 7 %

of the wells sampled in Texas, 13 % in California, 25 % in Delaware, 9 % in Pennsylvania, 22 % in

Washington, 20 % in Minnesota, and 37 % in South Dakota. Furthermore, the National Water

Quality Assessment (NAWQA) program of the United States Geological Survey (USGS) has

assessed the water quality of aquifer systems that cover the water resources of greater than sixty









percent of the population in the contiguous Unites States. The findings were that approximately

fifteen percent of shallow groundwater sampled beneath agricultural and urban areas had NO3-N

concentration above 10 mg N L^1 (Manassaram et al., 2006). The concentrations of NO3-N in

groundwater are associated with source availability, regional environmental factors [i.e., rainfall,

organic C, dissolved Oz] (Madison and Brunett, 1985) and man-induced factors [i.e., agricultural

activities] (Spalding and Exner, 1993). The NO3-N concentrations in the nation' s river are shown in

Table 2-2. The percentiles were determined from 383 different rivers through the United States.

Maddox et al. (1992) defined the background concentration of NO3-N in the Floridan

aquifer system to be 0.05 mg N L^1 while surface water within the SRWMD ranged in

concentration of NO3-N from 0.05 to 4.8 mg N L^1 (Hornsby and Mattson, 1998).

Concerns with nitrate-nitrogen

Methemoglobinemia which affects infants, is a result of NO3- being reduced to nitrite (NO2 )

in the gastrointestinal tract. The reduced species nitrite (NO2-), then oxidizes the ferrous iron (Fe2+)

in hemoglobin to ferric iron (Fe3+) which inhibits the hemoglobin from releasing oxygen to the cells

of the body (Kreitler, 1975). The cells of the body are thereby oxygen deprived, resulting in the

blue color of the skin of the effected infant; hence, the name "blue baby" disease.

Methemoglobinemia also affects animals (i.e., livestock). In the rumen, the bacteria convert

NO3- to NO2- when excess NO3~ is introduced into the rumen and causes NO2- to build up. NO2~ can

be adsorbed through the oral and/or GI tract into the blood and affects the hemoglobin similarly as

in human (MPCAMDA, 1991). The result is methemoglobinemia in livestock.

Another human health problem associated with NO3-N is the carcinogenic properties of N

compounds which are created in the digestive tract. The elevated concentrations NO3-N in

drinking water has been correlated to either mortality or incidence of stomach cancer










(MPCAMDA, 1991). Just like in methemoglobinemia, NO3~ is reduced to NO2- in the

gastrointestinal tract. The acidic conditions in the gastrointestinal tract is conducive to the

formation ofN-nitroso compounds (MPCAMDA, 1991). The EPA has classified N-nitroso

compounds as probable human carcinogens (EPA, 1991).

Nitrogen also causes eutrophication in surface water where N is the limiting nutrient. The

input of NO3-N into these surface waters results in increased bio-activity, favoring organisms able

to adapt to the environmental changes in the water (MPCAMDA, 1991). Thus, the bio-diversity

will be reduced.

In surface waters, nitrate provides the N, which is a macronutrient, needed by primary

producers. In surface waters where N is the limiting nutrient, the additional N introduced can

result in over production by the primary producers and result in a condition called

eutrophication. The over production by primary producers generates increased biomass in a

system which results in the depletion of available oxygen in the system to organisms for

respiration. Eutrophication results in the reduction of species in a water body and ultimately can

result in a dead water body. Nutrients delivered by the Mississippi River have been shown to

contribute to the "dead zone" in the Gulf of Mexico and nutrients (primarily P) are the main

problem in Lake Okeechobee (Zagier, 2003; Hey, 2002).

Water quality standards for nitrate-nitrogen

There is a numeric groundwater standard for NO3-N of 10 mg N L^1 which is for the

protection of human health. However, there is no numeric surface water standard for NO3-N in

the State of Florida. The Florida Administrative Code (F.A.C.) 62-302.530 for surface water

narrative standard for nutrients states "that nutrients shall not cause an imbalance to flora or









fauna". U.S. Department of Agriculture (1991) developed water quality indices for tidal and

freshwater based on NO3-N concentration. The water quality indices are presented in Table 2-3.

Water Quality Assessments

In 1979, the FDEP identified the Middle Suwannee River Basin (MSRB) as one of five

watersheds within the State of Florida for potential groundwater contamination by nonpoint

sources due to agricultural practices (FDEP, 1979). However, the ranking was based on

professional judgment due to the paucity of groundwater data within the watershed.

Furthermore, in Florida, ground water has few regulations in place to protect it from nutrient

contamination from non-point sources of pollution such as agriculture runoff (Hauserman, 2000).

In the late 1980's, a shift in agricultural practices occurred in dairy operations in the SRB

in Florida, primarily in Suwannee and Lafayette counties. The number of dairy operations and

the number of dairy cows increased. It was perceived that the dairy cow population was

increasing in the SRB due to the dairy buyouts in the Lake Okeechobee Basin in south Florida

and that the dairy operations from the Lake Okeechobee Basin were shifting to the SRB. The

dairy buyouts in the Okeechobee were designed to reduce surface runoff loadings of P, a

macronutrient, to Lake Okeechobee which was impacting the water quality of the lake due to the

lake being P limited. The loading of P was accelerating the eutrophication of the lake. This

perceived increase in dairy cows populations resulted in concern among local public health

officials as to the effects of the waste from the dairy operations in Suwannee and Lafayette

counties would have on groundwater quality. Since the Floridan aquifer is unconfined in

Suwannee and Lafayette counties, it is easily contaminated with water soluble contaminates,

such as, NO3-N (E. Wilson, 2004, Personal Communication).









The state health officials with the Florida Department of Health and Rehabilitative

Services (HRS) started private well surveys near dairy operations in Suwannee and Lafayette

counties (these counties comprise a region known as the MSRB) in 1990 (E. Wilson, 2004,

Personal Communication). These surveys revealed that 20 to 30 percent of the wells near dairy

operations had NO3-N concentrations in excess of the State Drinking Water Standard of 10.0 mg

N L Some of the wells sampled by the HRS in the MSRB in 1990-92 had NO3-N

concentrations in excess of 20 mg N L^1 (USDA, 1993). The NO3-N contamination in excess of

the Drinking Water Standard was observed in ten wells located on dairy operations (HRS, 1992).

At the same time, ambient monitoring for NO3-N in the surface water resources and springs in

the MSRB indicated a statistically significant increasing trend (Ham, 1996) while Mueller et al.

(1995) identified increasing concentrations ofNO3-N in the upper Floridan aquifer system in the

same region. The results of these monitoring activities prompted the FDEP to start requiring

industrial wastewater permits for any new dairy operations in the SRWMD in 1992 (E. Wilson,

2004, Personal Communication). Also, under the Clean Water Act the U. S. Environmental

Protection Agency (EPA) in 2002 began regulating through the state's Department of

Environmental Protection confined animal feeding operations (CAFO). A dairy is considered a

confined animal feeding operations if it has more than 700 dairy cows. In the MSRB, the

implementation of confined animal feeding operations regulation only affected seven of the

dairies since the maj ority of the dairy operations had less than 700 dairy cows (D. Smith, 2004,

Personal Communication).

In 1993, the United States Department of Agriculture Soil Conservation Service (now

known as the Natural Resource Conservation Service) submitted a watershed protection plan and

environmental assessment under the authority of the Watershed Protection and Flood Prevention









Act and in accordance with the National Environmental Policy Act to Secretary of Agriculture

(USDA, 1993). The obj ective of the plan was to reduce the potential for NO3-N leaching to the

Floridan aquifer from animal operations through the installation of best management practices

(BMPs) in the MSRB. The watershed protection plan setup public law 566 (PL-566) projects

that receive federal assistance with the implementation of projects that are consistence with the

actions outlined in the plan. Furthermore, in 1996 the Florida Legislature provided line item

funds to assist in the implementation of the Soil Conservation Services Watershed Protection

Plan. Federal and state funds are used to cost share the implementation of BMPs on animal

operations to help prevent leaching of NO3-N in to the upper Floridan aquifer.

A follow up study of private drinking water wells conducted in 1997 by the FDEP found

that wells near animal husbandry operation were 29 percent more likely to have NO3-N

concentrations greater than the Drinking Water Standard for NO3-N (Copeland et al., 1999). The

EPA has found that nutrients are the leading cause of water quality impairment in estuaries and

the second leading cause of water quality impairment in lakes and rivers (EPA, 1994). Also, the

EPA defined the number one source of impairment to rivers and lakes are from agriculture and

agriculture is the third source of impairment for estuaries (EPA, 1994).

The SRWMD ambient monitoring identified the MSRB as the largest contributor of the

NO3-N load to the Suwannee River. Figure 2-10 shows the loadings by sub-basins in the

Suwannee River system. The highest percentage of the NO3-N loading is derived from the

MSRB. In this region, ground water from the upper Floridan aquifer enters the Suwannee River

via springs and seeps. The ground water provides the base flow to the Suwannee River in this

region. Under base flow conditions, the flow in the Suwannee River doubles in volume from the

top of the MSRB (near Dowling Park, Florida) to the bottom the MSRB (near Branford, Florida).









In the MSRB, there are no tributaries to the river, thus, the increase in flow is directly due to

ground water influx from the upper Floridan aquifer via springs and seeps.

A series of studies added to the knowledge that NO3-N contamination of the upper

Floridan aquifer was occurring and the NO3-N contamination of the upper Floridan aquifer was

impacting the water quality of the springs along the Suwannee River and the river itself. The

average NO3-N concentration in the upper Floridan aquifer was observed to be 30 to 40 mg N L^1

under dairy lagoons and high intensity areas, 30 mg N L^1 under spray fields which receive dairy

effluent, 6.2 mg N L^1 on dairy pastures, and on average 4.25 mg N L^1 under property adj oining

dairy farms (USDA, 1993; Andrews, 1994). During base flow in the MSRB, Pittman et al.

(1997) observed a 160 percent increase in the NO3-N concentration in the Middle Suwannee

River (Dowling Park to Branford). Springs in the MSRB have NO3-N concentrations that range

from 10 to 300 times greater than the background concentration for NO3-N of 0.05 mg N L^1

(Maddox et al., 1992; Scott et al., 2002, Scott et al., 2004, Katz et al., 1999, Berndt et al., 1998,

Hornsby and Mattson, 1998; and Hornsby and Ceryak, 1999). Also, when the Suwannee River

was compared to the Altamaha River, St. Johns River, Satilla River, Ogeechee River,

Withlacoochee River (South), and the Ochlockonee River, the Suwannee River had the highest

in-stream TP and NO3-N load km-2 Of basin of the seven rivers (Asbury and Oaksford, 1997).

Based on N estimation from potential sources in the SRWMD, there are multiple sources of N in

the MSRB with fertilizer being the largest potential contributor, poultry the second largest

potential contributor, and dairy cows the third largest potential contributors as shown in Figures

2-11 and 2-12 (Hornsby and Mattson, 1998). Furthermore, the Suwannee River and its estuary

have been shown to be N limited (Quinlan, 2003). A study conducted by Katz et al. (1999 and

2001) showed that the mean age of the water discharging from the springs was between 12 and










25 years old in the MSRB. This study indicates that the observed NO3-N concentration in the

ground water, rivers and springs represents NO3-N that may have entered the aquifer under land

uses that occurred 12 to 25 years ago and from mixed sources.

All the sources of N within the MSRB (Suwannee and Lafayette counties) are

anthropogenic. Thus, the NO3-N from the MSRB accounts for 45 percent of the annual NO3-N

load for the Suwannee River for water year 1998 (Figure 2-10); there are multiple sources of N

within the basin and the travel time within the upper Floridan aquifer is between 12 and 25 years

(Katz et al., 1999).

The FDEP classified the waters of the MSRB as being impaired due to nutrients,

primarily NO3-N, in the FDEP Water Quality Assessment 305(b) Report to the U.S. EPA in

1998 (FDEP, 1998). The Water Quality Assessment 305(b) Report is required to be submitted

to the EPA every two years by the State's environmental assessment agency under the authority

of the Clean Water Act. The listing of the Suwannee River in the 305(b) report resulted in the

Suwannee River being listed on the FDEP, 2002 Section 303(d) List of Impaired Waters for the

development of TMDL. The listing of the Suwannee River on the 303(d) will result in FDEP

allocation of pollutants (i.e., nitrates) to permittees within the Florida portion of the SRB.

Groundwater Domain Delineation

Understanding the region/area from which ground water is derived aids in the

management of the resource. Groundwater studies have used various techniques to define

contributing areas (or basins) to the ground water. The two commonly used methods are

utilizing groundwater level or potentiometric surface and geochemical fingerprinting or

hydrochemical facies. The first method utilizes contours of potentiometric surface of

groundwater levels. This method used ground water moving perpendicular to the contours and









defines the basin at bend points in the potentiometric contour. Jones and Upchurch (1993) used

this method to define a study area for the contributing groundwater domain to Lithia and

Buckhorn springs. Davis (1996) used potentiometric surfaces to determine groundwater basins

in North Central Florida and Southwest Georgia. The basins defined by Davis delineated the

groundwater basins (spring sheds) for Spring Creek spring group, Wakulla spring, Saint Marks

spring, and Wacissa spring group. Also, Upchurch et al. (2001) referenced this method for

defining a preliminary groundwater domain (springshed) for springs within the SRWMD.

Furthermore, Upchurch et al. (2001) referenced the uses of geochemical fingerprinting to refine

groundwater domains.

Geochemical factor analysis (fingerprinting) has been used in the SRWMD to identify

recharge areas within the upper Floridan aquifer (Lawrence and Upchurch, 1982). From the

factor analysis, four distinct chemical distinct water masses were identified as well as the

impacts of the quality of the recharge water entering the upper Floridan aquifer. Factor analysis

was employed due to the combining of variables that are correlated into clusters in order of the

amount of variance explained (Lawrence and Upchurch, 1978; Lawrence and Upchurch, 1982).

Jones et al. (1996) used hydrochemical facies analysis geochemicall fingerprinting) to determine

groundwater quality domains to Rainbow Springs to ascertain distinctive water quality and relate

the observed water quality within the domain to specific spring vents within the Rainbow springs

group. The hydrochemical facies placed a series of water quality analyses into a spatial context

that allowed for patterns to be determined. Also, hydrochemical facies analyses were used by

Maddox et al. (1992) when determining the quality of waters within the Florida' s aquifers.

Variations in NO3-N concentrations within the groundwater domain of Rainbow Springs were

due to anthropogenic sources such as inorganic fertilizer (Jones et al., 1996).










In most published studies by geologists, the term factor analysis is used when the actual

analysis is Principal Component Analysis (Davis, 1973). Principal Component Analysis (PCA)

is used to interpret the structure within the variance-covariance matrix of a multivariate data set

(Davis, 1973). The PCA is a method that simplifies a dataset (Lawrence and Upchurch, 1982).

PCA is also called Karhunen-Loeve transform.

Based on this literature review, additional evaluation of water quality issues in the SRB

are needed to define the extent of nutrients, NO3-N and TP, and relationships between the water

resources, nutrients and possible sources of the nutrients. This dissertation will address the

interaction of ground and surface water, extent and changes over time of nutrients, NO3-N and

TP, in the water resources of the SRWMD and evaluate relationships of the possible sources of

the nutrients, NO3-N and TP, with observed concentrations in the water resources with the goal

of determining anthropogenic factors effecting NO3-N and TP concentrations in the water

resources.










Table 2-1. Reaches of the Suwannee River (Hornsby et al., 2000).
Reach Description
1 Upper River Blackwater
2 Cody Scarp Transitional
3 Middle River Calcareous
4 Lower River Calcareous
5 Tidal Riverine
6 Estuary (same as 5 with salinity)





Table 2-2. National NO3-N concentrations in 383 U.S. Rivers (USDA, 1991).
Percentile Concentrations
25t 0.21 mg N L^
50th 0.40 mg N L^1
75th' 0.89 mg N L^'





Table 2-3. Tidal-freshwater water quality indices based on NO3-N concentration (USDA, 1991)
Condition Nitrate-Nitrogen (mg N L^')
Healthy and High Quality < 0.6
Fair 0.6 to 1.0
Fair to Poor 1.0 to 1.8
Poor > 1.8
Note: For higher salinity levels N is more limiting and optimum N concentrations are much lower than 0.6 mg N L'






































~/District Boundary
[j County Boundaries
Northern Highlands
Gulf Coastal Lowlands
River Valley Lowlands





0 20 40 Miles







Th E mao a pmparsd for information
purposEs and does not confrmto
National Map Awnuray Standards.
No atlempt has been made to eiartbilah
or lamb~ speolis ~didional houndarm
of eaher f~deml, rshts, or luml agendmo.


Figure 2-1.


Physiography regions of the Suwannee River Water Management District (Hornsby and Ceryak, 1999).







































Legend LAKELAND

Soil Component MANDARIN
ADAMSVILLE ORLANDO
ALAGA ORSINO
ALPIN ORTEGA
APOPKA OSIER I *,~
PARENTS OTELA ; '
ASTATULA OUSLEY
BIGBEE PAOLA s
CHANDLER PNE
CASSIA PICKNEY
CHIPLEY PITS
CLARA PLACID
ELECTRAVARIANT POMPANO
FORT MEADE PSAMMAQUENTS
FORT MEADE VARIANT QUARTZIPSAMMENTS
FOXWORTH RESOTA
GAINESVILLE RIDGELAND
HURRICANE RIDGEWOOD
KERSHAW TAVARES
KUREB UDORTHENTS
LAKE VALDOSTA


Figure 2-2. High leaching soils in the Suwannee River Water Management District.





e0 Cross Section

c SRWMD Boundary i

Suwannee Basin Boundary






0 10 20 40 Miles
1 1 I I


B p ~Suwannee River e9-m __ $ 10


msI~ -- I ii3.lP msI O

OCALA LIM STONE
S-100


AVONW P4RK LifAIESTONE
S-200


Legend'
620 FGS Well Number LIEGTrLf1 OE--0
Ocala Formation Name
--- Inferred Top of Formation
S-400
-Top of Formation
msI Mean Sea Level 0 10 20 40 Miles







Figure 2-3. Generalized geologic cross section of the region (modified from Ceryak et al.,
1983).








































Floridan Confined/Sem i-confined
Floridan Unconfined



0 20 40 Miles


Figure 2-4. Confined and unconfined regions of the Floridan aquifer system (Hornsby and Ceryak, 1999).
















































Figure 2-5. Map showing the reaches of the Suwannee River in Florida (Hornsby et al., 2000).















57













o Reach 1 M Reach 2 M Reach 3 o Reach 4 M Reach 5


120.00

100.00 -

O 80.00

a 60.00

S40.00

20.00

0.00 m






Figure 2-6. Plot of mean alkalinity (mg L' as CaCO3) in the five reaches of the Suwannee River
in Florida (Hornsby et al., 2000).





o Reach 1 m Reach 2 m Reach 3 o Reach 4 m Reach 5

450
400
350
300
3 250
0. 2 00
150










Figure 2-7. Plot of mean color (PCU) in the five reaches of the Suwannee River in Florida
(Hornsby et al., 2000).












Solution P P inputs P loss


Figure 2-8. P cycle in soils.





Processes


Irrnmabilization


Volatilization


Figure 2-9. N cycle in soils.


Inputs


g





AnulNitrate-N Load
AnulTotal Phosphorus Load


SOkefenokee Swamp Boundary
/VCounty Boundaries
Reaches
SSuwannee Reach 1
[7Suwannee Reach 2
Suwannee Reach 3
Santa Fe Reach 1
Santa Fe Reach 2
Suwannee Reaches 4, 5, &6
Suwannee River Basin
Suwannee River Watershed
Alapaha River Watershed
Withlacoochee River Watershed
Santa Fe River Watershed


Figure 2-10. Nutrient loadings by watershed/reach in the Suwannee River System for water year
1998 (Hornsby and Mattson, 1998).



































Figure 2-11. Estimated N inputs for Suwannee County (Hornsby and Mattson, 1998).


Figure 2-12. Estimated N inputs for Lafayette County (Hornsby and Mattson, 1998).









CHAPTER 3
COMPARISONS OF PRE AND POST OUTSTANDING FLORIDA WATER
CONCENTRATIONS, TRENDS AND RECENT OCCURRENCES OF NITRATE-
NITROGEN AND TOTAL PHOSPHORUS

Introduction

The Florida Legislature in 1979 designated the Suwannee River in Florida an

Outstanding Florida Water (OFW) which means the River has significant cultural and ecological

value to the State of Florida. The Florida Department of Environmental Protection (FDEP) was

directed by Florida Statues Chapter 403.061 (27) which states "Establish rules which provide for

a special category of water bodies within the State, to be referred to as Outstanding Florida

Waters, which water bodies shall be worthy of special protection because of their natural

attributes. Nothing in this subsection shall affect any existing rules of the department." Thus,

the FDEP developed a rule 62-302.700 Florida Administrative Code (F.A.C.). Rule 62-302.700

(1) F.A.C. states "It shall be the Department policy to afford the highest protection to

Outstanding Florida Waters and Outstanding National Resource Waters. No degradation of

water quality, other than that allowed in subsections 62-4.242(2) and (3), F.A.C., is to be

permitted in Outstanding Florida Waters and Outstanding National Resource Waters,

respectively, not withstanding any other Department rules that allow water quality lowering."

This rule focuses on point source discharges into an OFW. Furthermore, rule 62-302.700 (8)

F.A.C. establishes the baseline definition for water bodies designated OFWs, as stated in the

following: "For each Outstanding Florida Water listed under subsection 62-302.700(9), F.A.C.,

the last day of the baseline year for defining the existing ambient water quality (paragraph 62-

4.242(2)(c), F.A.C.) is March 1, 1979, unless otherwise indicated. Where applicable,

Outstanding Florida Water boundary expansions are indicated by date(s) following "as mod."

under subsection 62-302.700(9), F.A.C. For each Outstanding Florida Water boundary which









expanded subsequent to the original date of designation, the baseline year for the entire

Outstanding Florida Water, including the expansion, remains March 1, 1979, unless otherwise

indicated." The Suwannee River falls in the initial induction into the OFW status; therefore, the

last day of the baseline year is March 1, 1979.

The Suwannee River at Branford, Florida, has been monitored for water quality analytes

by the United States Geological Survey (USGS) since 1954 and the Suwannee River Water

Management District (SRWMD) since 1989. Concurrently, with water quality monitoring, the

USGS monitors daily discharge for the Suwannee River at Branford (station number 02320500)

since 1931 to present. Due to the paucity of historical data for the Santa Fe River only the

Suwannee River at Branford will be discussed in this Chapter for long trend analysis and

comparisons to pre-OFW, baseline, and post-OFW concentrations of total phosphorus (TP) and

nitrate-nitrogen (NO3-N).

The SRWMD Water Assessment Regional network (WARN) has 67 surface water

quality stations (47 river and 20 spring stations) and 251groundwater quality stations as shown in

Figures 3-1 and 3-2, respectively (Hornsby et al., 2005C). The WARN data will be used to

determine the recent distribution and occurrences of TP and NO3-N in the SRWMD. The

WARN surfacewater quality stations have a period of record of sixteen years (Hornsby et al.,

2005A) and the WARN groundwater quality stations have a period of record of six years

(Hornsby et al., 2005B). The WARN surfacewater quality monitoring was started in 1989 while

the WARN groundwater quality monitoring was started in 2000. The WARN water quality data

provides a dataset that has been collected and analyzed in a consistent manner. This reduces

variation in the data due to collection and analyzed method differences.









The obj ectives of this chapter are to analyze and interpret changes in the TP and NO3-N

concentrations in the Suwannee River at Branford from pre-OFW conditions to post-OFW

conditions by combining several data sets, relate possible anthropogenic factors to observed

changes, and determine the recent occurrences of TP and NO3-N in surface water, springs and

ground water in the upper Floridan aquifer within the SRWMD using WARN data.

Materials and Methods

Long Term Trend Analysis

Data was collected from the USGS for the station on the Suwannee River at Branford,

Florida and the SRWMD. The USGS has been monitoring water quality at this site since 1954.

The USGS data contains NO3-N and potassium (K) concentrations from 1954 to 1989 and TP

concentration from 1971 to 1989. The SRWMD data contains NO3-N, K, and TP data from

1989 to 2006 for the Suwannee River at Branford. The data from the USGS and the SRWMD

were combined to form a time series (or period of record) from 1954 to 2006.

Period of record graphs were produced for TP, K, and NO3-N. The period of record for

NO3-N, K and TP were analyzed for linear correlation. Post-OFW median water year values for

NO3-N and TP were compared to median pre-OFW values using a Mann-Whitney test. The

anthropogenic factors, such as, fertilizer sales, crop acreages, and population, were gathered for

the period of record for correlation with riverine TP and NO3-N concentrations.

Recent Distribution and Occurrences of Total Phosphorus and Nitrate-Nitrogen

The SRWMD WARN data was analyzed using MiniTabO to generate descriptive

statistics (mean, standard deviation, median, 25th percentile, 75th percentile) for ground water

(upper Floridan aquifer and springs) and surfacewater quality. Surface water was further

subdivided by river basin. Annual mean upper Floridan aquifer concentrations contours of TP









and NO3-N were generated using SurferC with the kriging option with linear interpolation and

zero nugget.

Annual surfacewater basin loading was determined using water quality data collected by

the SRWMD, under my supervision, and discharge volume collected by the USGS and

SRWMD. Loads for TP and NO3-N were calculated by sub-basin.

Results and Discussion

Long Term Trends

The median annual TP concentration in the Suwannee River at Branford for the period of

record (1971 to 2006) ranged from 0.13 to 0.34 mg P L^1 as shown in Appendix A, Figure A-1.

Based on the data, there was an increasing trend from 1971 to 1985 and a declining trend starting

in 1986 in the Suwannee River at Branford for TP as seen in Figure 3-3. The TP concentrations

dropped in water years 1985 and 1986 and have continued to decline. The range of TP

concentrations observed by water year is shown in Figure 3-4. This drop in TP concentration in

1985-1986 and the declining trend is associated with the regulation of a point source discharge

for phosphate mining operations in northern Columbia and eastern Hamilton counties (J. Owens,

1998. Personal Communication). Also, the variations in the riverine concentrations observed

have been reduced since 1986 due to regulation of the point source. The Suwannee River has a

background concentration of TP of 0.3 mg L-1 due to the river coming into contact with the

Hawthorne Group that contains high levels of P (FDER, 1985). Thus, the TP concentration in

the Suwannee River is decreasing due to better management practices by the phosphate mining

operation.

The median annual NO3-N concentrations in the Suwannee River at Branford for the

period of record (1954 to 2006) ranged from 0. 14 to 1.21 mg N L^1 as shown in Appendix A,









Figure A-2. Based on the data, there is an increasing trend in the Suwannee River at Branford

for NO3-N (Figure 3-5). Ham and Hatzell (1996) documented this increasing trend for NO3-N

for the period of 1954 to 1995 for the Suwannee River at Branford. Recent data (1996 to 2006)

indicates that the increasing trend is still present. The range of NO3-N concentrations observed

by water year is shown in Figure 3-6.

Comparison of Pre and Post OFW Water Quality

The OFW language in F.A.C. establishes 1979 as the baseline year for water quality for

the Suwannee River and that the water quality should not degrade from the baseline water

quality. Changes in water quality in the Suwannee River can be determined by comparing the

water quality of a point in time to the water quality during the baseline year. Using the water

quality data prior to and including the baseline year defines the pre-OFW and water quality data

after the baseline year defined the post-OFW. A comparison of annual median NO3-N and TP

concentrations to 1979, the year the River was designated an OFW are given in Table 3-1. The

baseline annual median concentrations for NO3-N and TP are 0.50 mg N L^1 and 0.235 mg P L^1,

respectively; and post-OFW annual median concentrations for NO3-N and TP are 0.72 mg N L^1

and 0.152 mg P L^1, respectively. The comparison of baseline to post-OFW concentration shows

a decreasing trend at greater than the 99.9 % confidence level for TP and a increasing trend at

greater than the 99.9 % confidence level for NO3-N. Also, a comparison of water years 1954 to

1979 or pre-OFW designation median concentrations of NO3-N and TP of 0. 14 mg N L^1 and

0.21 mg P L^1, respectively; and water years 1979 to 2006 or post-OFW designation annual

median concentrations of NO3-N and TP of 0.72 mg N L^1 and 0. 152 mg P L^1, respectively,

yielded similar results to the pre-OFW to the post-OFW. The annual NO3-N loads for 1979 and

1998 to 2005 (post-OFW) are presented in Table 3-2. The annual NO3-N load for 1979 was










3,548,981 kg N yr- while the annual NO3-N load for water year 2005 was 6,197,855 kg N yr-

This shows an approximately 75 percent increase in the annual NO3-N load for the Suwannee

River to the Gulf of Mexico from 1979 to 2005 and is indicative of the increasing trend in NO3-

N concentrations in the river.

Anthropogenic Factors

The counties adj acent to the Suwannee River at Branford are Suwannee and Lafayette.

The reach of the Suwannee River that borders Suwannee and Lafayette counties receives little to

no surface water inputs due to the internal drainage of the counties; however, the River picks up

flow from groundwater discharge via springs and seeps in the riverbed during base flow

conditions. This pickup in flow from groundwater inputs can almost double the volume in the

River from upstream to down stream under certain flow conditions (T. Mirti, 2003, Personal

Communication). Data has shown that the reach of the Suwannee River, also known as the

Middle Suwannee River Basin (MSRB), bordering Suwannee and Lafayette counties has the

largest increase in NO3-N concentration than any other sub-basin in the Suwannee River system

and the NO3-N was associated with flow conditions that are dominated by groundwater inputs

(Hornsby et al., 2005A).

The population began increasing between 1970 to 1980 for Suwannee and Lafayette

counties (Figure 3-7). The combined populations for Suwannee and Lafayette counties were

plotted against annual median NO3-N and TP concentrations for the Suwannee River at Branford

as shown in Figures 3-8 and 3-9, respectively. The plot of population versus NO3-N

concentrations in the Suwannee River at Branford shows as population increases so does the

riverine NO3-N concentration. The increase in riverine NO3-N concentration associated with the

increase in population may be due to increased densities of onsite domestic systems (septic









tanks) and/or increased use of fertilizers associated with improved pasture and agricultural

production. Based on the data for TP, there is an inverse relationship with TP concentration and

population; however, this is a spurious correlation because the concentration of TP in the

Suwannee River is dominated by the mining discharge in the upper River.

Fertilizer sales data (N, K, P) for Suwannee and Lafayette counties from 1941 to 2006 are

shown in Figure 3-10. Florida Department of Agriculture and Consumer Services (DACS)

Fertilizer sales data represents the sale and use of fertilizer within a county (W. Cox, 1997,

Personal Communication). Florida Department of Agriculture and Consumer Services tracks the

sales and the designation of N fertilizers in the State as required by Chapter 576.041(7), Florida

Statues. Reports on fertilizer sales and destination county are reported to DACS on a monthly

basis as required by Chapter 576, Florida Statues. Thus, DACS can generate annual reports by

county that represents the fertilizer sales as well as fertilizer applied in each county within the

State. Figure 3-11 presents the annual median TP concentration in the Suwannee River at

Branford and P sales for 1971 to 2006. There is no correlation with sales data and riverine TP

concentrations. Based on the P sales data, a sharp increase in P sales occurred in 1998 and has

remained well above historic sales data from 1971 to 1998. The increase in P sales that occurred

in 1998 maybe attributed to reapplication ofP to crops during the growing season due to El Nifio

conditions; however, this is not the case for 1999 to 2006. The departure from historical sales

data is most likely associated with a change in the DACS methodology for the collection of P

sales data. A possible reason for the P sales remaining above the historical level since 1998 may

be a result of a change in reporting format that occurred in 1994 which the fertilizer dealers

submit to DACS (W. Cox, 2007, Personal Communication). Furthermore, since 1998, DACS

does not compile the fertilizer sales data or develop the annual fertilizer sales report. Florida










Department of Agriculture and Consumer Services now contracts the data management and

development of the annual report of fertilizer sales to the University of Kentucky (D. Terry,

2007, Personal Communication). Therefore, the potential exists that the historical P sales data

have been under reported. Figure 3-12 presents the annual median NO3-N concentrations in the

Suwannee River at Branford and N sales for 1954 to 2006. There was a linear increasing trend

in fertilizer sales and riverine NO3-N concentrations from 1954 to 1982. From 1982 to 1992,

sales data indicates dramatic fluctuations in N sales; however, the sales were lower than the time

period froml954 to 1982. The riverine NO3-N concentrations began dropping in 1988 and

shows similar fluctuations as the sales data. This drop in riverine concentrations reflects the drop

in total crop acres, primarily corn acreage, in Suwannee and Lafayette counties as shown in

Figure 3-13. In 1998, a spike in sales for N was reported similar to the spike of P in 1998. Also,

Figure 3-13 shows that from 1960 to 1999 N fertilizer sales data tracked the total crop acres in

Suwannee and Lafayette counties; however, since 1988, N fertilizer sales data has diverted from

the total cropped acres indicating that more fertilizer is being applied per acre than in the period

1960 to 1988. The correlation of the N fertilizer sales and riverine NO3-N concentration was

analyzed using MinitabO time series analysis with cross correlation. Based on a cross

correlation of N fertilizer sales and riverine NO3-N concentration, there is a one to six year time

lag between the relationship of N sales data and the observed riverine NO3-N concentrations

(Table 3-3). This time lag or residence time in sales data and riverine NO3-N concentrations is

most likely a result of rainfall and the path from the application through the upper Floridan

aquifer to river via springs and seeps in the riverbed. The variation in rainfall from year to year

greatly influences the rate at which NO3-N will be leached from the root zone and vadose zone

and reach the underlying aquifer. Furthermore, the residence time is related to tortuosity of the









flow path and aquifer properties, such as, head, porosity and transmissivity (Maddox et al.,

1992).

The annual median potassium (K) concentrations in the Suwannee at Branford were

plotted for water yearsl954 to 2006 in Appendix A, Figure A-3. An increasing trend for riverine

K was observed (Figure 3-14). The trend for K was similar to the trend observed for NO3-N.

The riverine annual median for K and NO3-N were plotted form 1954 to 2006 in Figure 3-15.

Figure 3-16 presents the annual median K concentrations in the Suwannee River at Branford and

K sales for 1954 to 2006. The K sales data shows that prior to 1998 the amount of K sold in

Suwannee and Lafayette counties was less than 100,000 kg y^l; however, in 1998 a spike in sales

occurred, sales for 1998 were ~500,000 kg and since 1998 have ranged between 225,000 to

300,000 kg. The increases in 1998 for K also occurred for P and N. This was possibly due the

heavy rainfall in the spring of 1998 that was generated by a strong El Nifio. The heavy

springtime rains result in leaching events and farmers reapplied fertilizer to replace the leached

nutrients. As with P and N, the reported K sales have been greater than historical levels since

1998. This might be attributed to a change in reporting format in 1994 that the fertilizer dealers

submit to DACS and different data management and report format developed by DACS

contractor, the University of Kentucky (W. Cox, 2007, Personal Communication)

Recent Distribution and Occurrences of Total Phosphorus and Nitrate-Nitrogen

Upper Floridan aquifer water quality

Background concentrations for TP and NO3-N in the upper Floridan aquifer is < 0.1 mg P

L^ and <0.05 mg N L^1, respectively (Maddox et al., 1992). The mean upper Floridan aquifer

concentrations for TP and NO3-N are 0.219 mg P L^1 and 0.94 mg N L^1, respectively (Table 3-

4). These concentrations (2001-2006) are three times above background and 23 times above










background concentrations for TP and NO3-N, respectively. Annual mean distributions for water

years 2001 to 2005 of TP, NO3-N, and K in the upper Floridan aquifer are presented in Appendix

B, Figures B-1A to B-1E, B-2A to B-2E, and B-3A to B-3E, respectively. The annual mean

distribution for water year 2006 for TP, NO3-N, and K are presented in Figures 3-17, 3-18, and

3-19, respectively. Lower TP concentrations are observed in the regions where the upper

Floridan aquifer is confined while the higher concentrations were observed in the unconfined

regions of the upper Floridan aquifer (Figure 3-17). Since the unconfined region receives

recharge almost directly from rainfall events, the pH of the recharge water is still slightly acidic;

thus, mobilizing TP. Thus, the distribution of TP in the upper Floridan aquifer seems to be

controlled by whether the upper Floridan aquifer is confined or unconfined. The highest NO3-N

concentrations were observed in the unconfined regions of the upper Floridan aquifer; while, the

lowest NO3-N concentrations are observed in the confined regions of the upper Floridan aquifer

(Figure 3-18). Nitrogen applied to the land surface in the unconfined regions leached into the

upper Floridan aquifer when recharge events occur. Thus, NO3-N concentrations seem to be

controlled by both geology and land use practices. The mean upper Floridan aquifer

concentration for K was 1.23 mg K L^1 compared to the background concentration of 1.1 mg K

L.The concentration of K observed in the upper Floridan aquifer has no relationship to

geology (Figure 3-19). Both the unconfined and confined regions have similar concentrations.

There are regions within the unconfined upper Floridan aquifer that show K depletion that may

correlate to zones where the ground water is discharging (i.e., conduct flow) and possibly

represents a groundwater basin.

A summary of all collected water quality parameters for the upper Floridan aquifer is

presented in Appendix B, Table B-1 and contour concentrations for TP, NO3-N, and K are









graphically presented in Appendix B, Figures B-1A to B-1E for TP, Figures B-2A to B-2E for

NO3-N, and Figures B-3A to B-3E for K.

Spring water quality

Spring water quality data are presented by specific river basin. The mean TP for the

springs of Aucilla River Basin is 0.053 mg P L^1, for the springs of Coastal Rivers Basin is 0.075

mg P L^1, for the springs of Lower Suwannee River Basin (LSRB) is 0.051 mg P L^1, for the

springs of Santa Fe River Basin is 0.083 mg P L^1, for the springs of Upper Suwannee River

Basin is 0. 102 mg P L^1, for the springs of Waccasassa River Basin is 0.045 mg P L^1, and the

springs of Withlacoochee River Basin is 0.054 mg P L^1 (Table 3-5). The TP observed in the

springs reflect the concentrations of TP observed in the upper Floridan aquifer which supplies

water to the springs. Springs in the unconfined regions of the upper Floridan aquifer have higher

TP concentrations than the springs in the confined region.

The mean NO3-N for springs of the Aucilla River Basin is 0. 16 mg N L^1, for the springs

of Coastal Rivers Basin is 0.05 mg N L^1, for the springs of LSRB is 3.01 mg N L^1, for the

springs of Santa Fe River Basin is 0.90 mg N L^1, for the springs of Upper Suwannee River Basin

is 0.40 mg N L^1, for the springs of Waccasassa River Basin is 0.43 mg N L^1, and the springs of

Withlacoochee River Basin is 1.34 mg N L^1 (Table 3-5). Similarly, to TP, the NO3-N

concentrations in the springs are a reflection of the concentrations in the upper Floridan aquifer.

The unconfined regions of the upper Floridan aquifer are producing springs with the highest

concentrations of NO3-N. The unconfined regions of the upper Floridan are subject to

contamination by water soluble contaminants, such as NO3-N.

A summary of all collected water quality parameters for the springs of Aucilla River

Basin is presented in Appendix B, Table B-2, for the springs of Coastal Rivers Basin is presented









in Appendix B, Table B-3, for the springs of LSRB is presented in Appendix B, Table B-4, for

the springs of Santa Fe River Basin is presented in Appendix B, Table B-5, for the springs of

Upper Suwannee River Basin is presented in Appendix B, Table B-6, for the springs of

Waccasassa River Basin is presented in Appendix B, Table B-7, and the springs of

Withlacoochee River Basin is presented in Appendix B, Table B-8.

Surface water quality

The mean TP for the Alapaha River Basin is 0.127 mg P L^1, for the Aucilla River Basin

is 0.026 mg P L^1, for the Coastal Rivers Basin is 0. 169 mg P L^1, for the LSRB is 0. 115 mg P

L^, for the Santa Fe River Basin is 0.151 mg P L^1, for the Upper Suwannee River Basin is 0.253

mg P L^1, for the Waccasassa River Basin is 0.075 mg P L^1, and the Withlacoochee River Basin

is 0. 137 mg P L^1 (Table 3-6). The exception of the Upper Suwannee River Basin which is

influenced by a point discharge and geological formation, the TP concentration seems to be

influenced by geological formation.

The mean NO3-N for the Alapaha River Basin is 0.48 mg N L^1, for the Aucilla River

Basin is 0.05 mg N L^1, for the Coastal Rivers Basin is 0.07 mg N L^1, for the LSRB is 0.57 mg

N L^1, for the Santa Fe River Basin is 0.34 mg N L^1, for the Upper Suwannee River Basin is 0.15

mg N L^1, for the Waccasassa River Basin is 0.10 mg N L^1, and the Withlacoochee River Basin

is 0.39 mg N L^1 (Table 3-6). The riverine NO3-N concentration seems to be influenced by the

NO3-N concentrations in the ground water of the upper Floridan aquifer adj acent to the rivers.

A summary of all collected water quality parameters for the Alapaha River Basin is

presented in Appendix B, Table B-9, for the Aucilla River Basin is presented in Appendix B,

Table B-10, for the Coastal Rivers Basin is presented in Appendix B, Table B-11, for the LSRB

is presented in Appendix B, Table B-12, for the Santa Fe River Basin is presented in Appendix










B, Table B-13, for the Upper Suwannee River Basin is presented in Appendix B, Table B-14, for

the Waccasassa River Basin is presented in Appendix B, Table B-15, and the Withlacoochee

River Basin is presented in Appendix B, Table B-16.

Annual TP and NO3-N loads for the Suwannee River to the Gulf of Mexico for water

years 1990 to 2005 are presented in Figures 3-20 and 3-21, respectively. Asbury and Oaksford

(1997) comparison of the Suwannee River to the Altamaha River, St. Johns River, Satilla River,

Ogeechee River, Withlacoochee River (South), and the Ochlockonee River, showed the

Suwannee River had the highest in-stream TP and NO3-N load km-2 Of basin of the seven rivers.

Quinlan (2003) demonstrated that the Suwannee River and its estuary are N limited. Thus,

increases in NO3-N loads in the Suwannee River and the estuary will increase the potential for

eutrophication. Figures 3-22 and 3-23 present the TP and NO3-N for water years 1998 to 2005

with annual rainfall. The TP loads increased with increased rainfall. This is likely due to

surfacewater runoff from the headwater in the Okefenokee Swamp that lowers the pH and results

in leaching of P from the Hawthorne Group and other sites where P is bound. The NO3-N loads

increases with rainfall is most likely due to the flushing of the NO3-N from the soil profile into

the upper Floridan aquifer that is connected to the rivers. Based on the regionalization of the

SRB developed by Hornsby and Mattson (1998), the mainstem of the Suwannee and Santa Fe

rivers are subdivided into six and two reaches, respectively. Annual TP loads for the sub-basins

of the SRB for each water year from 1998 to 2004 are presented in Appendix B, Tables B-17A to

B-17F and graphically presented in Appendix B, Figures B-4A to B-4G. The annual TP and

NO3-N loads for the sub-basins of the SRB for water year 2005 are presented in Table 3-7 and

graphically presented in Figure 3-24. The sub-basin that contributed the largest percentage of

the TP load is Reach 1 of the Suwannee River, followed by the Alapaha and Withlacoochee









rivers for water years 1998 to 2005. This is the region where the Suwannee River intersects the

Hawthorne Group and where a phosphate mining operation discharges to the Suwannee River.

The sub-basin that contributed the largest percentage of the NO3-N load is Reach 3 of the

Suwannee River, followed by Reach 2 of the Santa Fe River for water years 1998 to 2005.

Summary and Conclusions

The observed concentrations of TP and NO3-N in the Suwannee River at Branford has

significantly (>95% confidence level) changed since its designation as an Outstanding Florida

Water in 1979. The annual median TP concentrations in the Suwannee River have significantly

decreased from 0.235 mg P L^1 in water year 1979 to 0. 148 mg P L^1 in water year 2006. The

decrease in the annual median TP concentration in the Suwannee River that started in 1985

coincides with the increased regulation of a phosphate mining operation in Hamilton and

Columbia counties. The annual median NO3-N concentrations in the Suwannee River have

significantly increased from 0.50 mg N L^1 in water year 1979 to 1.21 mg N L^1 in water year

2006. There is an observed time lag between the sales data and riverine NO3-N concentrations

of one to six years. The increasing trend for NO3-N in the Suwannee River is supported by the

increased use of inorganic fertilizer. Therefore, anthropogenic factors are driving the changes in

water quality for TP and NO3-N from pre-OFW to post-OFW concentrations.

The mean upper Floridan aquifer concentrations for TP and NO3-N are three times above

background and 23 times above background concentrations, respectively, as defined by Maddox

et al (1992). Surfacewater NO3-N concentrations reflect the upper Floridan aquifer groundwater

concentrations for NO3-N in the adj acent surfacewater basin. Surfacewater basin concentrations

of TP are driven by geological formations, point sources and surface runoff. While, surfacewater

basins with low concentrations of NO3-N in the upper Floridan aquifer have low concentrations










of NO3-N observed in the surface water and surfacewater basins with high concentrations of

NO3-N in the upper Floridan aquifer have high concentrations of NO3-N observed in the surface

water. The basin with the highest percentage load of TP is Reach 1 of the Suwannee River. This

is a region of the Suwannee River where a point source discharges and where the River comes in

contact with a P bearing Hawthorne Group. The basins with the highest percentage loads of

NO3-N is Reach 3 of the Suwannee River and Reach 2 of the Santa Fe River. These are regions

that have high concentrations of NO3-N in the upper Floridan aquifer and the Suwannee and

Santa Fe rivers receives ground water from numerous springs and riverbed seeps during base

flow conditions. Thus, ground water from the upper Floridan aquifer plays a maj or role on the

quality of surface water in regions where the River intersects the top of the upper Floridan

aquifer.










Table 3-1. Comparison of pre and post OFW
the Suwannee River at Branford.
Water Year Median NO3-N (mg N L )
1954 to 1979 0.14
(pre OFW)
1979 to2006 0.72
(post-OFW)
1979 (Baseline) 0.50
Annual water year comparison to Baseline
1998 0.49
1999 1.05
2000 0.835
2001 0.680
2002 0.875
2003 0.595
2004 0.97
00; 2005 0.43
2006 1.21


concentrations of TP and N03-N to OFW baseline concentrations of TP and NO3-N for


Median TP (mg P L )
0.21


Trend


Significant


Trend


Significant


increasing


<0.0001


0.152

0.235

0.109
0.118
0.129
0.123
0.216
0.160
0.167
0.153
0.151


decreasing


<0.0001


Neutral
increasing
increasing
increasing
increasing
increasing
increasing
decreasing
increasing


0.6474
<0.0001
0.0001
0.0346
0.0003
0.6711
0.0051
0.3218
0.0040


decreasing
decreasing
decreasing
decreasing
decreasing
decreasing
decreasing
decreasing
decreasing


<0.0001
<0.0001
<0.0001
<0.0001
0.0215
<0.0001
<0.0001
<0.0001
<0.0001


Table 3-2. Comparison of OFW baseline annual NO3-N load to water years 1998 to 2005 annual NO3-N load.
Water Year Annual NO3-N Load (kg N yr- ) Departure from Baseline Mean Discharge [cfs/L s^)]l
1979 3,548,981 Baseline 8,657(245,139)
1998 6,402,033 Greater than 15,476(43 8,232)
1999 4,270,788 Greater than 6,415(181,653)
2000 2,358,000 Less than 3,406(96,447)
2001 2,35 6, 146 Less than 5,339(151,183)
2002 2,674,080 Less than 3,275(92,738)
2003 4,036,590 Greater than 10,088(285,660)
2004 4,789,350 Greater than 6,467(183,125)
2005 6,197,855 Greater than 16,310(461,848)










Table 3-3. Cross correlation of N fertilizer sales and annual median riverine NO3-N concentration for the Suwannee River at
Branford.


Lag time (years)
-8
-7
-6
-5
-4
-3
-2
-1
0
1
2
3
4
io 5
6
7
8


Cross correlation function
-0.0596
-0.0567
0.0228
0.0719
0.1256
0.2065
0.2917
0.4014
0.4312
0.5200
0.5547
0.5456
0.5540
0.4681
0.5090
0.4028
0.3469


Table 3-4. Summary of NO3-N and TP concentrations in the upper Floridan aquifer for the Suwannee River Water Management
District (2001 to 2006).


Standard
Deviation
2.73
1.558


25th
Percentile
0.00
0.000


75th
Percentile
1.00
0.156


Units
mg L
mgL


Median
0.17
0.07


Minimum
0.000
0.000


Maximum
52.0
45.0


Parameter
NO3-N
TP


Mean
0.94
0.219










Table 3-5. Summary of NOs-N and TP concentrations for the Springs by River Basin (1989 to 2006).


Standard
Deviation
0.14
0.053
0.07
0.020
3.11
0.031
1.60
0.058
0.40
0.046
0.25
0.006
0.35
0.016


25th
Percentile
0.05
0.036
0.02
0.068
1.30
0.032
0.39
0.048
0.02
0.060
0.42
0.044
1.17
0.044


75th
Percentile
0.26
0.056
0.05
0.078
3.45
0.064
1.01
0.101
0.70
0.136
0.65
0.048
1.58
0.060


Basin
Aucilla
Aucilla
Coastal
Coastal
Lower Suwannee
Lower Suwannee
Santa Fe
Santa Fe
Upper Suwannee
Upper Suwannee
Waccasassa
Waccasassa
00 Withlacoochee
Withlacoochee


Parameter
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP


Units
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
me, L-


Mean
0.17
0.054
0.05
0.075
3.01
0.051
0.91
0.084
0.40
0.102
0.44
0.046
1.35
0.054


Median
0.13
0.043
0.03
0.072
1.91
0.047
0.58
0.077
0.29
0.111
0.43
0.046
1.40
0.050


Minimum
0.00
0.009
0.00
0.047
0.00
0.004
0.00
0.004
0.00
0.004
0.03
0.039
0.27
0.040


Maximum
0.46
0.319
0.38
0.128
21.80
0.430
26.00
0.820
1.91
0.220
0.65
0.053
1.94
0.140










Table 3-6. Summary of NO3-N and TP concentrations for each River Basin in the Suwannee River Water Management District (1989


to 2006).

Basin
Alapaha
Alapaha
Aucilla
Aucilla
Coastal
Coastal
Lower Suwannee
Lower Suwannee
Santa Fe
Santa Fe
Upper Suwannee
00 Upper Suwannee
Waccasassa
Waccasassa
Withlacoochee
Withlacoochee


Standard
Deviation
0.44
0.097
0.05
0.027
0.11
0.707
0.33
0.094
0.32
0.368
0.31
0.535
0.09
0.036
0.28
0.098


25th
Percentile
0.14
0.110
0.01
0.037
0.02
0.054
0.31
0.111
0.07
0.080
0.03
0.100
0.02
0.050
0.20
0.093


75th
Percentile
0.72
0.250
0.07
0.070
0.06
0.139
0.81
0.181
0.56
0.210
0.20
0.280
0.16
0.098
0.51
0.147


Units

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L


Median
0.31
0.180
0.03
0.048
0.05
0.091
0.56
0.140
0.26
0.124
0.05
0.168
0.09
0.068
0.32
0.115


Minimum
0.00
0.041
0.00
0.011
0.00
0.010
0.00
0.004
0.00
0.001
0.00
0.004
0.00
0.023
0.00
0.010


Maximum
2.00
0.567
0.44
0.150
0.71
9.600
2.44
1.320
4.80
6.000
8.04
8.900
0.49
0.350
2.36
1.100


Parameter
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP
NO3-N
TP


Mean
0.48
0.191
0.05
0.054
0.07
0.285
0.57
0.161
0.34
0.204
0.15
0.299
0.10
0.075
0.39
0.137














340,891.6
297,750.6
507,256.9
340,207.0
167,049.8
748,258.8
201,830.1
237,689.3
145,558.5
-106,884.5
-29,667.8
2, 342, 683. 5


14.6%
12.7%
21.7%
14.5%
7.1%
31.9%
8.6%
10.1%
6.2%
-4.6%
-1.3%
100. 0%


Annual Load Contribution (kg/year)
Area (mi2) Nitrate-N % of Load Total Phosphorus % of Load


Tabl 3-. TPandN03- lodigs by watersheds/reach in the Suwannee River for water year 2005.


41,589.9
155,304.6
1,166,049.5
441,407.9
724,641.6
208,815.9
2,362,408.1
48,107.4
1,133,998.0
-421,452.7
1,503,034.7
6,1~97, 855. 5


Contributing Basin
Suwannee River Reach 1
Alapaha River
Withlacoochee River
Withlacoochee GA
Withlacoochee FL
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reach 4
Suwannee River Reaches 5 & 6
Total


2,430
1,801
2,382
2,118
264
443
824
820
564
342
344
9, 950


0.7%
2.5%
18.8%
7.1%
11.7%
3.4%
38.1%
0.8%
18.3%
-6.8%
24.3%
100%











\rr
F


Legend
SRiver Station
SSpring Station


Figure 3-1. Suwannee River Water Management District surfacewater quality monitoring network.


B















































Figure 3-2. Suwannee River Water Management District groundwater quality monitoring network.









0.6


0.4



8, y 0.010x +c 0.146







OOO









Figure 3-3. Median TP for the Suwannee River at Branford with linear trend lines.



















0 .0 ,,
Water year
Figure 3-4. TP concentration by water year for Suwannee River at Branford. Box represents 25th percentile, median, 75th percentile
and whiskers represents the upper and lower observed value.


0.-
0.9-
0.-
0.8
0.-
0.7-
0.-
0.5-


Q,,,q


Ip


B ~ B 9 o B 1 a i i ,4 1 a a Q i B
























































0.00


y = 0.0177x + 0.0504
R2 = 0.6839


1.20





1.00





E 0.80
z
O
co z

.50.60





0.40





0.20


Figure 3-5. Median NO3-N for the Suwannee River at Branford with linear trend line.













-
1.6


1.4-





0.8-

00.









Water Year


Figure 3-6. NO3-N concentration by water year for Suwannee River at Branford. Box represents 25th percentile, median, 75th
percentile and whiskers represents the upper and lower observed value.











HLafayette W Suwannee


40,000



35,000



30,000-



25,000-



00 20,000-



15,000-



10,000-



5,000-





1950 1960 1970 1980 1990 2000 2004


Figure 3-7. Population for Lafayette and Suwannee Counties, 1950 through 2004 (BEBR, 2001; BEBR, 2004).

















. .


-


-* Median NOx-N -a Suwannee and Lafayette Counties Population


1.1





1.2





1





E 0.8





.~0.6





0.4





0.2


-



-



-



-



-


50,000



45,000



40,000



35,000



30,000



25,000



20,000



15,000



10,000



5,000



0


Figure 3-8. Median NO3-N concentration for the Suwannee River at Branford and population for Lafayette and Suwannee counties

(BEBR, 2001; BEBR, 2004).


0
















































0


1,,, 11,,,,,,,,,,,,


STotal P + Population


50,000


45,000


40,000


35,000


30,000


25,000


20,000


15,000


10,000


5,000


O


rr


Water Year


Figure 3-9. Median TP concentration for the Suwannee River at Branford and population for Lafayette and Suwannee counties
(BEBR, 2001; BEBR, 2004).











+N N -- K


8,000,000 0 00,000



7,000,0008000


700,000
6,000,000


600,000
5,000,000

I t \ I ~- fA t500,000

S4,000,000

I I\ I t400,000 aL.

2 3,000,000 ,I II I
300,000


2,000,000
200,000


1,000,000
100,000







Figure 3-10. Fertilizer sales data for Suwannee and Lafayette counties.













SMedian total P + Phosphorus sales for Suwanneee and Lafayette counties


0.35 0 00,000



-800,000
0.3


-700,000

0.25

-600,000


-, 0 oooo

S0.25 00,000





-300,000
0.1

-200,000


0.05
-100,000








Figure 3-11. Median TP concentration for the Suwannee River at Branford and N fertilizer sale for Suwannee and Lafayette counties.



















































0


-*median Nox-N -aN Fertilizer Suwannee & Lafayette counties


8,000,000


7,000,000



6,000,000



5,000,000



4,0 ,0 0(


3,000,000






2,000,000



1,000,000



O


1





0.8






E
0..






0.2


Figure 3-12. Median NO3-N concentration for the Suwannee River at Branford and N fertilizer sales for Suwannee and Lafayette
counties.














120,000


-*-Median Nox-N Total Crops (acres) -aN Fertilizer (*100 kg)


1.2




1



-
3 0.8
z
O






0.4




0.2


-100,000





-80,000





-60,000





-40,000





-20,000


0


r-r~c


/V


01 '




Figure 3-13. Median NO3-N concentration for the Suwannee River at Branford and N fertilizer sales and total crop acres for
Suwannee and Lafayette counties.





















1.6




1.4




















y = 0.0195x + 0.2723
R2 = 0.7482

).4














Water Year


rr,

Y


io -rJ
o\ a,
I


Figure 3-14. Median K concentration for the Suwannee River at Branford with linear trend line.
















-* Median K -5 Median Nox-N


1.6



1.4



1.2



O


OJ
0.

0.


0.





0.


Water Year


Figure 3-15. Median K and median NO3-N concentrations for the Suwannee River at Branford.














SMedian K + K sales Suwannee and Lafayette counties


1.0 600,000



1.6

500,000

1.4



1.2 1 r \400,000





ioY ~300,000 u









0..4

8 8 100,000

0.2









Figure 3-16. Median K concentration for the Suwannee River at Branford and K fertilizer sale for Suwannee and Lafayette counties.












Mean Total Phosphorus Concentration (mg/L)

O~ctfober 2005 to September 2006


5 to 10


11to 5
0 5tol1


01 to 05

TP (mg/L)
0 05 to 0 1 is a measure of the
amount of total
phosphorus in the ground water.
O 01 to 0 05


0 to 0 01


SConfined Flonldan


Figure 3-17. Mean upper Floridan aquifer TP concentration contour map for water year 2006.












Mean Nitrate-Nitrogen Concentration (mg/L)

O~ctober 200 to September 2006


O 2 0to4 0


1 0to 20

Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


0 to 0.05



/VConfined Flondan


Figure 3-18. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2006.











IMean Potassiumn Concentration (mg/L) ~J


SOctober 2005 to Se'~~Optember 2006


Mean upper Floridan aquifer K concentration contour map for water year 2006.


SNote
This map represents a enrlzation
of groundwater quality


K (mglL
0 1S 'S sa me;
amount
0 125 potassi


-0.05
-0.025


/ Confined Flordan


Figure 3-19.


































1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005
Water Year


Figure 3-20. TP loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005.


- -


- -


- -


- -


- -


40


35


30


S25
o
a
S20


a- 15


10


5


I

































































2004


1991


1992


1999


1995


2003


1993


1994


1996


2002


Figure 3-21. NO3-N loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005.


2000 2001


-r


-r


-r


-r


-r


7-






6-






5-




o
o
4-
o
a





2-



1-




c1990


2005


1997 1998

Water Year












STP Load -5 Rainfall


25 200



180



20 --i 160



140



Y~15 -- 12 E ,
o a

o
a
100 1
O

-~~ 10 80



< t 60



5 -- III 40



20




1998 1999 2000 2001 2002 2003 2004 2005


Figure 3-22. Annual TP loads and rainfall by water year for the Suwannee River.














200


180


160


140


120



100


80


60


40


20


6


o


0-4

o



< a


I


-
0 !-


+ 0


1998


1999 2000 2001 2002 2003 2004
Water Year


2005


Figure 3-23. Annual NO3-N loads and rainfall by water year for the Suwannee River.


SNox-N Load + Rainfall




















































A nnual e- T odotal Phosphorus Load I



/\/County Boundaries
SSuwannee Reach 1
O Suwannee Reach 2
O Suwannee Reach 3
CZ Santa Fe Reach 1
II Santa Fe Reach 2
SSuwannee Reach 4
Ij Suwannee Reaches 5& 6
SAlapaha river Watershed
M Withlacoochee river Watershed


Figure 3-24. Suwannee River Basin loading by watershed/reach for water year 2005.









CHAPTER 4
NITROGEN LOADING FROM GROUD WATER TO SELECTED REACHES OF THE
SUWANNEE AND SANTA FE RIVERS

Introduction

Ground water can either contribute positively to river flow through riverbed inflows and

spring discharge or negatively by river water seepage through the riverbed and reverse spring

discharge, depending on hydrologic conditions (Winter et al., 1998; Dingman, 2002). Hornsby

et al. (2004) demonstrated that the Suwannee River has reaches that receive ground water from

the upper Floridan aquifer and reaches which lose surface flow to the aquifer. Water loss from

the Suwannee River to the upper Floridan aquifer occurs when the stage of the river is higher

than the adjacent groundwater levels. This results in a cessation of flow from the springs along

the Suwannee River and reverses flow or estevelle, which results in focus recharge. The river

has incised into the top of the upper Floridan aquifer in the lower reaches of the Suwannee River.

Under base flow conditions, the Suwannee River stage is lower than the adjacent groundwater

levels in the upper Florida aquifer. This results in the ground water discharging through the

springs and seeps along the riverbed. The numerous springs and the amount of ground water that

discharges to the river indicate the interaction of the Suwannee River and the upper Floridan

aquifer (Hull et al., 1981).

The Middle Suwannee River Basin (MSRB) has karstic geology and the region is

internally drained. The internal drainage results in karst features, such as sinkholes that capture

the surface water from streams. The result is that surface waters, such as streams, do not flow

for long distances and are directly connected to the underlying upper Floridan aquifer. In some

cases, surfacewater features, such as Rose Creek in the Lower Santa Fe River Basin (LSFRB),









that are captured by sinkholes have been shown to be directly connected by conduits in the upper

Floridan aquifer to springs within the surfacewater basin (FDEP, 2000).

The Lower Suwannee and the Lower Santa Fe Rivers and their associated springs flows

depend on the groundwater levels in the contiguous upper Floridan aquifer (Grubbs and

Crandall, 2007). This interaction of the ground water and surface water results in the ground

water having dramatic impacts of the surfacewater quality of the rivers (Hull et al., 1981).

Pittman et al. (1997) conducted a study of a 33 mile (53 km) reach of the MSRB

(Dowling Park to Branford), that was divided into an upstream and downstream segment, to

assess the impact of groundwater discharge on the quantity and quality of water in the Suwannee

River. The study was conducted under base flow conditions. The objective of the study was to

determine whether the measured springs and other groundwater inflows and NO3-N

contributions were similar in each segment. They found that 11 % of the 3,700 kg N d-l of NO3-

N load in the study area was from the upstream segment and 89 % was from the downstream

segment. Furthermore, in the upstream segment, the four springs accounted for 92 % of the 350

cubic feet per second (cfs) [9,911 L s^l] flow pickup with the remaining 8 % consisting of

riverbed seepage; while, the downstream segment the springs accounted for 41 % of the 600 ofs

(16,990 L s^l) flow pickup and the remaining 59 % flow pickup was associated with riverbed

seepage.

The Suwannee River Water Management District (SRWMD) monitoring stations on the

Suwannee and Santa Fe rivers are shown in Figures 4-1 and 4-2, respectively. Data from the

monitoring network for the period 1989 to 2006 has shown an increasing trend for NO3-N

concentrations in the Suwannee and Santa Fe rivers as they traverse from their headwaters to









downstream. The increase in the NO3-N concentrations is associated with regions of the river

that receive ground water inputs.

The largest increase in NO3-N concentration in the SRB occurred between Dowling Park

and Branford (MSRB), a 60.8 kilometer (km) segment of SRB (Figure 4-3). The largest increase

in NO3-N concentration occurred in the Santa Fe River between US 441 and State Road 47

(Figure 4-4).

To date, no study has identified the exact area within the MSRB or the LSFRB where the

NO3-N load is entering the river system from the groundwater system. This study will expand

on the work of Pittman at al. (1997) and the SRWMD monitoring program by sampling the

Suwannee River in the MSRB on 1.6 km segments from Dowling Park to Branford. Also, this

study will be expanded to include the LSFRB (River Rise to the confluence with the Suwannee

River). The initial sampling will identify the river segment where NO3-N concentrations

currently increase in the rivers. The sampling increment lengths will be decreased and in-stream

discharge measurements of the river and discharge measurement for the springs will be

conducted to define the segment or segments with the greatest increase in NO3-N load. The

results of this study will identify the segments) and springs within MSRB and LSFRB

associated with groundwater inputs that are contributing to the increase in NO3-N loads in the

surface water and qualitatively relate adj acent landuse to the segments) with the greatest

increase in NO3-N loads.

Materials and Methods

Water quality sampling and discharge measurements were performed over an

approximately 61 km stretch of the Middle Suwannee River from Dowling Park, Florida,

downstream to Branford, Florida on July 21 and 22, 2000; and an approximately 42 km stretch of









the Lower Santa Fe River, from its re-emergence in River Rise State Park to its confluence with

the Suwannee River on June 7, 2000. Measurements were made on subsequent sampling dates

on selected segments of the above reaches as indicated in Table 4-1. Sampling locations were

chosen at intervals not exceeding 2.2 km and at all inflow points (i.e., springs).

The distance between locations was determined using a global positioning system (GPS)

where the path between points was nearly straight. Where the curvature of the river made

straight-line distances difficult to determine, a combination of a USGS topographic map for the

area, a 1:24,000 scale mileage template, and site recognition of mapped features were used. GPS

points were collected in 1983 North American Datum (NAD83) and differentially corrected to

provide a 3-5 meter (m) accuracy range to ensure sampling locations.

Vertical-axis meter discharge measurements (i.e., Price AA and Pygmy current meters)

were conducted in springs, such that, no partial section contained more than five percent of the

flow from the spring; consequently, approximately 25 partial sections were used at each

measurement (Buchanan and Somers, 1969). The two-point method (velocity measurements at

the 0.2 and 0.8 tenths depths) was used primarily for velocity measurement in a partial section.

The six-tenths method, is where the velocity meter is placed six-tenths of the total depth from the

surface of the water being measured, was employed as necessary and appropriate to instrument

capabilities, velocity profile characteristics, and the partial section depth. Data obtained from the

spring discharge measurements included the spring name, date of measurement, beginning and

ending times of measurement, beginning and ending reference water level measurements, width

of measurement, total cross-sectional area, mean velocity, and discharge. Discharge

measurements were conducted on the river using Teledyne Workhorse Rio Grande Acoustic

Doppler Current Profiler (ADCP) and were performed by the FDEP. Discharge measurements









were performed using the ADCP following the guidelines established in ADCP manuals by RD

Instruments. The discharge measurements with the ADCP included five cross-sectional traverses

of the stream. The discharge from each traverses were sum and a mean was calculated to

determine the discharge. For springs discharging less than one efs (28.3 L s^)~, field estimates

were made.

Water chemistry samples were collected in mid channel and at a depth of 0.5 m while

spring samples were collected as near as possible to the spring vent. Samples were preserved in

accordance with FDEP Standard Operating Procedures (011/01) and analyzed using EPA

methods (EPA, 1983).

Results and Discussion

Middle Suwannee River Basin (MSRB)

The MSRB was sampled from Dowling Park to Branford at 1.6 km intervals for NO3-N

on July 21 and 22, 2000 (Figure 4-5). The NO3-N concentration increased from 0.32 mg N L^1 at

Dowling Park to 0.52 mg N L^1 at Branford (Figure 4-6). The highest rate of increase in NO3-N

concentration in the river was observed over a 12.8-km stretch sampling points 19 to 28 (circled

area on Figure 4-6). The NO3-N concentrations in the springs in the MSRB for July 21 and 22,

2000, ranged from 0.02 to 13.8 mg N L^1 (Table 4-2). The flow increased from 1,030 ofs (29, 166

L s^l) at Dowling Park to 1,480 ofs (41,908 L s^l) at Branford. The springs accounted for 277 ofs

(7,844 L s^l) of the flow increase or 62 % at low flow conditions (Table 4-2). Since, there are no

surfacewater inflow points in this stretch of the river; the increase not accounted for by measured

springs is presumably due to groundwater inputs through the riverbed. The NO3-N load

increased by 1,080 kg N d-l from Dowling Park to Branford and the springs in the reach

accounted for approximately 1,080 kg N d-l or 100 % of the load increase (Table 4-2). This









indicates that the NO3-N concentration in the adj acent upper Floridan aquifer is greater than the

NO3-N concentration in the Suwannee River. Based on the loading increase, the concentration

of NO3-N in the upper Floridan aquifer is 2 to 30O times that of the concentration observed in the

Suwannee River.

Pittman et al. (1997) study consisted of three river sites which had discharge gages

(Suwannee River near Dowling Park, FL station number 301259083143700, Suwannee River at

Luraville, FL station number 02320000, and Suwannee River at Branford, FL station number

02320500) and three springs in the upstream segment and eight (8) springs in the downstream

segment. The study area (Dowling Park to Branford) was divided into an upstream segment

(Dowling Park to Luraville) and a downstream segment (Luraville to Branford). The study

concluded that 11 % of the 3,700 kg N d-l of NO3-N load in the study area was from the

upstream segment and 89 % was from the downstream segment. Furthermore, the study found

that in the upstream segment the four springs accounted for 92 % of the 3 50 ofs (9,911 L s^l)

flow pickup with the remaining eight percent consisting of riverbed seepage; while, the

downstream segment the springs accounted for 41 % of the 600 ofs (16,990 L s^l) flow pickup

and the remaining 59 % flow pickup was associated with riverbed seepage. The findings of the

July 2000 sampling confirmed the findings of Pittman et al. (1997) that the maj or of flow and

NO3-N increase occurred in the MSRB below Luraville gage. This indicates that there is a

consistent supply of ground water and NO3-N entering the MSRB below Luraville gage.

Additional samplings were conducted from Luraville to Branford on October 24, 2000

and September 19, 2006. This river segment covers the area where the greatest increases in

NO3-N were observed in the July 2000 sampling event (Figure 4-5). In the MSRB on October

24, 2000, the highest rate of increase in NO3-N concentration in the river was observed over a









4.8 km stretch (Figure 4-7). The September 19, 2006 sampling yielded similar results (Figure 4-

8). Since there are no surfacewater inflow points in this stretch of the river, the increase not

accounted by measured springs is presumably due to groundwater inputs through the riverbed.

The NO3-N concentration increased from 0.61 mg N L^1 at Luraville to 1.07 mg N L^1 at

Branford on October 24, 2000 and 0.70 mg N L^1 at Luraville to 1.10 mg N L^1 at Branford on

September 19, 2006 (Figure 4-8). The increase in riverine NO3-N concentration is associated

with the increase in groundwater discharge. Figure 4-9 shows an inverse relationship of river

discharge and NO3-N concentration in the Suwannee River at Branford. Thus, as the flow

decreases the NO3-N concentration increases. Also, as ground water enters the river system, the

specific conductance of the river increases. Typically, surface water has specific conductance of

less than 100 Clohms cm- ; while ground water has specific conductance generally greater than

250 Clohms cm- As discharge increases the specific conductance in the Suwannee River at

Branford decreases (Figure 4-10). This is a result of the stage of the river overcoming the

groundwater head. The hydraulic gradient in the upper Floridan aquifer is toward the Suwannee

River during low flow conditions and away from the river during high flow conditions (Hirten,

1996). Hirten (1996) identified that the impacts of the high river stage on the potentiometric

surface during high flow conditions extended outward from the river for approximately 3 km.

As the specific conductance in the Suwannee River at Branford increases so does the NO3-N

concentration in the river (Figure 4-11). The increase in groundwater discharge is a result of the

river stage beginning lower in 2006 than 2000; thus, allowing more groundwater into the river.

Since discharge was measured in the river at six locations (as indicated by the red lines in

Figure 4-12), it is possible to calculate loading for each segment (Table 4-3). The load change

for each segment was calculated by subtracting the upstream segment load from the load for the









given segment. The highest NO3-N load change per m of river for both the 2000 and 2006

sampling events were observed in segment 3 (Figure 4-13).

The major landuse adjacent to segment 3 is row crops on the Suwannee County side. On

the Lafayette County side of segment 3, animal husbandry operations and improved pasture are

the major landuses. The recommended University of Florida, Institute of Foods and Agricultural

Science (IFAS) recommend N fertilizer rates for typical crops, corn, potatoes and watermelon,

grown in the MSRB are 200 lb acre-l (222 kg hectare- ), 200 lb acre-l ( 222 kg hectare- ) and 150

lb acre-l (168 kg hectare- ), respectively (Hochmuth and Hanlon, 2000). For hay, the IFAS

recommendation for N is 80 lb acre-l (89 kg hectare- ) in the spring and 80 lb acre-l (89 kg

hectare- ) following each cutting except for the final fall cutting (Mylavarapu et al., 2007).

Generally, hay fields are cut four times per year (M. Randall, 2004, Personal Communication).

Thus, hay fields may receive 320 lb acre-l (359 kg hectare- ) based on IFAS recommended rates.

While, IFAS N fertilizer recommendation for improved pasture range between 50 lb acre-l (56

kg N hectare- ) and up to 160 lb acre-l (179 kg N hectare- ) [Mylavarapu et al., 2007]. The

landuses are occurring primarily on Alpin and Penney soils. Both soils are Entisols. The Alpin

series consists of very deep, excessively drained, moderately rapidly permeable soils on uplands

and river terraces of the Coastal Plain. The soils formed in thick beds of sandy eolian or marine

deposits. (Soil Survey Staff, 2007). The Penney series consists of very deep, excessively

drained, rapidly permeable soils on uplands. The soils formed in thick beds of sandy eolian or

marine deposits (Soil Survey Staff, 2007). These landuse uses are occurring over the unconfined

Floridan aquifer on Entisols (Alpin and Penney) which have high leaching potential.

The contributions of the springs for October 2000 and September 2006 are given in Table

4-2. Also, Table 4-2 presents the discharge, NO3-N loading and percent of NO3-N load increase









in the segment that the spring discharges. The NO3-N concentration of the springs ranged from

0.09 to 18.6 mg N L^1 in 2000 and 0.33 to 15.0 mg N L^1 in 2006. The two springs (SUW718971

and SUW725971) with the highest NO3-N concentrations discharge in segment 3. These two

third magnitude springs were sampled by Katz et al. (1999 and 2001) and yielded NO3-N

concentrations of 29 and 3 8 mg N L^1 for SUW718971 and SUW725971, respectively. Katz et

al. (1999) used isotopic ratios of 14N and 15N to determine the source of the NO3-N in the spring

water from springs SUW718971 and SUW725971. Katz et al. (1999) findings showed that the

NO3-N was from an inorganic source. Also, Katz et al. (1999) used chlorofluorocarbons (CFC)

to date the spring water from springs SUW718971 and SUW725971. The findings of the age

dating were that the youngest water had a mean age of less than nine years reported by Katz et al.

(1999). This corresponds with the observed time lag in Chapter 3 of fertilizer sales data and

riverine NO3-N concentration of one to six years. Also, the Florida Department of

Environmental Protection (FDEP) on an every other week schedule from March 15, 2000 to

January 10, 2001 sampled these two springs (SUW718971 and SUW725971) for NO3-N and K

(T. Greenhalgh, 2005, Personal Communication). The springs SUW718971 and SUW725971

show a clear linear relationship between the concentration of NO3-N and K, which indicates an

inorganic (fertilizer) source as shown in Appendix C, Figures C-1 and C-2, respectively. There

is a major agricultural operation (row crop) within 1.6 km of these springs. Based on the

findings that inorganic fertilizer is correlated to the increasing NO3-N trend in the Suwannee

River at Branford (Chapter 3), the activities that occur adj acent to segment 3 (Figure 4-12) of the

MSRB should be investigated.









Lower Santa Fe River Basin (LSFRB)

The LSFRB begins at River Rise, which is where the Santa Fe River re-emerges from the

upper Floridan aquifer after traveling approximately 3.2 km underground from River Sink.

River Sink is located in O'Leno State Park and is a karst feature, which captures the entire Santa

Fe River during all but extremely high flow conditions. The LSFRB has 58 identified spring and

six siphons (Hornsby and Ceryak, 1998). Thus, the LSFRB is highly connected to the upper

Floridan aquifer. This connection with the upper Floridan aquifer has impacts on the water

quality and quantity of the LSFRB.

Unlike the springs in the MSRB, the springs in LSFRB do not typically reverse flow or

estevelle. Due to the morphology of the river system, the surface stage cannot overcome the

head in the upper Floridan aquifer. Also, should the river overcome the groundwater head at a

spring vent, the groundwater pressure is relieved by discharging from karst features within the

floodplain. Thus, the observed decrease in riverine NO3-N concentrations in high flow

conditions is related to dilution of ground water by surface water not by excluding the ground

water from the surface water, as is the case for the MSRB.

On June 7, 2000, the LSFRB was sampled on 1.6 km intervals for NO3-N (Figure 4-14).

There was little discharge at River Rise due to the drought conditions and limited flow in the

upper Santa Fe River. This created a base flow condition that was virtually all ground water with

little surface water inputs from the upper Santa Fe River. This allowed for the sampling of the

LSFRB to determine the impacts of groundwater discharge on the NO3-N concentration in the

river. The highest rate of increase in NO3-N concentration in the LSFRB was observed over a

4.8 km stretch (Figure 4-15). The NO3-N concentration increased from 0.09 mg N L at the

Santa Fe Rise to 0.88 mg N L^1 near Fort White, with the concentration decreasing to the









confluence with the Suwannee River. Ground water inputs accounted for 100 % of the flow

increase. The NO3-N concentrations in the springs in the LSFRB for June 7, 2000, ranged from

0.11 to 4.8 mg N L^1

Based on the sampling results from June 2000 sampling event, the sampling intervals

were reduced and the sampling reach of the LSFRB was reduced to the Santa Fe River above

Rum Island to the USGS gage near Fort White and the sampling was conducted on September 5,

2001 and October 10, 2006. In the LSFRB, the highest rate of increase in NO3-N concentration

in the river was observed over a 0.3 km stretch (Figure 4-16) for September 5, 2001 and October

10, 2006. The NO3-N concentration increased from 0.28 mg N L above Rum Island to 0.79 mg

N L^1 near Fort White on September 5, 2001 and 0.26 mg N L above Rum Island to 0.82 mg N

L^ near Fort White on October 10, 2006. As the case for the MSRB, the flow in the Santa Fe

River was lower in 2006 than 2000. This results in less dilution of ground water by surface

water in 2006 than 2000. Also, the percentage of flow increase in the river from the springs was

greater in 2006 than 2000. Therefore, the riverine NO3-N concentration increased due to less

quantity of the receiving surface water to dilute the NO3-N concentration in the groundwater that

was discharge into the surfacewater system.

Since discharge was measured in the river at three transects (as indicated by the red lines

in Figure 4-17) on September 5, 2001 and at seven transects on October 10, 2006 (as indicated

by the red lines in Figure 4-18), it is possible to calculate loading for each segment (Tables 4-4

and 4-5). The set of transects used in 2006 incorporated the three transects for 2001 by adding

additional transects between the 2001 transects to better define the NO3-N inputs. A comparison

of 2001 to 2006 loading increase per m of river is shown in Table 4-4 and Figure 4-19. The

greatest increase in NO3-N loads change per m of river was observed in segment 1 for 2001 and









2006 when the sampling reach was divided into three segments. The refined seven segments for

2006 segments indicated that segment 4 as the highest NO3-N load change per m of river for

2006 sampling events (Table 4-5 and Figure 4-20). The discharge contribution of the springs for

September 5, 2001 and October 10, 2006 are given in Table 4-6. The NO3-N concentration of

the springs ranged from 0.55 to 1.59 mg N L^1 in 2001 (Table 4-6) and 0.27 to 1.9 mg N L^1 in

2006 (Table 4-6). Segment 1 (for the 3 segment sampling) and segment 4 (for the 7 segment

sampling) had the highest increase in NO3-N loads and contain the lotus of springs known as the

Devil's complex. Based on the 2006 sampling, the NO3-N load is associated with the Devil's

complex that consists of two Birst magnitude springs (Devil's Ear and July).

The landuses adj acent to segments 1 in 2001 and 4 in 2006 are improved pasture,

recreational park, and low density residential. These landuse uses are occurring over the

unconfined Floridan aquifer on Entisols (Lakeland and Penney) with high leaching potential.

Sabasan (2004) identified NO3-N concentrations in various landuse on Entisols, Ultisols, and

Spodosols in the Santa Fe River Watershed. For landuse improved pasture, the NO3-N

concentrations for Entisols, Ultisols, and Spodosols were 0.51, 1.80 and 1.65 Clg N g- of soil,

respectively. The Entisols which are in landuse improve pasture have lower soil NO3-N due to

the leaching of the NO3-N. And where these Entisols are over the unconfined Floridan aquifer

there is potential for leaching of NO3-N into the upper Floridan aquifer.

Katz et al. (1999) sampled the July and Ginnie Springs for 15N and 14N. The result of

Katz's study indicated that the NO3-N was from an inorganic source (i.e., fertilizer). As with the

MSRB springs, the springs in the LSFRB in the segment where the NO3-N load in the river

increases are discharging NO3-N whose source is inorganic fertilizer.









Summary and Conclusions

The regions of the Middle Suwannee and Lower Santa Fe rivers where the greatest

increase in NO3-N concentrations occur are relatively small segments of studied river reach. The

greatest increase in NO3-N load occurs in segment 3 of the MSRB, which is 3,408 m of river

channel, and Segment 4 of the LSFRB, which is 425 m of river channel. The NO3-N is moving

into the surfacewater system via ground water through springs and seeps in the riverbed during

base flow conditions. The soils adj acent to these segments are Entisols that have high leaching

potential. Furthermore, the upper Floridan aquifer is unconfined in these regions. The coupling

of the upper Floridan aquifer being unconfined and overlain by soil with high leaching potential

with landuses that are adding NO3-N via fertilizer creates the potential for contamination of the

upper Floridan aquifer and ultimately the Suwannee and Santa Fe river which receive base flow

from the upper Floridan aquifer by the NO3-N.

Two springs sampled in segment 3 of the MSRB, where the highest increase in NO3-N

loading occurred, showed a linear relationship with K and NO3-N. Also, these two springs were

sampled by the USGS for NO3-N sourcing and age dating. The result from the USGS sampling

showed the NO3-N source as inorganic and the age of the water was less than nine years (Katz et

al., 1999) which is similar to the results observed in the lag time between fertilizer sales and

riverine NO3-N concentrations in the Suwannee River at Branford in Chapter 3. Furthermore,

for the Suwannee River at Branford, this confirms that fertilizer is the maj or component of the

observed increasing NO3-N trend in the Suwannee River at Branford (see Chapter 3). Segment 4

of the LSFRB springs was also sampled by Katz et al. (1999). The results indicated that the

maj or springs in segment 4 were discharging NO3-N that was primarily from inorganic fertilizer.

The MSRB and LSFRB showed increased NO3-N concentrations from 2000-2001 to 2006










sampling events. This indicates that the NO3-N loading from the ground water to the surface

water is increasing for the studied areas of the Suwannee and Santa Fe rivers and the NO3-N is

primarily from inorganic fertilizer. Thus, understanding of fertilizer use and contribution areas

to the upper Floridan aquifer, which supplies the water to segment 3 of the MSRB and segment 4

of the LSFRB, is needed to focus management activities.












Table 4-1. Suwannee River and Santa Fe River segments used in this study along with sampling
dates and other pertinent information.
River Segment Sampling Date Comments
Middle Suwannee River Basin


Dowling Park to Branford
See Figure 4-5 for
locations.

Luraville to Branford
See Figure 4-12 for
locations.











Luraville to Branford


July 21-22, 2000 Wat
mea
inte:
spri:
October 24, 2000 Wat
mea
segr
sho~
Sam
inte:
to 0
was
sam
segr
incr
redux
September 19, 2006 Rep
sam
Lower Santa Fe River Basin


ter samples and discharge
Isurements taken at 1.6 km
rvals and at all identified
ngs of 61 km river segment.
ter samples and discharge
Isurements taken at the
ment (34 km) of the river
wiing high NO3-N input.
Iples were taken at irregular
rvals ranging from 2 km down
.7 km. The sampling interval
based on the previous
pling event (i.e., in the
ments with the greatest NO3-N
ease the interval was
Iced).
leat of the October 24, 2000
pling.


River Rise State Park to July 7, 2000
confluence with the
Suwannee River.
See Figure 4-14 for
locations.
Above Rum Island spring to September 5, 2001
USGS discharge gage near
Fort White. See Figure 4-
17 for locations.


Water samples and discharge
measurements taken at 1.6 km
intervals of 42 km river segment
and at all identified springs.

Water samples taken at 0.3 km
intervals of 5.4 km river segment
and at all identified springs.
Discharge measurements were
taken at 3 transects and all
flowing springs.
Water samples taken at 0.3 km
intervals of 5.4 km river segment
and at all identified springs.
Discharge measurements were
taken at 7 transects and all
flowing springs.


River Rise State Park to
confluence with the
Suwannee River. See
Figure 4-18 for locations.


October 10, 2006










Table 4-2. Middle Suwannee River Basin spring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N load and
contribution of the total NO3-N load increase in the study reach.


NO3-N
(mg L1)
2000


NO3-N Load


NO3-N Load change


Discharge[cfs/( L s^l))


(kg d- )
2006 2000


River
Segment


(oA)
2000

2.43
3.84
6.02

0.11
0.43
0.98
0.11

6.19

7.92
4.42

7.07

1.74
12.21
0.00

3.19
3.80
<0.01
0.88


Spring


2000


2006


2006


2006

4.09
4.69
7.21

0.28
0.29
1.96
0.27

2.27

4.87
4.18

8.04

1.36
13.39
0.02

0.53
4.26
Dry
0.25


LAF924971
Telford
Running

LAF919972
Bathtub
Convict
SUW919971
Suwannee
Blue

SUW718971
SUW725971


15(425)
38(1,076)
49(1,388)

1.5(43)
6(170)
2.3(65)
4(113)

18(510)


12(340)
25(708)
45(1,274)


3.05
1.93
2.32

1.36
1.34
7.9
0.52


111
175
275


2(57)
3(85)
3(85)
7(198)


2.00
1.4
9.4
0.56

3.6


4.95
19.5
44.5
5.05

282


9.71
10.2
68.4
9.51

79.1


3.6(102) 6.5


8(226)
5(142)

62.4(1,767)

15(425)
111.9(3,169)
0.5(14)

10.9(309)
63.7(1,804)
0.5(14)
15(425)


5(226)
4(142)

55(1,557)

15(425)
87.4(2,475)
1(28)

1.6(45)
51(1,444)
0(0)
8(226)


18.6
16.6


169
145

280

47.3
467
0.80

18.5
149
Dry
8.54


Mearson


2.13 2.1 323


LAF718972
Troy
LAF1024001

Ruth
Little River
LAF93971
LAF718971


2.18
2.05
0.12

5.5
1.12
0.09
1.1


1.3
2.2
0.33

4.7
1.2
Dry
0.44


79.4
557
0.15

145
173
0.11
40.0











Table 4-3. Middle Suwannee River Basin NO3-N change profie 2000 and 2006.
NO3-N Load change NO3-N Load change per meter of river
MSRB River Segment (kg d- ) (kg d-l m l)
Segment (m) 2000 2006 2000 2006
1 6,361 284 1,043 0.045 0.164
2 6,220 903 494 0.145 0.079
3 3,408 1,663 937 0.488 0.275
4 5,152 523 98 0.101 0.019
5 5,477 995 403 0.182 0.074
6 7,502 192 510 0.026 0.068


Table 4-4. Lower Santa Fe River Basin NO3-N change profie 2001 and 2006.
LSFR River Segment NO3-N Load change (kg d- ) NO3-N Load change per meter of river
Segment (m) 2001 2006 2001 2006
S1 2 171 894.6 1 171.0 0.412 0.539
2 2,127 309.2 108.2 0.145 0.051
3 813.8 -725.9 22.0 -0.892 0.027


Table 4-5.
LSFR
Segment
1
2
3
4
5
6
7


Lower Santa Fe River Basin refined NO3-N change
River Segment NO3-N Load change (kg d')
(m) 2006
914.5 -20.5
351.2 176.9
481.0 -20.2
424.7 1,034.8
1,141 188.7
985.9 -80.5
813.8 22.0


profie for 2006.
NO3-N Load change per meter of river
2006
-0.022
0.504
-0.042
2.437
0.165
-0.082
0.027










Table 4-6. Lower Santa Fe River Basin spring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N Load and
contribution of the total NO3-N load increase in the study reach.
River Discharge [cfs/( L s^)]l NO3-N (mg L^1) NO3-N Load (kg d- ) % NO3-N Load change
Segment Sprinns 2001 2006 2001 2006 2001 2006 2001 2006


Rum Island
Blue

July
Devil's Ear


30(850)
50(1,416)


14.3(405)
14.1(399)


1.06 1.5
1.59 1.9

1.28 1.6
1.37 ns


77.2
193


52.2
64.9

271.8
ns

42.7
10.1
7.57
1.61


16.2
40.6

49.0
70.0

25.3
6.59
2.93
4.21


4.01
4.99

20.89
ns

3.28
0.77
0.58
0.12


75(2,124) 70(1,982)
100(2,831) ns


Gmnnie
Dogwood
Sawdust
Twin
ns = no sample


40(1,133)
15(425)
7(198)
15(425)


13.5(382)
5.2(146)
4(113)
2.5(71)


1.24
0.86
0.82
0.55


1.3
0.79
0.78
0.27


120
31.3
13.9
20.0










Table 4-7. Discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the study reach for
Lower Santa Fe River Basin springs in refined segments (October 10, 2006).
River
Segments Springs Discharge [cfs/ L s^)]l NO3-N (mg L^1) NO3-N Load (kg d- ) % NO3-N Load change


Rum Island
Blue

No springs

No springs

July

Gmnnie
Dogwood
Sawdust
Twin

No springs

No springs


14.3(405)
14.1(399)


52.2
64.9


4.01
4.99


70(1,982)

13.5(382)
5.2(147)
4(113)
2.5(71)


1.6

1.3
0.79
0.78
0.27


271.8

42.7
10.0
7.57
1.61


20.9

3.28
0.77
0.58
0.12



























h~L~ ~Y
T


P~ 54:~;?~


~ ~2-~


I
h'~15 ~ea,.s


~d9~ iikP~~P2?

--s~~.: ;L!


Figure 4-1. Suwannee River Water Management District stations on the Suwannee River with aerial photography.














































Figure 4-2. Suwannee River Water Management District stations on the Santa Fe River with aerial photography.





SNOx-N H Total P


Georgia

S.R. at SR6


White Springs


Suw. Springs


S.R. above Withla.


Ellaville


Dowling Park


Luraville


Branford


Rock Bluff


Wilcox


S.R. at Gopher R.

Gulf of Mexico


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Concentration (mg/L)


Figure 4-3. Mean NO3-N and TP for Suwannee River Water Management District Suwannee River stations (1989 to 2006).













I Total P NOx-N


Brooker





Worhtington Springs




O'leno





SFR at US 441





SFR at SR 47





SFR at US 129



Suwannee River


0 0.1 0.2 0.3 0.4 0.5


Concentration (mg/L)

Figure 4-4. Mean NO3-N and TP for Suwannee River Water Management District Santa Fe River stations (1989 to 2006).





.egend


I Note idloll men stillons inclic 110 mellest slicisise III ING -NI


Figure 4-5. Middle Suwannee River Basin sampling points (July 21, 2000) for NO3-N profile.


4


t























0.5


Dowling Park

0.4 Branford





0.3





0.2



Luraville

0.1






1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37

Note: circle represents the vellow river stations on Figure 4-5 Sampling Point


Figure 4-6. Middle Suwannee River Basin (Dowling Park to Branford) NO3-N profile on July 21, 2000.














1.10



1.05


1.00Bran od



0.00



0.85


-0.


0.80




0.5Lu raville











0.60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Note: Circle represents segment 3 in Figures 4-8 and 4-12. Sampling Points


Figure 4-7. NO3-N profile of the Middle Suwannee River Basin (October 2000).
















-*20000 -2006




























Segment 1 2 3 4 5 6


1.1







0.9



0.8



0.7



0.6



0.5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Note: Segments are disolaved on Figure 4-12 Sampling Points


Figure 4-8. NO3-N profiles of Middle Suwannee River Basin (October 2000 and September 2006).









1.5


1.2


... 1


0.8-










05,000 10,000 15,030 20,000 25,000 30,000 35,000 40,000

D i schtarge ( cfs)

Figure 4-9. The relationship of discharge and NO3-N concentration for the Suwannee River at Branford (1989 to 2006).





\~


45000U

40000
35000
30000

25000
20000
15000

10000
5000
0


100


300


400


5300


600


200


Specific Clonductance (piohms/cm)


Figure 4-10. The relationship of specific conductance and discharge for the Suwannee River at Branford (1989 to 2006).





-f

''+~~


1.4





0.8



0.4


0.2


100


200


300


400


500


6500


Specific Co~nductance (plohms/cm)


Figure 4-11. The relationship of specific conductance and NO3-N concentration for the Suwannee River at Branford (1989 to 2006).












Te
L
F


11


.GgenCI


River Stallon

SSorina Slaliol


Figure 4-12. Middle Suwannee River Basin sampling points and discharge cross-sections [segments] (October 2000 and September
2006).


~:~lh "
l.d i._~


~S~lrL


_r c~
rr


~.g~i"





5 2000 5 2006


'


*


*


*


0.6


0.5





0.4





0.3





0.2





0.1


I


I


I


I


I


I


1 2


Segment


Figure 4-13. Comparison of segment NO3-N load change per m
September 2006).


of river in the Middle Suwannee River Basin (October 2000 and
































I

Q'


'I


mmmw m m n' C -ms -- Mak m


Figure 4-14. Lower Santa Fe River Basin sampling points (June 7, 2000) for NO3-N profile.














Near Fort White

0.0 ~



0.8



0.7



0.6



0.5

O
0.4


Near High Springs
0.3



0.2



0.1




1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29

Note: Circle represents the vellow river stations on Figure 4-14 SapigPnt


Figure 4-15. NO3-N profile of the Lower Santa Fe River Basin on June 7, 2000.






















0.7



0.6



0.5











0.2
2001 Segment 1 1 2 1 13


0.1
2006 Segment 12 3 14 15 6 117



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

Note: Segments are disolaved on Figures 4-17 and 4-18. Segment


Figure 4-16. NO3-N profile of the Lower Santa Fe River Basin (September 2001 and October 2006).















































Figure 4-17. Lower Santa Fe River Basin segments for September 2001 NO3-N profile.















































Figure 4-18. Refined Lower Santa Fe River Basin segments for October 2006 NO3-N profile.


~C~CI



E













0.8
S2001 2006


=


*


Segment


Figure 4-19. Comparison of segment NO3-N load change per m of river in the Lower Santa Fe River Basin (September 2001 to
October 2006).


01


I


-0.2



-0.4



-0.6



-0.8



-1





1


I I


Segment


Figure 4-20. Refined segments NO3-N load change per m of river in the Lower Santa Fe River Basin in October 2006.


2




1.5




1




0.5


01 .


3









CHAPTER 5
GROUNDWATER DOMAIN DELINEATION AND LANDUSE INFLUENCES ON
GROUNDWATER QUALITY

Introduction

A Chinese proverb states "When you drink the water, remember the spring". This

statement is a good way to think about the influences of human activities on the land surface and

the ultimate impacts to the ground water beneath the landuse. The springs are the sentinels of the

Floridan aquifer's overall status with respect to water quality. The geologic conditions in the

Suwannee River Water Management District (SRWMD) are karstic which means that there are

interconnections of surface and ground water. The landuse can be reflected in the ground water

of the underlying Floridan aquifer. Also, agricultural activities and other landuses have impaired

the quality of springs by contributing large quantities of nutrients to groundwater recharge in

parts of the world (Katz et al., 2001; Dietrich and Hebert, 1997; Focazio et al., 1998; Burg and

Heaton, 1998; Buzek et al., 1998).

The SRWMD operates the Water Assessment Regional Network (WARN) which has 181

wells monitored monthly for groundwater levels (Hornsby et al., 2005C). Also, the WARN

network monitors 25 1 groundwater quality stations. About half of the WARN groundwater

quality stations were randomly located and the remaining wells were placed to define regional

trends (Upchurch and Goodwin, 2000). Also, approximately every five years the SRWMD and

the United States Geological Survey (USGS) collect groundwater levels from approximately

1,000 wells to develop a potentiometric surface map of the Floridan aquifer in the SRWMD.

Groundwater domains can be approximated using potentiometric surfaces) of the aquifer

or by using computer models) to simulate the groundwater domain (Scott et al., 2004). The

approximation of a groundwater domain is determined by using potentiometric surfaces) to









delineate groundwater divides and assumes that groundwater movement is perpendicular to the

potentiometric surface isopleths (Freeze and Cherry, 1979).

Groundwater flow modeling provides a valuable tool in understanding the hydrologic

system, assessing the needs for additional data and information, and providing water managers a

means to determine effects of changing hydrologic conditions (Planert, 2007). Groundwater

computer models are mathematical representations of an aquifer and have been used to simulate

groundwater flow and solute transport (Fetter, 1988). Most computer models for groundwater

quality assumes a source of a water quality constituent and models transport rates, reactions and

flow paths within the aquifer system. These transport models use theoretical leaching and uptake

coefficients to simulate observed conditions. Thus, computer models are useful for conceptual

understanding of the groundwater system.

The computer model MODFLOW simulates an aquifer system by assuming that the

aquifer has saturated flow, Darcy's Law applies, and constant groundwater density within the

aquifer (USGS, 1997). MODFLOW has been used to characterize the regional groundwater

flow of the SRWMD (Planert, 2007; Grubbs and Crandall, 2007). Also, Davis (1996) used

MODFLOW to assist in the delineating capture zones of well fields in the Woodville Karst plain

areas of the panhandle of Florida.

Shoemaker et al. (2004) to identify areas contributing recharge to the springs in north-

central Florida used groundwater flow models. The results yielded springshed and time based

capture zones. Also, springsheds of Silver and Rainbow Springs in Marion County, Florida,

were developed using two different flow models by identified areas of groundwater that could

be expected to reach the springs in 10 and 100 years (WRA and SDII, 2005). The identified land









area associated with the groundwater was classified a Spring Protection Zone for land use

planning and management.

Other studies try to relate observed isotopic nitrogen (N) ratios in NO3-N to the source of

the NO3-N and the landuse that possibly can be associated with the observed isotopic

composition. Gormly and Spalding (1979) collected ground water samples from Buffalo, Hall and

Merrick counties in the Central Platte Region of Nebraska and compared the isotopic values of the

ground water samples to those of potential NO3-N sources. The potential sources were inorganic

fertilizer, soil organic N and animal waste with 8 "N ranges of -2.1 to +1.9 %o, +5.9 to +9.0 %o and

+10.0 to +18.0 %o, respectively. The ground water in the Central Platte Region during 1976-1977

had 183 of 256 ground water samples in excess of 10 mg N L^1 of NO3-N. The study indicated that

the primary source of NO3-N contamination in the ground water was due to fertilizers and a small

fraction of the samples indicated NO3-N contamination due to animal waste. Samples for which the

source could not be identified were assumed to be a combination of two or more sources of

contamination.

Kreitler and Browning (1983) used N isotope analyses in ground water samples from

Cretaceous Edwards aquifer in Texas, U.S.A. and Pleistocene Ironshore Formation on Grand

Cayman Island, West Indies. Both aquifers are carbonate aquifers. The 6 5N classification ranges

used were -2.0 to +1.9 %o (inorganic fertilizer), +2.0 to +8 %o (soil cultivation without fertilizer) and

+10. 1 to +22.0 %o (animal waste). The ground water samples from Cretaceous Edwards aquifer had

6 5N values that ranged from +1.9 to +10.0 %o; while, the sample from Pleistocene Ironshore

Formation had 6 "N values that ranged from +18 to 23.9 %o. Cretaceous Edwards aquifer 6 5N

values indicate fertilizer and mineralization of soil organic matter as the sources of the NO3-N in the









ground water; while, Pleistocene Ironshore Formation 61 N values indicates animal wastes as the

source of NO3-N contamination in the ground water.

Flipse and Bonner (1985) used isotopic ratios for the identification of NO3-N in the ground

water under fertilized fields. Two sites were used. Site one was a potato farm where the fertilizer

applied had an average 6 5N value of 0.2 %o and the NO3-N had an average 6 5N value of +6.2 %o.

Site two was a golf course where the fertilizer applied had an average 6 5N value of -5.9 %o and the

NO3-N had an average 6 5N value of +6.5 %o. The difference between the 6 5N of the fertilizer and

the 6 5N of the NO3-N was possibly due to the isotopic fractionation in the volatile loss of NH3

during (or after) application of ammonium fertilizer. The 6 5N values are consistent with

characteristic range determined for NO3-N resulting from agricultural operations (non-animal

waste).

Kreitler (1975) used 15N/14N ratios of groundwater NO3-N to determine the sources) of

NO3-N. 8 5N value ranges were -3 to +2 %o (inorganic fertilizer), +2 to +8 %o (unfertilized

cultivated fields) and +10 to +20 %o (animal waste). From the isotopic ratios ofNO3-, the source of

NO3-N indicates a mixed source of NO3-N (mean 61 N value +6.8 %o). Due to the age of the water

in the aquifer, the 6 5N value is representative of older landuse pattern where agriculture was widely

practiced and both inorganic fertilizer and manure were used.

Mytyk and Delfino (2004) reviewed a 50-year period of record for NO3-N concentrations

in the Ocklawaha Basin and linked changes to landuse based on isotopic composition. While

Katz et al. (2001) used isotopic composition of NO3-N and age dating techniques from collected

spring water to link landuse within the basin and estimate travel times. Isotopic studies were

able to show relative composition of the sources of N in the form of NO3-N. However, the

potential sources of N for the isotopic studies were inorganic, organic or mixed.










In hydrochemical studies, classification on the basis of water quality serves the purpose

of identification of representative clusters (hydrochemical facies) of samples that reflect the

processes generating the natural variability found in hydrochemical parameters (Guler and

Thyne, 2004). The use of hydrochemical facies was demonstrated by Back (1961), Back and

Hanshaw (1965), Morgan and Winner (1962), Seaber (1962), Jones et al. (1996), and Maddox et

al. (1992) to indicate distinct regions of ground water which contain similar composition of

cations and anions. The use of hydrochemical facies analysis depends on pattern recognition.

Methods for defining and displaying hydrochemical facies patterns range from the use of Piper

diagrams, Stiff diagrams, and star diagrams to statistical methods, such as fuzzy c-mean

clustering or factor analysis or principal component analysis (Kwansirikul et al., 2005; Guler and

Thyne, 2004; Lawrence and Upchurch, 1982). Lawrence and Upchurch (1982) used factor

analysis to delineate regions of similar groundwater quality in Northern Suwannee County. For

small data sets, graphical methods are useful to display the relative patterns among

hydrochemical facies; while, for large data sets, statistical techniques are used to filter the data

set and identify patterns.

This study will identify groundwater domains based on potentiometric surface maps from

1985, 1990, 1995, 2002, and 2005. Hydrochemical facies analysis will be used to refine the

groundwater domains determined from the potentiometric surface data. Water quality statistics

of the upper Floridan aquifer water will be determined for each groundwater domain. Then each

groundwater domain will be related to the observed groundwater domain median TP and NO3-N

concentrations to percent of the groundwater domain in specific level 2 Florida Landuse Code

(FLUC). This study will provide an examination of relationships of groundwater quality and

land uses on a groundwater domain wide analysis.









Materials and Methods

The groundwater domains for potentiometric surface maps from 1985, 1990, 1995, 2002

and 2005 were approximated by using the methods outlined by Freeze and Cherry (1979) and

Upchurch et al. (2001). Principal components analysis (PCA) of the WARN groundwater

quality monitoring well data was used to confirm and refine the groundwater domains which

were delineated from the potentiometric surfaces. The PCA used potassium (K), sodium (Na),

magnesium (Mg), calcium (Ca), chloride (Cl), sulfate (SO42-) and NO3-N to cluster samples

according to the hydrochemical facies, or geochemical fingerprints, of the groundwater domains

within the upper Floridan aquifer (Back, 1961; Lawrence and Upchurch, 1982). The PCA used

Eigen analysis that created a correlation matrix for the components. The resulting component

scores were imported into SurferC and contoured using the kriging option with a linear

interpolation and zero nugget. The resulting contours were imported into ArcGIS. In ArcGIS,

the groundwater domains from delineated potentiometric surface data were overlaid with the

component score contours to delineate the final groundwater domains.

The WARN well coverage was clipped to groundwater domains. Mean, standard

deviation, median, 25th percentile, 75th percentile, maximum, and minimum for groundwater

quality were generated for each groundwater domain. The median NO3-N and TP were

compared using a series of Kruskal-Wallis tests (Ott and Longnecker, 2001) to ensure that each

basin was statistically different at the 95% confidence level.

The 1995 landuse/landcover (SRWMD, 1997) coverage for the SRWMD was clipped to

the groundwater domains using ArcGIS. The hectares of basin in landuse/landcover at level 2

Florida landuse codes (FLUCs) were determined for each groundwater domain. The median










groundwater domain concentrations of TP and NO3-N were correlated to each of the level 2

Florida landuse codes.

Results and Discussion

The potentiometric surface maps for SRWMD for 1985, 1990, 1995, 2002 and 2005 are

presented in Appendix D, Figures D-1 through D-5. Figures 5-1 to 5-5 present the groundwater

domains based on the potentiometric surface maps for 1985, 1990, 1995, 2002 and 2005,

respectively. In the 1985 groundwater domains, a east-west domain was not delineated in the

center of Taylor County due to the groundwater withdrawals in the region causing an artificial

bend in the potentiometric surface. The groundwater domains for 1985, 1990, 1995, 2002 and

2005 potentiometric surface maps were overlaid and the maximum extent of each basin was used

to determine the composite potentiometric surface groundwater domains.

The PCA revealed two distinct water types based on water quality parameters potassium

(K), sodium (Na), magnesium (Mg), calcium (Ca), chloride (Cl), sulfate (SO4), and NO3-N. The

PCA yielded two principal components that were significant and accounted for 77.8 % of the

total variability (Table 5-1). Principal component 1 includes K, Na, Mg, Cl, and SO4, which are

positively correlated Figure 5-6 shows the component contours for principal component 1. The

higher contours are associated with the regions of the upper Floridan aquifer that has a confining

unit. Principal component 1 represents geological influences on recharge and weathering of the

Hawthorne Group. Therefore, principal component 1 represents the confined Floridan aquifer.

Principal component 2 includes Ca and NO3-N, which are negatively correlated. Figure 5-7

shows the component contours for principal component 2. The higher component contours

indicate recharge or surfacewater influences. The region in the southwest corner of Dixie

County indicates water quality that is different from the surrounding ground water. This resulted









in the delineation of a ninth groundwater domain. The difference in the groundwater quality in

southwest Dixie County may be associated with sand/limestone mining. Principal component 2

represents more rapid recharge of the upper \Floridan through karst features. Therefore,

principal component 2 represents the unconfined Floridan aquifer.

The results from the composite potentiometric surface groundwater domains yielded

eight distinct groundwater domains. The eight potentiometric surface groundwater domains

were coupled with the component contours. The component contours were used to confirm that

the potentiometric surface groundwater domains did not contain water quality differences. The

component contours for principal component 2 identified two groundwater domains in Dixie

County instead of one groundwater domain as identified from the potentiometric surface. This

resulted in the delineation of a ninth groundwater domain, Dixie, which is the smallest

groundwater domain delineated in the SRWMD. The potentiometric surface groundwater

domain most likely did not account for the ninth basin due to the resolution of the potentiometric

surface and the density of wells in the region used to create the potentiometric surface maps. The

refined groundwater domains were adjusted to include the additional basin identified from the

component contours. The refined groundwater domains map for the SRWMD are shown in

Figure 5-10. Names were assigned to the groundwater domains based on their relationship to

surfacewater features (Alapaha, Aucilla, Coastal, Dixie, Ichetucknee, Santa Fe, Suwannee,

Steinhatchee, and Waccasassa).

The statistical summary by groundwater domain for NO3-N and TP are presented in

Table 5-2. A statistical summary for the period of record of the remaining groundwater quality

parameters from the WARN network (temperature, specific conductance, pH, DO, turbidity,










TDS, alkalinity, TOC, DOC, K, Na, Mg, Ca, Cl, F, SO42-, Fe, TKN, NH4 -N) is presented in

Appendix D, Table D-1.

A series of Kruskal-Wallis tests were conducted on the median TP and NO3-N

concentrations to show that each groundwater domain was statistically different at the 95 percent

confidence level (Appendix D, Tables D-2A to D-2H). The median TP and NO3-N

concentrations for each of the groundwater domains were examined. The first test included all

nine basins. The model was found to be significant at the 95 % confidence level. The

groundwater domain with the highest concentrations was removed and the remaining basins were

analyzed using the Kruskal-Wallis test. This process was continued until all the basins were

determined to be statistically different at the 95 % confidence level for TP and NO3-N. These

results provide a method for evaluating the groundwater conditions for TP and NO3-N on a

regional scale.

Figure 5-9 shows the median TP concentration with Kruskal-Wallis statistical separation

for each groundwater domain. The groundwater domain with the highest TP concentration was

the Waccasassa. Waccasassa groundwater TP may be associated with the weathering of

carbonate-hydroxylapatite [Cas(PO4*CO3)3*(OH)] in the Waccasassa Flats (Maddox et al., 1992).

Carbonate-hydroxylapatite is the mineral produced by precipitation of phosphate which was

liberated by weathering of carbonate-fluorapatite [Ca5(PO4*CO3)3*F] under acidic conditions.

The precipitation of carbonate-hydroxylapatite occurs when the phosphate rich water encounters

an alkaline environment, such as the upper Floridan aquifer (Maddox et al., 1992).

Furthermore, the groundwater domains closest to the Gulf of Mexico had the highest TP

concentrations in the SRWMD. The possible sources of the P are organic rich recharge water

containing P or leaching from the geological formations providing P as the acidic water is









recharging to the upper Floridan aquifer. The groundwater domains adj acent to the Gulf of

Mexico have large areas of swamps which are groundwater discharge zones. The swamps result

from low lying topography and in some case, overlying clayey sands and the high potentiometric

surface which results in surficial waters being unable to infiltrate into the ground (Arthur, 1991).

The surface water conditions in these swamps result in an acidic environment, largely due to

organic acids, in which P may be dissolved in the water column or suspended with organic

material. As the water in the swamps move to the edge of the swamps which have karst features

which can provide recharge points into the underlying upper Floridan aquifer. The ortho-P

fraction of the TP will precipitate when it comes in contact with the alkaline water of the upper

Floridan aquifer (Maddox et al., 1992). The organic P fraction of TP may precipitate or remain

suspended or dissolved. Lawrence and Upchurch (1982) demonstrated that recharge water

containing P could maintain the P in solution for several kilometers within karst features, such as

conduits in the upper Floridan aquifer, due to the lack of contact with limestone. Also, Lawrence

and Upchurch (1982) noted that the weathering of apatite minerals from the Hawthorn Group

introduced phosphate into surface and ground water. Erosion of the Hawthorn Group in the

Highlands during various sea level stands and deposition of the erosion products from the

Hawthorn Group within the groundwater domains adj acent to the Gulf of Mexico may account

for the P bearing materials within the groundwater domains.

Figure 5-10 shows the median NO3-N concentration with Kruskal-Wallis statistical

separation for each groundwater domain. The groundwater domain with the highest median

NO3-N concentration was the Santa Fe. Three groundwater domains, Santa Fe, Ichetucknee, and

Suwannee, had elevated NO3-N concentrations. The elevated NO3-N is due to anthropogenic

factors, such as atmospheric deposition, septic tanks, wastewater spray fields, or fertilization









(Andrews, 1994). Also, there are no known natural sources of NO3-N in the upper Floridan

aquifer. Katz et al. (1999) sampled springs within Santa Fe, Ichetucknee, and Suwannee

groundwater domains. Nitrate-nitrogen in two springs in the Suwannee groundwater domain

with NO3-N concentrations greater than 10 mg L^1 was from an inorganic source; while other

springs had mixed or organic source signatures based on the 1N/14N isotopic ratio. The results

for the Santa Fe groundwater domain yielded that one spring (GIL917971) with NO3-N

concentrations greater than 10 mg N L^1 was from a mixed source; while other springs had

inorganic or organic source signatures. Only one spring was sampled in the Ichetucknee

groundwater domain and it had an inorganic signature. Furthermore, the limitation of using

1sN/14N ratio is potential sources are limited to inorganic, organic and mixed and that it cannot be

traced to a specific landuse practice on a specific site.

The groundwater domains, as shown in Figure 5-8, were used to clip the 1995

landuse/landcover (Figure 5-11) to determine the landuse/landcover for each groundwater

domain. The 1995 landuse/landcover coverage is the best available source of landuse data

available at the time of this study. Level 2 FLUC landuse/landcover for each groundwater

domain is presented in Table 5-3 to 5-11. The single largest landuse/landcover for all the

groundwater domains is tree plantations, which confirms the rural nature of the SRWMD.

The percentage of each level 2 FLUC landuse/landcover was correlated to the median

groundwater domain concentrations of TP and NO3-N. The only level 2 FLUC

landuse/landcover with a correlation was crop and pasture land to NO3-N (Figure 5-12). No

correlation was observed for TP for crop and pasture land landuse/landcover (Figure 5-13) or any

other landuse/landcover, which suggests that either TP is not influenced by landuse/landcover at

this time or the ortho-P component of TP is precipitated in the upper Floridan aquifer, so









concentration in the groundwater is a result of the chemical equilibrium. Figure 5-14 shows the

median groundwater domain NO3-N and the percentage of the domain in crop and pasture land.

Based on the correlation of median NO3-N concentrations and percent of the basin in level 2

FLUC crop and pasture land landuse/landcover there are elevated NO3-N concentrations in the

upper Floridan aquifer within the groundwater domain when the groundwater domain has greater

than 12 percent of the groundwater domain in crop and pasture land landuse/landcover. The

Santa Fe groundwater domain has the highest median NO3-N concentration and the highest

percentage of the domain in crop and pasture land landuse/landcover followed by the Suwannee

and Ichetucknee (Figure 5-14). The landuse crop and pasture land in Santa Fe, Suwannee and

Ichetucknee domains are occurring over the unconfined Floridan aquifer on primarily Entisols

with high leaching potential. Sabasan (2004) identified NO3-N concentrations in various landuse

on Entisols, Ultisols, and Spodosols in the Santa Fe River Watershed. For landuse improved

pasture, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 0.51, 1.80 and 1.65

Clg N g of soil, respectively. The Entisols which are in landuse improved pasture have lower

soil NO3-N due to the leaching of the NO3-N. Furthermore, where these Entisols are over the

unconfined Floridan aquifer there is potential for leaching of NO3-N into the upper Floridan

aquifer. For the Santa Fe, Suwannee and Ichetucknee groundwater domain, the level 2 FLUC

crop and pasture land landuse/landcover is composed of improved pasture, row crop and

woodland pasture. The improved pasture makes up greater than 65 percent of the level 2 FLUC

crop and pasture land landuse/landcover as shown in Figure 5-15. Also, hay fields are classified

as improved pasture in the level 2 FLUC system which receives applications of N fertilizers.










Summary and Conclusions

There are nine distinct groundwater domains in the upper Floridan aquifer within the

SRWMD based on groundwater levels (potentiometric surface) and groundwater quality. The

Santa Fe, Ichetucknee and Suwannee groundwater domains have the highest median NO3-N

concentrations of the groundwater domains within the SRWMD. Variation in the concentrations

of TP is most likely due to geological properties of the upper Floridan aquifer while the variation

in the concentrations of NO3-N is due to anthropogenic factors, such as, fertilizer use in the

groundwater domain.

Median concentrations of TP and NO3-N was related to various level 2 FLUC

landuse/landcover classes in each groundwater domain. The only correlation was observed for

crop and pasture land for groundwater domain NO3-N concentration. Based on the observed

relationship in the SRWMD, when the percentage of a groundwater domain is greater than 12

percent crop and pasture land, the groundwater domain will have elevated NO3-N concentrations.

The landuse crop and pasture land in Santa Fe, Suwannee and Ichetucknee domains are

occurring over the unconfined Floridan aquifer on primarily Entisols with high leaching

potential. The major component of the level 2 FLUC crop and pasture land class is improved

pasture. Furthermore, improved pasture can also be Hields for the production of hay that can

receive N fertilizer to maximize hay crop yields and protein content. Thus, this study identified

for the SRWMD a direct relationship tool for determining when a groundwater domain may be

impacted by NO3-N concentrations in the upper Floridan aquifer by landuse crop and pasture

lands.









Table 5-1. Principal component analysis showing significant components.
Variable Units Principal Component 1 Principal Component 2
Sodium mg L^1 0.463 -0.099
Chloride mg L^1 0.461 -0.099
Potassium mg L^1 0.456 -0.065
Sulfate mg L^1 0.421 0.061
Magnesium mg L^1 0.419 0.043
Calcium mg L^1 0.112 0.654
Nitrate-nitrogen mg L^1 0.006 0.737

Eigenvalue 4.418 1.030
Accounted percent of variability 63.1 14.7










Table 5-2. Statistical summary for N03-N and TP by groundwater domain.


25th
Percentile
0.00
0.01
0.00
0.00
0.01
0.02
0.00
0.00
0.00

0.040
0.050
0.081
0.010
0.035
0.040
0.040
0.044
0.189


75th
Percentile
0.09
0.62
0.11
0.03
0.73
1.62
0.03
1.31
0.01

0.109
0.480
0.522
0.042
0.100
0.105
0.461
0.145
0.209


Standard
Deviation
0.56
1.12
0.17
0.02
1.74
1.73
0.09
3.56
0.02

0.087
0.545
0.228
0.019
0.359
0.204
3.936
1.781
0.037


Variable
NO3-N


Units Basin
mg L^' Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa

mg L^' Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
0.18
0.62
0.09
0.02
0.62
1.41
0.03
1.32
0.01

0.087
0.325
0.258
0.028
0.144
0.102
1.005
0.248
0.195


Median
0.01
0.03
0.02
0.02
0.25
1.21
0.01
0.31
0.01

0.070
0.133
0.151
0.030
0.053
0.055
0.068
0.070
0.196


Minimum
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.078


Maximum
3.94
4.16
1.05
0.07
27.20
10.60
0.73
52.0
0.09

0.598
4.870
0.814
0.056
3.640
2.240
25.000
45.000
0.303











Table 5-3.


1995 level 2 Florida Landuse Code for the Alapaha groundwater domain.
Land Cover Hectares
Tree Plantations 160,459
Wetland Forested 30,762
Crop and Pasture Land 26,808
Wetland Coniferous 17,515
Wetland Hardwood 8,353
Upland Hardwood 5,145
Extractive 3,167
Streams and Waterways 929
Freshwater or Salt Marshes 625
Upland Coniferous 332
Industrial 314
Residential, Medium Density 310
Residential, Low Density 272
Utilities 232
Commercial and Services 229
Transportation 96
Recreational 57
Animal Feeding Operation 40
Specialty Farms 20
Nurseries and Vineyards 8.3
Residential, High density 8.0
Disturbed land 7.8
Major Springs 1.2









Table 5-4.


1995 level 2 Florida Landuse Code for the Aucilla groundwater domain.
Land Cover Hectares
Tree Plantations 105,890
Wetland Forested 105,017
Embayments opening directly into the Gulf of Mexico 40,470
Crop and Pasture Land 31,021
Wetland Coniferous 13,049
Wetland Hardwood 7,478
Freshwater or Salt Marshes 4,266
Upland Hardwood 4,097
Upland Coniferous 663
Utilities 533
Residential, Low Density 414
Extractive 393
Residential, Medium Density 326
Nurseries and Vineyards 244
Streams and Waterways 198
Commercial and Services 184
Transportation 173
Recreational 107
Industrial 93.0
Specialty Farms 37.1
Disturbed land 20.5
Animal Feeding Operation 17.9
Open Land 15.0
Residential, High density 9.78
Non-Vegetated Wetland 6.49
Major Springs 4.64
Ovster Bars 0.91










Table 5-5.


1995 level 2 Florida Landuse Code for the Coastal groundwater domain.
Land Cover Hectares
Embayments opening directly into the Gulf of Mexico 145,729
Tree Plantations 117,688
Freshwater or Salt Marshes 10,068
Wetland Forested 9,375
Wetland Coniferous 9,072
Crop and Pasture Land 4,216
Wetland Hardwood 3,386
Upland Hardwood 1,164
Residential, Low Density 808
Utilities 755
Upland Coniferous 586
Residential, Medium Density 484
Industrial 380
Commercial and Services 231
Non-Vegetated Wetland 176
Extractive 79.1
Streams and Waterways 68.2
Recreational 50.8
Coastal Scrub 48.9
Open Land 29.6
Animal Feeding Operations 27.5


20.4
14.6
1.51
0.95


Embayments not opening directly into the Gulf of Mexico
Residential, High Density
Major Springs
Disturbed Land












Table 5-6.


1995 level 2 Florida Landuse Code for the Dixie groundwater domain.
Land Cover Hectares
Embayments opening directly into the Gulf of Mexico 105,241
Tree Plantations 22,006
Freshwater or Salt Marshes 6,613
Wetland Forested 5,076
Wetland Coniferous 1,135
Residential, Low Density 341
Crop and Pasture Land 230
Non-Vegetated Wetland 206
Residential, Medium Density 196
Upland Hardwood 108
Commercial and Services 66.9
Wetland Hardwood 50.8
Embayments not opening directly into the Gulf of Mexico 41.5
Recreational 12.2
Upland Coniferous 10.3
Coastal Scrub 7.22
Open Land 3.16
Residential, High Density 1.97
Disturbed land 1.37
Utilities 1.17









Table 5-7.


1995 level 2 Florida Landuse Code for the Ichetucknee groundwater domain.
Land Cover Hectares
Tree Plantations 276,578
Crop and Pasture Land 66,861
Wetland Forested 40,965
Upland Hardwood 19,916.
Wetland Coniferous 13,968
Upland Coniferous 10,089
Wetland Hardwood 3,726
Residential, Low Density 3,292
Residential, Medium Density 1,754
Utilities 1,040
Commercial and Services 716
Extractive 390
Recreational 339
Freshwater or Salt Marshes 319
Nurseries and Vineyards 250
Industrial 247
Streams and Waterway 224
Disturbed land 214
Transportation 199
Animal Feeding Operations 173
Open Land 142
Residential, High Density 113
Specialty Farms 69.7
Tree Crops 30.3
Palmetto Prairies 19.3
Major Springs 1.47









Table 5-8.


1995 level 2 Florida Landuse Code for the Santa Fe groundwater domain.
Land Cover Hectares
Tree Plantations 86,217
Crop and Pasture Land 68,046
Upland Hardwood 28,252
Wetland Forested 18,924
Residential, Medium Density 6,726
Residential, Low Density 6,465
Wetland Coniferous 5,033
Upland Coniferous 2,460
Freshwater or Salt Marshes 2,221
Wetland Hardwood 1,755
Commercial and Services 1,495
Utilities 1,353
Residential, High Density 1,142
Recreational 902
Extractive 718
Industrial 509
Transportation 499
Specialty Farms 449
Nurseries and Vineyards 307
Open Land 263
Streams and Waterway 176
Disturbed Land 60.8
Animal Feeding Operations 60.0
Tree Crops 12.8
Major Springs 1.81










Table 5-9.


1995 level 2 Florida Landuse Code for the Steinhatchee gro
Land Cover


,undwater domain.
Hectares
166,446
105,222
62,042
11,709
4,706
2,440
797
443
407
318
184
99.1
97.6
20.7
18.9
16.5
9.68
5.95
3.90
2.45
1.56
1.52
0.34


Tree Plantations
Embayments opening directly into the Gulf of Mexico
Wetland Forested
Wetland Coniferous
Freshwater or Salt Marshes
Wetland Hardwood
Upland Hardwood
Crop and Pasture Land
Residential, Low Density
Non-Vegetated Wetland
Residential, Medium Density
Upland Coniferous
Streams and Waterways
Commercial and Services
Embayments not opening directly into the Gulf of Mexico
Recreational
Industrial
Disturbed land
Open Land
Coastal Scrub
Utilities
Extractive
Major Springs









Table 5-10


1995 level 2 Florida Landuse Code for the Suwannee groundwater domain.
Land Cover Hectares
Tree Plantations 283,108
Crop and Pasture Land 145,374
Upland Hardwood 90,396
Wetland Forested 86,362
Residential, Low Density 31,182
Wetland Coniferous 26, 164
Wetland Hardwood 15,387
Open Land 9, 153
Shrub and Brush Land 7,468
Upland Coniferous 4,340
Lakes 4,020
Other Open Lands 3,340
Streams and Waterway 3,299
Residential, Medium Density 1,698
Non-Vegetated Wetlands 1,082
ODC Institutional (Education, religious, health, military) 1,080
Commercial and Services 1,035
Extractive 965
Reservoirs 934
Tree Crops 929
Specialty Farms 737
Nurseries and Vineyards 687
Animal Feeding Operations 668
Industrial 360
Residential, High Density 106
Disturbed Lands 81.4
Major Springs 12.9
Bays and Estuaries 8.07














Table 5-11. 1995 level 2 Florida Landuse Code for the Waccasassa groundwater domain.
Land Cover Hectares
Embayments opening directly into the Gulf of Mexico 105,233
Tree Plantations 57,782
Wetland Forested 12,706
Crop and Pasture Land 10,060
Upland Hardwood 7,647
Freshwater or Salt Marshes 7,443
Upland Coniferous 3,013
Wetland Hardwood 2,305
Wetland Coniferous 1,759
Extractive 473
Nurseries and Vineyards 242
Residential, Low Density 207
Utilities 46.3
Commercial and Services 34.9
Recreational 23.9
Specialty Farms 22.9
Streams and Waterway 12.9
Open Land 8.25


Embayments not opening directly into the Gulf of Mexico
Coastal Scrub
Palmetto Prairies
Residential, Medium Density
Residential, High Density
Disturbed Land


7.87
7.64
5.31
2.81
1.45
0.70


















































-20- Potentiometric Contour
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure 5-1. Groundwater domians based on 1985 potentiometric surface (Rosenau and Meadows, 1986).














































0 40 Miles


-20- Potentiometric Contour -
Groundwater level in feet above msl. of
Contour intervals 10 feet



Figure 5-2. Groundwater domains based on 1990 potentiometric surface (Meadows, 1991).















































0 40 Miles


-20- Potentiometric Contour-
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure 5-3. Groundwater domains based on 1995 potentiometric surface (Mahon et al., 1997).















































0 40 Miles



-20- Potentiometric Contour-
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure 5-4. Groundwater domains based on 2002 potentiometric surface (SRWMD, 2002).












































-20- Potentiometric Contour-
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure 5-5. Groundwater domains based on 2005 potentiometric surface (SRWMD, 2005).



































4 Component Contours

2







Figure 5-6. Principal component 1 contours for hydrochemical facies analysis.





















































-2







-4



-6



Figure 5-7. Principal component 2 contours for hydrochemical facies analysis.












































0 40 Miles





Figure 5-8. Refined groundwater domains based on composite potentiometric surfaces basins and hydrochemical facies analysis.












0.25







0.2


SDifferent letters indicated significant difference at 0.05 confidence lev~el.


0.05 t


I


Alapaha Aucilla Coastal Dixie Ichetucknee Santa Fe Steinhatchee Suwannee Waccasassa


Figure 5-9. Median groundwater TP concentration by groundwater domains.(


u,0.15
-
O
O

o

1-0.1
-c

















































Alapaha Aucilla Coastal Dixie Ichetucknee Santa Fe Stei nhatchee S uwannee Waccasassa


Figure 5-10. Median groundwater NO3-N concentration by groundwater domains.


1.4




1.2




1




S0.8




.!! 0. 6


SDifferent letters indicated significant difference at 0.05 confidence level.



























































C) 40 MileS


I


County Boundaries
Land Cover
Residential, Low Density
Residential, Mledium Density
Residential, High Density
Commercial and Services
I InIIIIIIIdustrial
Extractive
Institutio nal
Recreational
Open Land
Cro p and Pasture Land
Tree Crops
Animal Feeding Operations
Nurseries and Vineyards
Specialty Farms
Other Open Lands (Rural)
Shrub and Brushland
Upland Coniferous Forest
IIIIIUpland Hardwood Forests
SUpland Hardwood Forests
Tree Plantations
Streams and Waterways
Lakes
Reservoirs
Bays and Estuaries
Major Sp ring s
Wetland Hardwood Forests
Wetland Con iferous Fo rests
Wetland Forested Mlixed
Freshwater or Salt Mlarshes
Non-Vegetated Wetlands
IIIIIIIICut over Wetlands
IDisturbed Lands
Tran sp ortatio n
Uti lities


Figure 5-11. 1995 level 2 Florida Landuse Code landuse/landcover for the Suwannee River Water Management District.

















30

y = 4.3078Ln(x) + 24.076
R2 = 0.7326










O
00~15




S10









04
0 0.2 0.4 0.6 0.8 1 1.2 1.4
median NOx-N (mg/L)


Figure 5-12. Median groundwater NO3-N concentration versus percentage of groundwater domains in crop and pasture lands.


















30






O,



O 2








S10






5*




0 0.05 0.1 0.15 0.2 0.25

Median Total P (mg/L)


Figure 5-13. Median groundwater TP concentration versus percentage of groundwater domains in crop and pasture lands.











I 1M Land use CNOx-N


-
S25
(I

-al 20

o
o-
15



S10
-


1



0.8
o

0.6.~


i


I 0.4


Alapaha Aucilla Coastal Dixie Ichetucknee Santa Fe Steinhatchee Suwannnee Waccasassa

Figure 5-14. Median groundwater NO3-N concentration and percentage of groundwater domains in crop and pasture lands.












HImproved Pasture Row Crop OWoodland Pasture


90


80


70


30


20


10


Ichetucknee Santa Fe Suwannee


Figure 5-15. Landuses within crop and pasture lands code for the groundwater domains with elevated median NO3-N.


e 60


-050


o









CHAPTER 6
SYNTHESIS

The station on the Suwannee River at Branford is a sentinel or integrator station for the

Suwannee River. This station has been monitored for water quality since 1954. Total

phosphorus (TP) concentration has significantly (>99.9% confidence level) declined since the

river was designated an Outstanding Florida Water (OFW) in 1979. The decrease in the TP

concentrations that started in 1985 coincides with increased regulation of a phosphate mining

operation in Hamilton and Columbia counties. Nitrate-nitrogen (NO3-N) concentrations have

significantly increased since its designation as an OFW in 1979. Also, there was an observed

increasing trend for potassium (K). The increases in NO3-N and K concentrations suggest a

fertilizer signature. There was an observed time lag between N fertilizer sales data for Suwannee

and Lafayette counties and riverine NO3-N concentrations of one to six years. This increasing

trend is supported by the increased use of inorganic fertilizer in Suwannee and Lafayette

counties. This suggests that the NO3-N concentration observed at the Branford station was likely

related to fertilizer use in the groundwater domains that feed ground water to the Suwannee

River via the numerous springs and seeps in the Middle Suwannee River Basin (MSRB). The

MSRB was consistently the highest contributor of the annual NO3-N load from water years 1998

to 2005 and reach 1 of the Suwannee River was consistently the highest contributor of the annual

TP load from water years 1998 to 2004 excluding 2005 when it was the third largest contributor.

The range of the annual NO3-N loading for the MSRB was 29.3 to 46.9 percent of the annual

NO3-N load for the entire Suwannee River Basin (SRB) from 1998 to 2005. The range of the

annual TP loading for reach 1 of the Suwannee River was 14.6 to 100 percent of the annual TP

load for the entire SRB from 1998 to 2005. This suggests that anthropogenic factors are driving

the changes in water quality from pre-OFW to post-OFW conditions for TP and NO3-N.









The current mean upper Floridan aquifer concentrations for TP and NO3-N were three

times above background (or <0. 10 mg P L^1) and 23 times above background (or <0. 10 mg N

L^) concentrations, respectively, as defined by Maddox et al. (1992). Surfacewater NO3-N

concentrations reflected the adj acent Floridan aquifer' s groundwater concentrations for NO3-N.

Surfacewater basin concentrations of TP were driven by geological formations, point sources,

and surface runoff. Thus, ground water from the upper Floridan aquifer plays a major role on the

quality of surface water in regions where the Suwannee and Santa Fe rivers intersects the top of

the upper Floridan aquifer.

The regions of the MSRB and Lower Santa Fe River Basin (LSFRB) where the greatest

increase in NO3-N concentrations occur are relatively small segments of river channel within

each river system. The NO3-N was likely moving into the surfacewater system via ground water

through springs and seeps in the riverbed. The soils adjacent to these segments were Entisols

that have high leaching potential. Furthermore, the upper Floridan aquifer is unconfined in these

regions. The coupling of the upper Floridan aquifer being unconfined and overlain by soil with

high leaching potential with landuses that are adding NO3-N via fertilizer creates the potential for

contamination of the upper Floridan aquifer. This resulted in increased NO3-N concentrations in

reaches of the Suwannee and Santa Fe river which receive base flow from the upper Floridan

aquifer. Two springs sampled in the segment of the MSRB where the highest increase in NO3-N

loading occurred showed a linear relationship with K and NO3-N. Results from a USGS study

showed that the NO3-N was from an inorganic source and the age of the water was less than nine

years (Katz et al., 1999). This is similar to the observed relationship of N fertilizer sales data and

riverine NO3-N concentration and the apparent lag time of one to six years. Furthermore, for the

Suwannee River this suggests that fertilizer is the maj or component of the observed increasing









NO3-N trend in the Suwannee River at Branford. The Middle Suwannee and Lower Santa Fe

rivers showed increased NO3-N concentrations from 2000-2001 to 2006 sampling events. This

suggests that the NO3-N loading from the ground water to the surface water was increasing for

the studied areas of the MSRB and LSFRB. Thus, understanding the aerial extent of the

groundwater domains of the upper Floridan aquifer that supplies the water to the MSRB and the

LSFRB and landuses that occur within the domains is needed to focus management activities.

Groundwater domains were defined in the Suwannee River Water Management District

(SRWMD) using potentiometric surface maps and water quality data of the upper Floridan

aquifer. Nine distinct groundwater domains were identified in the upper Floridan aquifer within

the SRWMD. The Santa Fe, Ichetucknee and Suwannee domains had the highest median NO3-N

concentrations of the groundwater domains within the SRWMD. These domains generally

occurred in areas where the unconfined Floridan aquifer underlies Entisols with high leaching

potential. Variation in the concentrations of NO3-N was due to anthropogenic factors, primarily

the use of inorganic fertilizer.

Relating landuse in a groundwater domain to observed upper Floridan NO3-N and TP

concentrations yielded a correlation for level 2 Florida landuse codes (FLUC) for crop and

pasture land and groundwater domain median NO3-N concentration. No other correlations with

TP and NO3-N concentrations and other level 2 FLUC were identified. When the percentage of a

groundwater domain area was greater than 12 percent crop and pasture land, the domain

generally had elevated NO3-N concentrations. The major component of the level 2 FLUC crop

and pasture land class is improved pasture which also includes areas used for forage production.

It is important that the regulating agencies continue to work with the point source

discharges associated with phosphate mining in the upper Suwannee River Basin to maintain the









declining trend in TP concentrations. Reducing NO3-N concentration in the Suwannee River

will require continued implementation of best management practices (BMPs) by the agricultural

producers. The Floridan aquifer is especially vulnerable in areas where the aquifer is

unconfined and soils have high leaching potential. Development/implementation ofBMPs on

these areas should be given priority.

















0.4




0.35




0.3




2 0.25



iD)




0..








0.15


APPENDIX A
HISTORICAL TOTAL PHOSPHORUS AND NITRATE-NITROGEN


~Ob~~~~~O~~Ob~~~~~O~~Ob~~~~~O~~Ob~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~0000000
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~0000000
hlhlhlhlhlhlhl
Water year


Figure A-1. Median TP concentration for the Suwannee River at Branford.















I.-ty





1.20





1.00







O .8



-E 0.60





0.40





0.20





0.00





Figure A-2. Median NO3-N concentration for the Suwannee River at Branford.













1.0



1.6



1.4



1.2

















0.4



0.2








Water Year


Figure A-3. Median K concentration for the Suwannee River at Branford.










APPENDIX B
WATER QUALITY SUMMARY


Table B-1. Summary of upper Floridan groundwater quality for the SRWMD (2001 to 2006).


Standard
Deviation
4.21

171.6
17.14
10.67
47.12


25th
Percentile
21.2

282
6.85
0.4
0.5

162
133

0.638

0.85
0.19
2.64
2.37
43.1
4.45
0.07
2.16
0.031

0.00
0.11
0.037
0.000


75th
Percentile
22.7

437
7.4
3.73
8.4

260
207


Parameter
Temperature
Specific
Conductance
pH
Dissolve Oxygen
Turbidity (NTU)
Total Dissolved
Solids
Alkalinity
Total Organic
Carbon
Dissolve Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
Iron
Nitrate +Nitrite-
nitrogen
TKN
Ammonia-nitrogen
Total Phosphorus


Units
oC

Clmhos cm l
su
mg L^
NTU

mg L 1
mg L 1

mg L 1

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1
mg L 1
mg L 1
mg L 1


Mean
22.0

369
7.64
2.68
11.57


Median
21.9

352
7.15
1.37
1.9

205
170


Minimum
13.23


3.45

0.04

4
0.3

0.38

0.07
0.007
0.044
0.004
0.004
0.15
0.02
0.11
0.003

0.002
0.04
0.016
0.005


Maximum
225

2714
586
373
986

36800
660

79.6

61.6
243
4800
536
913
9870
29.9
1140
131

52.0
8.5
10.1
45.0


251.8 856
171.44 64.36


3.45

4.05
1.23
11.14
8.61
62.78
18
0.17
12.75
0.94

0.94
0.33
0.10
0.219


5.83

5.67
8.56
148.51
17.27
36.20
281.63
0.60
46.24
3.30

2.73
0.43
0.29
1.558


1.4 3.68


2.08
0.401
3.4
5.1
58.5
5.65
0.12
5.17
0.159

0.17
0.2
0.04
0.07


5
0.824
5.24
11.8
79.225
8.02
0.2
10.8
0.909

1.00
0.4
0.100
0.156










Table B-2. Summary of water equality parameters for the Springs of Aucilla River Basin


(1989 to 2006).


Standard
Deviation
2.85

84.9
0.36


25th
Percentile
20.1

224.5
6.91

3.3

0.4

0.38
0.3
2.9
4.4
20.4
4.3
0.06
2
0.14

0.05

0.02

0.036


75th
Percentile
21.4

318
7.52

5.68

24.4

0.63
0.7
4.1
8.6
45.4
7
0.12
9
0.63

0.26

0.027


Basin
Aucilla


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble reactive
Phosphorus


Units
oC

Clmhos cm
su

mg L 1

mg L 1

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


Mean
20.4

263
7.20


Median
20.5

279.5
7.25

4.75

6.5

0.45
0.4
3.2
6.7
41.4
5.3
0.08
5
0.36

0.13

0.02


Minimum
13.3

72
6.49

0.7

0.3

0.3
0
2.1
1.5
3.5
0.5
0.04
0.1
0.04

0

0

0.009


Maximum
26.6

459
7.79

9.7

31.7

5.6
2.3
19.1
16.2
73.5
32
0.26
15
0.93

0.46

0.07

0.319


4.66 1.92

11.96 11.52


1.1
0.54
4.05
6.89
35.61
6.43
0.09
5.9
0.39


1.82
0.44
3.14
3.28
17.25
5.27
0.05
4.2
0.29


0.16 0.14

0.024 0.015

0.053 0.052


0.043 0.056


mg L 1


0.031 0.009 0.029


0.032 0.037 0.016 0.05










Table B-3. Summary of water equality parameters for the Springs of Coastal Rivers Basin (1989 to 2006).


Standard
Deviation
2.67

5511.3
0.24

2.58


25th
Percentile
20.3

428
6.84

0.5


75th
Percentile
22.3

878
7.12

4.7

12.95

23.3
0.575
6.75
17.75
127.5
14.15
0.31
68.23
0.48


Basin
Coastal


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble reactive
Phosphorus


Units Mean
oC 21.3

Clmhos cml 2927
su 6.99

mg L1 2.89

mg L1 14.23

mg L1 18.3
mg L1 0.53
mg L1 6.24
mg L1 16.09
mg L1 115.07
mg L1 10.04
mg L1 0.27
mg L1 56.59
mg L1 0.43

mg L1 0.05

mg L1 0.14

mg L1 0.075


Median
21.3

755
6.96

2.8

10.7

13.9
0.5
5.7
16.15
120.5
11.2
0.29
62.8
0.43


Minimum
10.5

213
6.4

0.1

8.1

10.7
0
4.2
5.9
42.9
1
0.08
3
0.16

0


Maximum
25.5

23700
7.65

8.7

35.8

31.9
1.5
9.9
20.3
132
16
0.35
74
0.82

0.38


8.60 10.4


9.09
0.34
1.47
3.513
22.93
4.90
0.06
18.51
0.14

0.06

0.05


11.7
0.4
5.4
15.73
113.5
5.5
0.27
50.5
0.37

0.02

0.119


0.025 0.05


0.16


0.186


0.01

0.047


0.216

0.128


0.019 0.068


0.072 0.078


mg L 1


0.057 0.018 0.054


0.063 0.066 0.002 0.087










Table B-4. Summary of water equality parameters for the Springs of Lower Suwannee River Basin (1989 to 2006).


Standard 25th
Mean Deviation Percentile


75th
Median Percentile


Basin


Parameter


Units


Minimum Maximum


Lower
Suwannee Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble reactive
Phosphorus


21.6


0.82

59.5
0.18


21.4

366
7.16

1

0.7

0.9
0.5
2.7
6
54.4
5.4
0.08
12
0.04

1.3

0.02

0.032


21.7

412
7.26

1.6


22.1

455
7.38

2.3


10.2

77
6.05

0.1

0

0.2
0
0.1
0
0
0
0.02
0.2
0

0

0.001

0.004


25.9

543
7.95

8

54.8

47.6
8.6
28.7
28.7
119
39
0.39
54.7
17.8

21.8

0.205

0.43


Clmhos cm l
su

mg L 1

mg L 1

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


407
7.25


1.85 1.31

3.77 4.84


1.8 5.4


4.01
1.30
3.66
8.92
63.5
7.39
0.11
19.9
0.16

3.01


4.90
1.24
1.41
4.29
13.69
3.06
0.051
11.11
0.64

3.11


2.2
0.8
3.5
7.3
61.6
7
0.11
16.3
0.1

1.91

0.02


5.92
1.6
4.4
11.6
71.1
9
0.15
24.1
0.16

3.45

0.04


0.035 0.030

0.051 0.030


0.047 0.064


mg L 1


0.034 0.017 0.022


0.031 0.045 0.002 0.129










Table B-5.

Basin
Santa Fe


Summary of water quality parameters for the Springs of Santa Fe River Basin (1989 to 2006).


Standard
Deviation
0.93

67.2
0.24

2.11

7.20


6.64
0.48
3.08
2.49
10.08
4.95
0.067
104.7
0.23

1.60


25th
Percentile
21.7

334
7.22

0.3

0.52


0.8
0.3
2.9
5.6
52.8
5.5
0.1
9.47
0.05

0.39

0.02

0.048


75th
Percentile
22.4

426.3
7.49


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
reactive


Units
oC


Mean
22.2


Median
22.2

370.5
7.34


Minimum
17.1

86
5.71

0.1

0


0.1
0
1.8
2.2
10.6
3
0.02
3.2
0

0

0.001

0.004


Maximum
28.1

675
8.25

9.5

52.9


53.9
5.4
19.8
15.7
103
62
0.66
2550
1.56

26

0.369

0.82


Clmhos cm l
su

mg L 1

mg L 1


mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


382
7.33

2.28

4.36


4.30
0.67
5.76
7.45
60.13
9.38
0.15
30.6
0.19

0.90


1.7 4

1.6 5.3


1.9
0.5
5.2
6.8
59.4
8
0.15
16.5
0.1

0.58

0.02


5.6
1
8.4
8.9
66.85
13.2
0.19
38.5
0.23

1.01

0.04


0.035 0.034

0.083 0.057


0.077 0.101


Phosphorus mg L 1


0.064 0.038 0.033 0.06


0.088 0.004 0.309










Table B-6. Summary of water equality parameters for the Springs of Upper Suwannee River Basin (1989 to 2006).


Standard 25th
Mean Deviation Percentile


75th
Median Percentile


Basin Parameter
Upper
Suwannee Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
reactive


Units
oC


Minimum Maximum


21.0


1.29

68.6
0.24

1.20

6.59


6.10
0.51
3.82
2.46
13.72
1.91
0.04
8.11
0.33

0.39


20.5

285.3
7.14

0.2

2.9


3.6
0.4
2.8
4.6
37.3
4.8
0.11
8.85
0.105

0.02

0.02

0.060


20.8

320
7.22

0.4

6.3


6.7
0.6
3.4
6.7
50
5.3
0.13
10.4
0.28

0.29

0.04


21.3

370
7.32

0.7

10.8


10.8
1.25
4.1
8.55
56.1
6.77
0.16
15.1
0.48

0.7

0.099


17

126
6.57

0

0


0.8
0
0
0
0.1
1
0.02
1
0

0

0.001

0.004


27.6

458
8.66

10.2

24.8


26.4
3
37.7
11.6
72
11.1
0.32
35.9
1.8

1.91

1.1

0.22


Clmhos cm l
su

mg L 1

mg L 1


mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


312
7.20

0.75

8.04


8.38
0.73
4.17
6.71
47.02
5.51
0.14
13.23
0.36

0.40


0.064 0.10

0.102 0.045


0.110 0.136


Phosphorus my L 1


0.077 0.039 0.041 0.08


0.112 0.002 0.146










Table B-7. Summary of water quality parameters for the Springs of Waccasassa River Basin


(1989 to 2006).


Standard
Deviation
0.30

11.6
0.25

0.89


25th
Percentile
22.1

194
6.59

2.4


75th
Percentile
22.7

216
7.05

3.7


Basin
Waccassasa


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
reactive
Phosphorus


Units
oC

Clmhos cm l
su

mg L 1


Mean
22.4

207
6.86

3.32


Median
22.3

213
7.03

3.7


Minimum
22.1

194
6.59

2.4


Maximum
22.7

216
7.05

4.4


mg L1


mg L1
mg L1
mg L1
mg L1
mg L1
mg L 1
mg L1
mg L1
mg L1

mg L 1

mg L 1

mg L 1


4.25


0.50


4





0.42

0.02

0.043


4





0.43

0.02


4.25





0.65

0.02


4





0.03

0.02

0.039


5





0.65

0.02

0.053


0.436 0.25


0.02


0.00


0.045 0.01


0.045 0.048


mg L1 0.0317 0.00 0.0295 0.032 0.034


0.028 0.035










Table B-8. Summary of water equality parameters for the Springs of Withlacoochee River Basin (1989 to 2006).


Standard
Deviation
0.3

17.2
0.21


25th
Percentile
20.8

278.3
7.42

1

0.5


0.8
0.4
3.2
7.95
39.5
5
0.13
11.75
0.11

1.17

0.02

0.044


75th
Percentile
21

289.2
7.63

2.3

1.1


1.35
0.5
3.9
8.9
42.7
6.2
0.17
13.65
0.25

1.58

0.099

0.06


Basin
Withlacoochee


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Dissolved
Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
reactive


Units
oC

Clmhos cm l
su

mg L 1

mg L 1


mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


Mean
20.9

287
7.50


Median
20.9

286
7.55

1.7

0.65


0.85
0.4
3.4
8.4
41.1
5.7
0.15
12.7
0.12

1.39

0.04

0.05


Minimum
19.6

237
6.78

0.2

0.3


0.3
0.2
2.9
6.3
33.1
4.3
0.05
10.6
0.04

0.27

0.02

0.04


Maximum
22.8

383
7.92

5.3

5.8


7.1
3
35.4
9.8
48.9
7.7
0.25
16.4
0.627

1.94

0.235

0.14


1.85 1.03

1.18 1.23


1.48
0.51
4.20
8.33
40.9
5.74
0.14
12.8
0.19


1.51
0.39
4.49
0.64
2.80
0.88
0.043
1.4
0.15


1.34 0.34

0.05 0.04

0.054 0.016


Phosphorus mg L 1


0.035 0.01 0.0277


0.034 0.0435 0.019 0.056










Table B-9. Summary of surfacewater quality parameters for the Alapaha River Basin (1989 to 2006).
Standard 25th 75th
Basin Parameter UmsMean Deviation Percentile Median Percentile Minimum Maximum


20.6 4.74


17.0


24.50


Alapaha


21.50

77
6.25

7.5

17.15
1.80
6.20
1.90
3.90
9.80
0.11
6.0
0.79

0.31

0.03

0.180


8.20


3.98

3.8

0.8
0.30
1.50
0.40
1.40
0
0.02
0.8
0

0


Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


84
6.14


36.7
0.70


56.5
5.60

6.7

12.3
1.50
3.90
1.50
3.00
8.00
0.09
3.0
0.56

0.14

0.02

0.110


104
6.7

8.7

23.575
2.20
10.30
2.50
4.90
11.30
0.18
10.4
0.96

0.72

0.04


27.10

210
7.51

11.9

46.1
5.90
27.00
7.10
62.50
18.20
0.32
45.3
2.00

2.00

0.33

0.567


7.78 1.53


18.622
1.93
7.91
2.04
4.64
9.65
0.13
7.7
0.79


8.384
0.74
5.60
0.74
5.61
2.76
0.06
6.5
0.32


0.48 0.44

0.04 0.03

0.191 0.097


0.250 0.041


mgL


0.127 0.085 0.056 0.105


0.193 0.014 0.460










Table B-10. Summary of surfacewater quality parameters for the Aucilla River Basin (1989 to 2006).
Standard 25th 75th
Basin Parameter UmsMean Deviation Percentile Median Percentile Minimum Maximum


19.7 5.3


15.4

69
6.35

6.1

4.38
0.30
2.60
2.13
8.60
5.00
0.07
0.8
0.22

0.01

0.02


23.8


Aucilla


20.7

257
7.31

7.4

10.9
0.40
3.00
6.40
37.85
5.50
0.12
4.0
0.51

0.03

0.04


4.4

28
4.67

2.5

0.5
0
1.70
0.80
0.40
0.5
0.02
0.1
0.05

0

0


28.8

330
8.32

10.9

55.2
1.90
8.10
10.60
51.70
11.10
0.29
12.3
2.50

0.44

0.12

0.150


Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


194
7.03

7.37

16.73
0.56
3.05
5.15
28.65
5.62
0.11
3.4
0.68

0.05

0.04


109.4
0.98

1.80

14.41
0.35
0.77
2.77
17.55
1.36
0.05
2.5
0.53

0.05

0.03


293
7.86

8.9

26.48
0.78
3.30
7.60
44.55
6.18
0.15
5.4
1.09

0.07

0.06


0.054 0.027 0.037


0.026 0.014 0.018


0.048 0.070 0.011


mgL


0.025 0.032 0.002 0.078










Table B-11. Summary of surfacewater quality parameters for the Coastal Rivers Basin (1989 to 2006).
Standard 25th 75th
Basin Parameter UmsMean Deviation Percentile Median Percentile Minimum Maximum


20.6 4.86


17

170
6.77

3.8

18.9
0.20
2.90
3.65
26.00
5.90
0.09
2.1
0.57

0.02

0.02


24.3


Coastal


21.15


6.2

33
3.29


32.3

4084
8.41

10.4

213
570.00
15050.00
6890.00
352.00
118000.00
24.00
4360.0
26.00

0.71

17.00

9.600


Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


2485
6.86

4.92

42.41
13.58
377.40
50.90
56.76
704.00
0.20
119.6
1.46

0.07

0.39

0.285


7331
0.89

1.99

33.07
52.18
1385.30
285.90
51.01
4710.00
0.88
349.2
1.94

0.11

1.22


364
7.1


586
7.33


5.1 6.3 0.2


36
0.50
3.92
7.20
47.20
8.70
0.13
8.0
1.00

0.05

0.04


53.6
1.00
13.10
13.60
70.93
13.70
0.20
29.1
1.53

0.06

0.10


2.5
0
1.00
0.20
1.00
0
0.02
0.1
0.09

0

0


0.707 0.054


0.091 0.139 0.010


mg L^


0.169 0.389 0.027


0.050 0.082 0.000 4.000










Table B-12. Summary of surfacewater quality parameters for the Lower Suwannee River Basin (1989 to 2006).
Standard 25th 75th
Basin Parameter Units Mean Deviation Percentile Median Percentile Minimum Maximum


Lower
Suwannee


Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


21.2


4.6

105.8
0.62

1.41

10.59
0.89
4.80
2.78
15.91
8.25
0.05
8.0
0.39

0.33

0.03


17.5

163
6.82

5.5

7.6
0.80
4.40
3.50
20.00
6.50
0.11
9.8
0.28

0.31

0.02

0.111


21.6

263
7.24

6.4

14
1.00
5.40
6.00
34.40
7.50
0.13
17.0
0.53


25.3

337
7.6

7.37

23.2
1.40
6.60
7.90
46.20
8.50
0.18
22.6
0.80


9

29
3.79

1.2

0.8
0.10
0.70
0.60
2.30
0
0.02
0.8
0

0

0


29.4

918
9.83

26.3

69
27.10
110.00
28.40
85.20
170.00
0.53
47.3
5.90

2.44

0.35

1.320


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


247
7.15

6.43

16.14
1.18
6.00
5.86
32.94
8.07
0.14
16.4
0.58

0.57

0.04


0.56 0.81


0.03

0.14


0.04


0.161 0.094


0.181 0.004


mg L^


0.115 0.068 0.078


0.1 0.134 0.002 1.290





Standard 25th 75th
Umts Mean Deviation Percentile Median Percentile Minimum Maximum


Basin
Santa Fe


Table B-13. Summer
y of surfacewater quality
y parameters for the Santa Fe River Basin
(1989 to 2006).


20.5 4.3


18.1


23.6


21.3

250
7.09

5.5

15.9
0.80
6.25
6.00
25.70
12.20
0.14
13.0
0.60

0.26

0.03


5


31.3

1948
8.36

14.4

139.6
98.80
94.10
15.70
111.00
88.30
1.30
105.0
5.25

4.80

2.70

6.000


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


245
6.81

5.70

21.09
1.01
7.25
5.80
31.45
14.06
0.15
17.6
0.71

0.34

0.05

0.204


129.2
0.92

1.71

18.29
2.53
4.48
3.01
21.89
8.53
0.08
16.2
0.61

0.32

0.12

0.368


125
6.41

4.6

6.1
0.50
4.90
3.30
11.00
9.00
0.10
5.2
0.22

0.07

0.02

0.080


350
7.45

6.7

32.4
1.10
8.40
7.40
52.20
16.70
0.20
25.0
1.04

0.56

0.05


22
3.21

0.5

0
0
1.80
0.10
0.90
0
0.02
0.8
0

0

0

0.001


0.124 0.210


mgL


0.151 0.274 0.053


0.092 0.159 0.001 3.800










Table B-14. Summary of surfacewater quality parameters for the Upper Suwannee River Basin (1989 to 2006).
Standard 25th 75th
Basin Parameter Units Mean Deviation Percentile Median Percentile Minimum Maximum


Upper
Suwannee


Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive


20.8


5.6

93.8
1.45

1.92

18.51
0.65
2.91
2.51
12.93
2.64
0.21
11.3
5.04


16.5

65.25
4.01

5

24.7
0.20
3.40
1.00
1.80
6.00
0.08
1.1
0.70

0.03

0.02

0.100


21.5

79
5.38

6

40.9
0.50
4.20
1.80
4.90
7.60
0.12
5.5
0.99

0.05

0.03

0.168


25.3

161.3
6.93

7.3

52
1.00
5.60
4.10
18.28
8.70
0.20
15.0
1.22

0.20

0.06

0.280


5.6

34
2.34

0

2.8
0
0
0
0.10
0
0.02
0.2
0.04

0

0

0.004


32.5

1570
8.05

22.4

98
5.90
46.30
15.00
55.00
65.00
4.90
120.0
128.00

8.04

1.10

8.900


Clmhos cm l
su

mg L 1

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


124
5.47

6.14

38.89
0.68
5.02
2.81
11.48
7.53
0.17
9.9
1.25


0.15 0.31

0.05 0.07

0.299 0.535


Phosphorus my L 1


0.253 0.531 0.060 0.128


0.230 0.000 8.800











































Phosphorus mg L 1


0.039 0.015 0.028


0.038 0.050 0.002 0.083


Standard 25th 75th
Units Mean Deviation Percentile Median Percentile Minimum


Basin
Waccasassa


Table B-15. Summer
y of surfacewater quality
y parameters for the Waccasassa River Basin
(1989 to 2006).


4.74


17

273
7.115

5.2

7.2
0.20
4.54
6.10
38.20
8.55
0.10
10.1
0.29

0.02

0.02

0.050


24.5


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive


20.6

409
7.30

6.23

16.64
1.16
26.32
10.25
50.93
30.48
0.14
17.4
0.66

0.10

0.04


21.5

358
7.34

5.8

14.8
0.40
6.40
8.70
49.30
12.00
0.13
15.7
0.59

0.09

0.03


8.2

52
5.36

2.8

1.6
0
1.80
1.40
8.40
2.7
0.03
3.0
0.10

0

0


Maximum
27.1

3792
7.83

10.6

45.9
37.70
1030.00
133.00
140.00
554.00
0.38
318.0
2.80

0.49

0.16

0.350


Clmhos cm l
su

mg L 1

mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1
mg L 1

mg L 1

mg L 1

mg L 1


369.2
0.35

1.56

10.97
3.75
101.85
12.69
18.54
73.87
0.06
8.8
0.44

0.09

0.03


434
7.53

7.4

24.5
0.80
10.35
10.40
60.05
17.00
0.17
45.5
0.90

0.16

0.04


0.075 0.036


0.068 0.098 0.023











































0.067 0.095 0.015 0.461


Standard 25th 75th
Umts Mean Deviation Percentile Median Percentile Minimum Maximum


Basin
Withlacoochee


Table B-16. Summer
y of surfacewater quality
y parameters for the Withlacoochee River Basin
(1989 to 2006).


19.9 5.03


16.15

105.5
6.56

5.3

6.2
1.50
4.50
2.40
8.21
7.00
0.10
6.2
0.30

0.20

0.02

0.093


24.1

264
7.42


oC


21

177
7

6

10.8
2.10
6.60
3.70
17.80
8.40
0.13
10.0
0.56

0.32

0.03


5.7

41
4.84


29

786
8.15

11.2


Parameter
Temperature
Specific
Conductance
pH
Dissolved
Oxygen
Total Organic
Carbon
Potassium
Sodium
Magnesium
Calcium
Chloride
Fluoride
Sulfate
TKN
Nitrate+Nitrite-
nitrogen
Ammonia-
nitrogen
Total
Phosphorus
Soluble
Reactive
Phosphorus


Clmhos cm l
su

mg L^

mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^
mg L^

mg L^

mg L^

mg L^


194
6.96

6.30

11.39
2.17
10.42
4.13
19.99
8.81
0.14
14.2
0.57

0.39

0.04


107.22
0.60

1.46

6.44
1.15
10.23
2.43
12.60
2.84
0.06
12.1
0.33

0.28

0.06


7.05

16

11.75
5.20
32.00
10.10
0.18
18.6
0.77

0.51

0.05


0.1
0.10
2.10
0.90
2.60
0
0.02
1.0
0.04

0

0


45.5

74.00
26.00
52.10
23.30
0.74
79.8
2.10

2.36

0.86

1.100


0.137 0.098


0.115 0.147 0.010


mg L^


0.082 0.058 0.048












Table B-17A. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 1998.


Annual Loads kg/year)
Nitrate-N % of Load
197,791.5 3.09
264,561.0 4.13
841,213.9 13.14
959,161.3 14.98
2,910,823.9 45.47
59,007.1 0.92
1,017,344.3 15.89
152,126.8 2.38
6,402,029.7 100.00


Contributing Basin
Suwannee Reach 1
Alapaha River
Withlacoochee
Suwannee Reach 2
Suwannee Reach 3
Santa Fe Reach 1
Santa Fe Reach 2
Suwannee Reach 4,5, & 6
TotalLoad


Area (mi2)
2,430
1,801
2,382
443
824
820
564
686
9, 950


Total Phosphorus
755,461.8
195,610.3
263,494.5
228,319.3
188,536.7
108,270.9
107,829.0
-87,569.7
1, 759, 952. 8


% of Load
42.93
11.11
14.97
12.97
10.71
6.15
6.13
-4.98
100. 00


oo Table B-17B. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 1999.
Annual Loads (kg/year)
Contributing Basin Area (mi2 Nitrate-N % of Load Total Phosphorus


% of Load
33.12
10.03
11.95
10.31
10.04
4.82
10.93
8.79
100. 00


Suwannee Reach 1
Alapaha River
Withlacoochee
Suwannee Reach 2
Suwannee Reach 3
Santa Fe Reach 1
Santa Fe Reach 2
Suwannee Reach 4,5, & 6
Total


2,430
1,801
2,382
443
824
820
564
686
9, 950


75,192.5
175,187.9
508,185.2
383,006.3
2,005,222.0
19,245.9
884,718.9
220,026.0
4,2 70, 784. 8


1.76
4.10
11.90
8.97
46.95
0.45
20.72
5.15
100. 00


206,590.9
62,560.6
74,562.0
64,285.4
62,619.6
30,083.4
68,190.7
54,856.9
623, 749. 4



























Table B-17D. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2001.
Annual Load (kg/year)
Contributing Basin Area (mi2) Nitrate-N % of Load Total Phosphorus % of Load


Table B-17C. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2000.
Annual Load (kg/year)


Contributing Basin
Suwannee River Reach 1
Alapaha River
Withlacoochee River
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reaches 4, 5, & 6
Total


Area (mi2)
2,430
1,801
2,382
443
824
820
564
686
9, 950


Nitrate-N
36,900.6
158,688.2
256,733.5
281,498.4
848,107.2
2,671.4
705,113.7
69,110.1
2, 358, 000.0


% of Load
1.6%
6.7%
10.9%
11.9%
36.0%
0.1%
29.9%
2.9%
100. 0%


Total Phosphorus
82,096.2
71,765.6
39,748.6
61,740.0
0.0
5,748.8
52,714.2
13,634.3
32 7,600.0


% of Load
25%
22%
12%
19%
0%
2%
16%
4%
100%


Suwannee River Reach 1
Alapaha River
Withlacoochee River
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reaches 4, 5, & 6
Total


2,430
1,801
2,382
443
824
820
564
686
9, 950


30,716.1
344,868.4
543,940.1
45,340.7
1,227,440.1
3,748.2
427,311.4
75,818.6
2, 699,1~83. 5


1.1%
12.8%
20.2%
1.7%
45.5%
0.1%
15.8%
2.8%
100. 0%


241,761.3
142,372.5
128,279.3
-112,024.0
103,347.9
10,820.0
26,890.0
93,448.0
634, 895.1


38%
22%
20%
-18%
16%
2%
4%
15%
100%










Table B-17E. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2002.
Annual Load (kg/year)
Contributing Basin Area (mi2) Nitrate-N % of Load Total Phosphorus % of Load


Suwannee River Reach 1
Alapaha River
Withlacoochee River
Withlacoochee GA
Withlacoochee FL
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reach 4
Suwannee River Reaches 5 & 6
Total


2,430
1,801
2,382
2,118
264
443
824
820
564
342
344
9, 950


17,576.2
96,958.3
236,861.6
72,453.6
164,408.0
174,178.7
783,503.0
2,698.4
522,922.8
-161,535.1
1,000,872.2
2, 674, 036.1


0.7%
3.6%
8.9%
2.7%
6.1%
6.5%
29.3%
0.1%
19.6%
-6.0%
37.4%
100%


268,841.5
50,264.8
49,680.2
53,895.0
-4,214.8
-10,530.3
18,312.5
6,447.7
54,320.7
6,461.7
207,890.2
651, 689.0


41.3%
7.7%
7.6%
8.3%
-0.6%
-1.6%
2.8%
1.0%
8.3%
1.0%
31.9%
100. 0%


Table B-17F. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2003.
Annual Load Contribution (kg/year)
Contributing Basin Area (mi2) Nitrate-N % of Load Total Phosphorus % of Load


Suwannee River Reach 1
Alapaha River
Withlacoochee River
Withlacoochee GA
Withlacoochee FL
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reach 4
Suwannee River Reaches 5 & 6
Total


2,430
1,801
2,382
2,118
264
443
824
820
564
342
344
9, 950


30,913.9
491,223.4
960,163.0
801,011.6
159,151.4
-64,733.3
1,386,940.1
26,674.5
626,407.0
-184,172.2
763,194.1
4, 036, 610. 7


0.8%
12.2%
23.8%
19.8%
3.9%
-1.6%
34.4%
0.7%
15.5%
-4.6%
18.9%
100%


792,541.7
271,328.3
346,609.1
337,420.6
9,188.5
-145,933.2
158,491.5
129,706.1
86,853.1
-121,628.5
-53,499.8
1, 464, 468. 5


54.1%
18.5%
23.7%
23.0%
0.6%
-10.0%
10.8%
8.9%
5.9%
-8.3%
-3.7%
100. 0%










Table B-17G. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2004.
Annual Load Contribution (kg/year)
Contributing Basin Area (mi2) Nitrate-N % of Load Total Phosphorus % of Load


Suwannee River Reach 1
Alapaha River
Withlacoochee River
Withlacoochee GA
Withlacoochee FL
Suwannee River Reach 2
Suwannee River Reach 3
Santa Fe River Reach 1
Santa Fe River Reach 2
Suwannee River Reach 4
Suwannee River Reaches 5 & 6
Total


2,430
1,801
2,382
2,118
264
443
824
820
564
342
344
9, 950


66,713.9
464,351.4
891,320.4
309,349.1
581,971.4
-240,949.5
1,660,115.3
13,469.1
1,014,996.9
15,550.1
903,821.5
4, 789, 389.1


1.4%
9.7%
18.6%
6.5%
12.2%
-5.0%
34.7%
0.3%
21.2%
0.3%
18.9%
100%


867,015.6
174,172.1
172,898.5
148,264.2
24,634.3
-491,391.4
116,851.5
118,561.1
50,334.5
-121,249.5
-22,290.9
864, 901. 4


100.2%
20.1%
20.0%
17.1%
2.8%
-56.8%
13.5%
13.7%
5.8%
-14.0%
-2.6%
100. 0%
















































Figure B-1A. Mean upper Floridan aquifer TP concentration contour map for water year 2001.
















































Figure B-1B. Mean upper Floridan aquifer TP concentration contour map for water year 2002.












Mean Total Phosphorus Concentrati'on (mg/L)

October 2002 to September 2003


5 to 10


0 5tol1


01 to 05


TP (mg/L)
0 05 to 0 1 is a measure of the
amount of total
phosphorus in the ground water.
O 01 to 0 05


|0to 001


Figure B-1C. Mean upper Floridan aquifer TP concentration contour map for water year 2003.












Mean Total Phosphorus Concentration (mg/L)

October 2003 to September 2004


5 to 10


0 5tol1


01 to 05


TP (mg/L) 1
0 05 to 0 1 is a measure of the
amount of total
phosphorus in the ground water.
O 01 to 0 05


0 to 0 01


Figure B-1D. Mean upper Floridan aquifer TP concentration contour map for water year 2004.












Mean Total Phosphorus Concentration (mg/L)

October 2004 to September 2005


5 to 10


11 to 5


|05 tol1


10 1 to 0 5


TP (mg/L)
0 05 to 0 1 is a measure of the
amount of total
phosphorus in the ground water.
O 01 to 0 05


0 to 0 01


Figure B-1E. Mean upper Floridan aquifer TP concentration contour map for water year 2005.












Mean Nitrate Nitrogen Concentration (m g/L)

October 2000 to September 2001


20Oto 40


10Oto 20


Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


Note


0 to 0 05


Figure B-2A. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2001.












Mean Nitrate Nitrogen Concentration (m g/L)

October 2001 to September 2002


O to 40


O to 20


Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


Note


|0 to 0 05


Figure B-2B. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2002.












Mean Nitrate-Nitrogen Concentration (m g/L)

October 2002 to September 2003


Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


|0 to 0 05


Figure B-2C. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2003.












Mean Nitrate-Nitrogen Concentration (m g/L)

October 2003 to September 2004


Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


|0 to 0 05


Figure B-2D. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2004.












Mean Nitrate-Nitrogen Concentration (mg/L)

October 2004 to September 2005


O to 40


O to 20


Nitrate-nitrogen (mg/L)
is a measure of the amount
0 5 to 1 0 of nitrate dissolved in the
ground water expressed in
terms of the amount of
nitrogen in the form of
nitrate.
0 05 to 05


|0 to 0 05


Figure B-2E. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2005.











Mean Potassium Concentration (m g/L)

O~cto~ber 2000 to September 2001


50
40
10
5.1
2.65
1.425


0.2
S 0820.175
0.15
0.125
0.1
0.05
t0.025


K (mglL)
is a measure of the
amount of dissolved
potassium In the ground water.


Il:li


Figure B-3A. Mean upper Floridan aquifer K concentration contour map for water year 2001.












Mean Potassium Concentration (m g/L)

O~cto~ber 2001 to September 2002


50
40
10
5.1
2.65
1.425


0.2
0.175
0.15
0.125
0.1
0.05
t0.025


K (mglL)
is a measure of the
amount of dissolved
potassium In the ground water.


"ll


Figure B-3B. Mean upper Floridan aquifer K concentration contour map for water year 2002.













Mean Potassium Concentration (m g/L)

O~ctfober 2002 to S tfember 2003


50
40




2.65
1.425


0.2
0.175
0.15
0.125
0.1
-0.05
-0.025
-0


K (mglL)
is a measure of the
amount of dissolved
potassium In the ground water.


Figure B-3C. Mean upper Floridan aquifer K concentration contour map for water year 2003.









Mean Potassium Concentration (mg/)


I '
Figure B-3D. Mean upper Floridan aquifer K concentration contour map for water year 2004.


I


October 2003 to September 2004 :











50



5.1
2.65
1.425
K (mglL)
0.2 is a measure of the
amount of dissolved T. 4
0.15 potassium In the ground water.
0.125
0.1
Note
0.05 This map represents aenrlzto
of groundwater quality
-0.025











Mean Potassium Concentration (mg/L)

October 2004 to September 2005


K (mg/L)
is a measure of the
amount of dissolved
potassium In the ground water.


0.125
0.1
0.05
0.025


i~..-..


Figure B-3E. Mean upper Floridan aquifer K concentration contour map for water year 2005.


50
40
10
5.1
2.65
1.425
0.2
0.15



























































/ County Boundaries
SSuwannee Reach 1
O Suwannee Reach 2
i Suwannee Reach 3
e0 Santa Fe Reach 1
I Santa Fe Reach 2
O Suwannee Reaches 4, 5 &6
SAlapaha river Watershed
II Withlacoochee river Watershed


Figure B-4A. Suwannee River Basin loading by watershed/reach for water year 1998.


AnulNitrate-N Load
AnulTotal Phosphorus Load























































T ota Phs rus Load y



/VCounty Boundaries
Suwannee Reach i
SSuwannee Reach 2
B Suwannee Reach 3
CZ Santa Fe Reach 1
It Santa Fe Reach 2
O Suwannee Reaches 4, 5 & 6
SAlapaha river Watershed
I Withlacoochee river Watershed


Figure B-4B. Suwannee River Basin loading by watershed/reach for water year 1999.

















































/ County Boundaries
Suwannee Reach 1
Suwannee Reach 2
SSuwannee Reach 3
Santa Fe Rea ch 1
SSn F e Suwannee Reaches 4, 5, & 6
Ht Alapaha River Watershed
Withlacoochee River Watershed


Ania,~~ t~lltidLJs Lst d
AnulTotal Phosphorus Load


Figure B-4C. Suwannee River Basin loading by watershed/reach for water year 2000.


229


Total Loadings foit .I
Water Year 2000 /
S2.Q5il&DA hgLxt

327,600 kg lyr 6 J




























































/V County Boundaries
Suwannee Reach 1
Suwannee Reach 2
I Suwannee Reach 3
Santa Fe Reach 1
B at eRahSuwannee Reaches 4, 5, & 6
WAlapaha River Watershed
Withlacoochee River W~atershed


Figure B-4D. Suwannee River Basin loading by watershed/reach for water year 2001.


230


Al ia aemi-N JLnil
Manual Total Phosphorus Load
























































A nnual e- T odotal Phosphorus Load



\/ County Boundaries
SSuwannee Reach 1
O Suwannee Reach 2
O Suwannee Reach 3
Santa Fe Reach 1
SSanta Fe Reach 2
Suwannee Reach 4
SSuwannee Reaches 5 & 6
SAlapaha river Watershed
M Withlacoochee river Watershed


Figure B-4E. Suwannee River Basin loadings by watershed/reach for water year 2002.



















































Ann~ua l TtlPospru Load


/ County Boundaries
SSuwannee Reach i
0 Suwannee Reach 2
O Suwannee Reach 3
Cj Santa Fe Reach 1
II Santa Fe Reach 2
O Suwannee Reach 4
0 Suwannee Reaches 5 & 6
rr Alapaha River Watershed
SWithlacoochee River Watershed


Figure B-4F. Suwannee River Basin loading by watershed/reach for water year 2003.






















































AnulNitrate-N Load
AnulTotal Phosphorus Load



/ County Boundaries
SSuwannee Reach 1
O Suwannee Reach 2
O Suwannee Reach 3
0 Santa Fe Reach 1
I Santa Fe Reach 2
SSuwannee Reach 4
O Suwannee Reaches 5& 6
SAlapaha river Watershed
rC Withlacoochee river Watershed


Figure B-4G. Suwannee River Basin loading by watershed/reach for water year 2004.











APPENDIX C
SELECTED MIDDLE SUWANNEE SPRINGS


6.0





5.0





4.0





S3.0





2.0





1.0





0.0


2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0

NOx-N (mg/L)


Figure C-1. Plot of NO3-N versus K concentrations for spring SUW718971.













6.0





5.0**





4.0


E 3.+






y = 0.2499x 0.006
R2 = 0.7016
2.0





1.0







4 6 8 10 12 14 16 18 20

NOx-N (mg/L)


Figure C-2. Plot of NO3-N versus K concentrations for spring SUW725971.











APPENDIX D
WATER QUALITY SUMMARY BY GROUNDWATER DOMAINS


Table D-1. Groundwater quality statistical summary by groundwater domain.


Standard
Deviation
1.08
2.31
1.40
1.67
4.02
7.77
5.25
7.93
6.89


25'"
Percentile
20.90
20.40
20.60
20.93
21.60
21.77
20.90
21.20
22.89

240.0
217.0
340.0
410.5
284.0
258.8
341.0
284.0
329.5

7.14
6.52
6.70
6.53
7.01
7.18
6.47
6.81
6.75


Variable
Temperature












Specific Conductance












pH


Units
oC


Basin
Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Stein hatchee
Suwannee
Waccasassa


Mean
21.42
20.72
21.56
22.22
21.17
19.60
20.18
20.80
21.26

375.1
273.1
499.9
474.7
361.8
294.2
461.8
360.9
370.2

7.33
9.60
6.88
6.77
7.03
7.04
6.63
7.58
6.86


Median
21.20
21.00
21.80
21.90
22.00
22.64
21.20
21.99
23.08

363.0
258.5
396.0
475.5
334.0
301.5
469.0
358.5
353.0

7.24
6.90
6.85
6.80
7.33
7.37
6.77
7.10
7.01


Percentile
21.70
21.40
22.40
23.70
22.56
23.17
21.80
22.70
23.57

498.0
344.5
497.0
534.0
420.0
355.0
541.0
440.0
537.0

7.50
7.31
7.14
6.99
7.53
7.53
6.98
7.33
7.24


Minimum
17.70
0.00
16.90
18.80
0.00
0.00
0.00
0.00
0.00

6.0
0.0
174.0
385.0
0.0
0.0
0.0
0.0
0.0

6.58
0.00
5.50
5.72
0.00
0.00
0.00
0.00
4.22


Maximum
24.00
23.60
27.50
24.30
24.14
24.56
25.83
225.00
30.02

695.0
695.0
2301.0
590.0
1170.0
617.0
2714.0
1815.0
588.0

8.05
542.00
8.02
7.76
8.67
8.42
7.64
586.00
7.68


p~mho cml Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


141.9
129.4
373.0
62.4
140.0
103.7
273.0
171.6
183.5

0.29
39.05
0.43
0.44
1.30
1.59
0.91
19.33
0.69


Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa











Table D-1. continued.


25tn
Pe rce nti le
0.15
0.55
1.00
0.28
0.24
0.24
3.80
0.35
1.72


75tn
Median Percentile


Standard
Deviation
3.30
45.98
19.86
1.19
11.22
7.53
103.38
51.95
9.46

86.85
80.83
4395.00
91.90
100.08
45.55
359.50
299.10
79.30


75.20
77.38
57.95
76.00
48.62
41.10
89.45
62.57
76.20


Variable
Turbidity


Units Basin
NTU Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L' Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
2.34
12.28
14.86
1.14
3.94
2.33
29.50
13.30
8.62

230.20
168.47
1002.00
239.40
222.09
170.29
326.80
231.40
228.70


190.99
135.80
197.62
208.40
161.38
141.23
234.48
171.03
211.20


Minimum Maximum


0.85
4.63
11.00
0.85
0.75
0.64
9.00
1.55
4.03

217.00
145.00
234.00
265.00
204.00
173.00
319.00
208.00
200.50


174.00
124.50
190.00
237.50
164.00
142.00
275.00
176.00
184.50


3.60
10.33
16.50
1.68
3.00
1.65
18.10
7.80
15.45

293.00
204.50
291.00
295.00
250.00
201.00
345.00
260.00
302.00


243.00
178.75
265.00
255.80
188.00
163.00
293.00
211.00
283.00


0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00


18.20
508.00
110.00
4.90
175.00
77.50
986.00
750.00
44.50


Total Dissolved Solids












Alkalinity


149.50
123.00
201.00
232.80
169.00
144.00
211.00
168.30
176.50


125.00
89.03
141.50
201.80
132.00
127.75
184.00
139.00
173.50


102.00
22.00
120.00
0.00
0.00
40.00
0.00
0.00
26.00


52.50
0.30
88.00
0.00
0.00
15.00
0.00
0.00
5.60


480.00
440.00
36800.00
325.00
972.00
312.00
4040.00
10200.00
341.00


369.00
359.00
310.00
270.00
294.00
343.00
660.00
486.00
293.00











Table D-1. continued.

Variable
Total Organic carbon


25tn
Percentile
0.68
0.64
0.75
0.60
0.38
0.38
3.07
0.59
1.06


75tn
Median Percentile


Standard
Deviation
2.78
5.36
4.75
1.03
3.13
2.18
12.29
5.45
2.67


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
2.54
3.33
4.40
1.31
1.76
1.47
11.44
2.93
3.24

3.11
4.14
5.44
3.39
2.52
2.82
11.74
3.98
4.74


Minimum Maximum


1.70
1.13
2.48
1.18
0.71
0.64
8.30
1.10
2.68

2.37
2.08
4.44
1.69
1.14
1.82
8.30
1.96
5.04

1.31
0.33
0.26
0.05
0.51
0.30
0.18
0.41
0.17


3.71
3.48
7.94
2.07
1.79
1.63
16.60
3.00
5.61

4.29
4.92
8.08
4.51
2.92
4.20
17.54
4.71
6.45

1.62
0.44
0.40
0.15
0.90
0.68
0.51
0.81
1.27


0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.38
0.38
0.80
0.85
0.00
0.38
0.00
0.00
0.85

0.14
0.01
0.05
0.02
0.05
0.01
0.00
0.00
0.05


15.90
33.20
21.20
3.99
35.20
20.64
79.60
57.20
10.80

16.00
48.40
19.50
19.10
34.70
21.07
56.76
61.60
18.70

2.80
4.22
243.00
0.16
49.30
16.70
68.10
200.00
1.55


mg L 1


Dissolved Organic carbon


Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


2.75
5.76
4.45
4.22
3.47
2.66
9.87
5.93
3.67


1.00
0.91
1.53
0.85
0.85
0.85
4.04
0.85
1.51

0.49
0.21
0.17
0.04
0.28
0.16
0.11
0.20
0.13


mg L


Potassium


1.13
0.37
7.57
0.08
0.76
0.67
1.08
1.26
0.63


0.59
0.35
38.75
0.05
2.29
1.62
6.00
6.07
0.60











Table D-1. continued.


25tn
Pe rce nti le
3.14
2.36
3.13
6.90
2.97
2.47
3.94
2.52
2.99


75tn
Median Percentile


Standard
Deviation
6.01
15.67
785.20
2.50
4.43
2.10
67.51
16.04
1.11


Variable
Sodium


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
7.25
5.82
156.10
8.08
5.79
4.00
14.65
5.44
3.95

14.12
7.94
32.35
1.34
8.81
5.21
7.77
7.02
8.83

54.16
43.18
64.60
94.98
59.27
51.54
80.67
67.48
69.46


Minimum Maximum


4.30
2.80
3.54
7.92
4.30
2.98
4.45
3.11
3.18


10.45
3.39
4.67
9.52
6.52
6.04
5.00
4.56
5.16

25.50
7.32
20.25
1.46
14.80
7.72
10.40
9.05
9.75

66.75
62.60
80.15
101.75
74.30
63.98
107.00
83.80
96.23


0.94
0.71
2.77
1.79
0.38
0.42
0.00
0.04
2.20


21.50
107.00
4800.00
13.60
23.00
13.50
722.00
329.00
5.64

41.10
41.70
536.00
1.86
32.80
17.80
28.80
290.00
10.40

86.30
112.00
221.00
108.00
215.00
118.00
138.00
913.00
105.00


Magnesium












Calcium


11.77
8.60
74.05
0.22
7.56
4.68
4.76
11.27
2.32

17.62
23.11
26.80
9.89
27.59
16.41
35.03
43.37
27.61


3.63
2.41
16.05
1.20
2.81
1.48
3.86
1.98
9.01

40.20
32.10
47.65
89.90
40.40
39.83
67.60
48.30
54.30


10.50
4.50
18.40
1.37
5.45
3.53
7.86
4.27
9.30

59.90
39.10
56.50
96.15
52.30
52.90
95.10
62.70
58.50


1.17
0.00
10.50
0.87
0.03
0.35
0.00
0.03
0.49

7.14
0.09
22.70
67.80
3.52
6.70
0.00
0.02
0.66


mg L 1


Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa











Table D-1. continued.


25tn
Pe rce nti le
3.65
3.97
5.32
10.13
4.66
4.80
6.97
4.19
4.98


75tn
Median Percentile


Standard
Deviation
3.58
1.88
1496.00
5.63
11.29
3.64
56.51
11.64
1.44


Variable
Chloride


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
6.36
4.94
292.00
11.66
9.41
6.93
17.93
7.66
6.06

0.29
0.21
0.61
0.05
0.20
0.14
0.12
0.11
0.15

9.28
2.25
53.40
7.93
15.80
3.92
2.34
11.85
1.18


Minimum Maximum


6.07
4.51
5.99
11.70
5.93
5.48
8.15
5.44
5.54

0.32
0.16
0.20
0.04
0.15
0.10
0.11
0.10
0.14

5.27
1.72
6.38
7.82
4.86
4.18
0.96
6.37
0.53


8.46
5.43
6.96
15.13
8.46
7.37
9.43
7.87
7.44

0.45
0.27
0.25
0.06
0.31
0.22
0.15
0.15
0.18

11.50
3.09
40.20
9.89
10.60
5.51
3.53
13.30
1.30


1.56
1.62
3.22
0.00
0.00
0.15
0.00
0.00
3.00

0.02
0.02
0.03
0.00
0.00
0.02
0.00
0.00
0.05

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00


30.10
18.20
9870.00
21.90
76.10
24.30
457.00
222.00
9.02

0.78
0.76
29.90
0.17
0.84
0.51
0.53
1.14
0.25

99.10
18.30
1140.00
18.70
271.00
13.20
22.40
52.00
19.60


Fluoride












Sulfate


0.18
0.14
3.15
0.04
0.15
0.09
0.09
0.09
0.05

14.22
2.56
191.00
4.39
40.20
2.55
3.71
3.56
2.93


0.11
0.11
0.14
0.02
0.07
0.07
0.06
0.05
0.11

2.05
0.40
1.01
6.99
1.92
1.88
0.18
2.48
0.18











Table D-1. continued.


25tn
Pe rce nti le
0.02
0.03
0.04
0.01
0.02
0.03
1.28
0.03
0.50


75tn
Median Percentile


Standard
Deviation
0.43
4.55
1.63
0.88
0.91
1.46
2.47
4.07
1.14


Variable
Iron


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
0.25
1.26
1.32
0.21
0.31
0.31
2.70
1.02
1.62

0.003
0.004
0.003
0.002
0.003
0.002
0.003
0.005
0.002

0.18
0.62
0.09
0.02
0.62
1.41
0.03
1.69
0.01


Minimum Maximum


0.08
0.49
0.72
0.01
0.06
0.10
1.68
0.13
1.72

0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003

0.01
0.03
0.02
0.02
0.25
1.21
0.01
0.31
0.01


0.36
1.48
2.45
0.02
0.23
0.25
3.57
0.97
2.63

0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003

0.09
0.62
0.11
0.03
0.73
1.62
0.03
1.31
0.01


0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.42


2.84
54.10
9.01
3.94
12.50
16.70
15.50
131.00
4.46

0.025
0.043
0.009
0.003
0.064
0.010
0.064
2.100
0.006

3.94
4.16
1.05
0.07
27.20
10.60
0.73
488.00
0.09


Lead


0.002
0.006
0.001
0.001
0.003
0.002
0.007
0.058
0.001

0.56
1.12
0.17
0.02
1.74
1.73
0.09
13.79
0.02


0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002

0.00
0.01
0.00
0.00
0.01
0.02
0.00
0.02
0.00


0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00


mg L 1


Nitrate+N itrite-N~itrogen


Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa











Table D-1. continued.


25tn
Pe rce nti le
0.14
0.11
0.16
0.11
0.11
0.11
0.30
0.11
0.20


75tn
Median Percentile


Standard
Deviation
0.37
0.37
0.87
0.13
0.23
0.33
0.70
0.44
0.23


Variable
TKN


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L' Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
0.36
0.33
0.52
0.20
0.24
0.24
0.69
0.32
0.40


0.13
0.06
0.18
0.03
0.06
0.06
0.16
0.09
0.19

0.087
0.325
0.258
0.028
0.144
0.102
2.610
0.321
0.195


Minimum Maximum


0.26
0.24
0.30
0.17
0.18
0.15
0.53
0.20
0.37


0.04
0.04
0.04
0.04
0.04
0.04
0.12
0.04
0.18

0.070
0.133
0.151
0.030
0.053
0.055
0.068
0.070
0.196


0.50
0.37
0.56
0.25
0.31
0.27
0.91
0.38
0.60


0.10
0.05
0.20
0.04
0.06
0.04
0.22
0.09
0.31

0.109
0.480
0.522
0.042
0.100
0.105
0.461
0.145
0.209


0.04
0.04
0.05
0.05
0.04
0.04
0.00
0.00
0.05


2.43
3.00
6.00
0.60
2.00
3.70
5.22
8.50
0.94


Ammonia-nitrogen












Total Phosphorus


0.30
0.08
0.58
0.03
0.10
0.22
0.15
0.33
0.16

0.087
0.545
0.228
0.019
0.359
0.204
9.960
1.758
0.037


0.04
0.02
0.02
0.02
0.02
0.02
0.04
0.02
0.04

0.040
0.050
0.081
0.010
0.035
0.040
0.040
0.044
0.189


0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.078


2.40
0.50
5.25
0.10
1.01
3.54
0.59
10.10
0.61

0.598
4.870
0.814
0.056
3.640
2.240
25.000
45.100
0.303











Table D-1. continued.


25tn
Pe rce nti le
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000


75tn
Median Percentile


Standard
Deviation
0.001
0.002
0.001
0.001
0.001
0.002
0.002
0.007
0.002


Variable
Cadmium


Units Basin
mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


mg L1 Alapaha
Aucilla
Coastal
Dixie
Ichetucknee
Santa Fe
Steinhatchee
Suwannee
Waccasassa


Mean
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002
0.002

0.009
0.011
0.010
0.009
0.010
0.009
0.011
0.011
0.010


Minimum Maximum


0.002
0.002
0.001
0.002
0.002
0.002
0.002
0.002
0.002

0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010


0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003
0.003

0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010


0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000


0.004
0.007
0.004
0.004
0.004
0.005
0.010
0.257
0.004

0.023
0.050
0.023
0.023
0.037
0.050
0.100
0.286
0.023


Arsenic


0.006
0.007
0.006
0.006
0.007
0.008
0.014
0.013
0.006


0.005
0.009
0.007
0.005
0.005
0.005
0.005
0.005
0.009










Table D-2A. The Kruskal-Wallis Test for the groundwater domains differences using nine domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0.005 794.4 -8.45
Aucilla 188 0.033 1180.2 -2.90
Coastal 93 0.018 822.6 -6.55
Dixie 20 0.017 657.5 -3.95
Ichetucknee 479 0.253 1318.3 -0.60
Santa Fe 262 1.205 1681.9 7.60
Steinhatchee 131 0.010 684.7 -9.92
Suwannee 1320 0.306 1495.0 10.41
Waccasassa 44 0.005 476.6 -7.46
Overall 2674 1337.5


388.20
388.93


DF = 8
DF= 8


0.000
0.000


(adjusted for ties)


Table D-2B. The Kruskal-Wallis
Groundwater Domain N
Alapaha 137
Aucilla 188
Coastal 93
Dixie 20
Ichetucknee 479
Steinhatchee 131
Suwannee 1320
Waccasassa 44
Overall 2414


Test for the
Median
0.005
0.033
0.018
0.017
0.253
0.010
0.306
0.005


groundwater domains differences using eight domains.
Ave Rank Z
738.8 -8.09
1097.5 -2.23
767.4 -6.20
609.2 -3.85
1232.2 0.90
635.7 -9.65
1383.4 13.71
442.4 -7.35
1206.5


344.82
345.52


DF = 7
DF = 7


0.000
0.000


(adjusted for ties)











Table D-2C. The Kruskal-Wallis Test for the groundwater domains differences using seven domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0.005 604.4 -7.89
Aucilla 188 0.033 884.2 -2.14
Coastal 93 0.018 631.9 -5.93
Dixie 20 0.017 504.9 -3.72
Steinhatchee 131 0.010 525.5 -9.38
Suwannee 1320 0.306 1110.9 16.64
Waccasassa 44 0.005 365.1 -7.24
Overall 1933 967.0

H = 330.08 DF = 6 P = 0.000
H = 330.77 DF = 6 P = 0.000 (adjusted for ties)


Table D-2D. The Kruskal-Wallis Test for the groundwater domains differences using six domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0.005 287.4 -1.47
Aucilla 188 0.033 376.1 6.42
Coastal 93 0.018 307.1 0.00
Dixie 20 0.017 264.6 -1.09
Steinhatchee 131 0.010 271.4 -2.60
Waccasassa 44 0.005 198.1 -4.23
Overall 613 307.0

H = 53.36 DF = DF= 5 P = 0.000
H = 53.99 DF = DF= 5 P = 0.000 (adjusted for ties)










Table D-2E. The Kruskal-Wallis Test for the groundwater domains differences using five domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0.005 221.0 0.92
Coastal 93 0.018 236.9 2.12
Dixie 20 0.017 203.7 -0.35
Steinhatchee 131 0.010 209.0 -0.45
Waccasassa 44 0.005 154.0 -3.37
Overall 425 213.0


14.50
14.73


DF = 4
DF = 4


P= 0.006
P= 0.005


(adjusted for ties)


Table D-2F. The Kruskal-Wallis Test for the groundwater domains differences using four domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0.005 176.8 1.63
Dixie 20 0.017 166.2 -0.01
Steinhatchee 131 0.010 169.9 0.52
Waccasassa 44 0.005 124.6 -3.11
Overall 332 166.5


10.11
10.29


DF = 3
DF = 3


P= 0.018
P= 0.016


(adjusted for ties)










Table D-2G. The Kruskal-Wallis Test for the groundwater domains differences using three domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 1 37 0 0.005 165.9 1.64
Steinhatchee 1 31 0 0.010 159.8 0.55
Waccasassa 44 0 0.005 117.3 -3.11
Overall 3 12 156.5

H = 9.98 DF = 2 P= 0.007
H = 10.16 DF = 2 P= 0.006 (adjusted for ties)


Table D-2H. The Kruskal-Wallis Test for the groundwater domains differences using two domains.
Groundwater Domain N Median Ave Rank Z
Alapaha 137 0 5000.000 97.2 2.81
Waccasassa 44 0 5000.000 -71.7 2.81
Overall 181 91.0

H = 7.88 DF = 1 P= 0.005
H = 8.10 DF = 1 P= 0.004 ( (adjusted for ties)











































-20- Potentiometric Contour
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure D-1. 1985 potentiometric surface map for the Suwannee River Water Management District (Rosenau and Meadows, 1986).









































-20- Potentiometric Contour
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure D-2. 1990 potentiometric surface map for the Suwannee River Water Management District (Meadows, 1991).











































-20- Potentiometric Contour-
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure D-3. 1995 potentiometric surface map for the Suwannee River Water Management District (Mahon et al., 1996).









































-20- Potentiometric Contour
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure D-4. 2002 potentiometric surface map for the Suwannee River Water Management District (SRWMD, 2002).








































-20- Potentiometric Contour
Groundwater level in feet above msl.
Contour intervals 10 feet


Figure D-5. 2005 potentiometric surface map for the Suwannee River Water Management District (SRWMD, 2005).










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BIOGRAPHICAL SKETCH

H. David Hornsby was born on October 4, 1966, in Baton Rouge, Louisiana. David

received a bachelor' s in chemistry from the University of Florida in 1991. He earned a Master of

Science in soil and water science with a minor in environmental engineering sciences from the

University of Florida in 1994. He worked for the Suwannee River Water Management District

from 1994 to 2005 as a water quality analyst and a water resources scientist, for the Florida

Department of Environmental Protection from 2005 to 2007 as an environmental administrator

and the St. Johns River Water Management District starting 2007as a water supply planning

proj ect manager.





PAGE 1

1 INFLUENCES ON THE DISTRIBUTION AND OCCURRENCE OF NITRATE-NITROGEN AND TOTAL PHOSPHORUS IN THE WATER RESOURCES OF THE SUWANNEE RIVER WATER MANAGEMENT DISTRICT By H. DAVID HORNSBY A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2007

PAGE 2

2 2007 H. David Hornsby

PAGE 3

3 To my wife, Jennifer, my children Laure n, Jenna, and Kyra, and the Suwannee River

PAGE 4

4 ACKNOWLEDGMENTS I thank my advisor, Dr. Donald Graetz, fo r his guidance, assistance and encouragement through out this study. I thank my committee members, Dr. Thomas Obreza, Dr. Wendy Graham, Dr. Vimala Nair and Dr. Sam Upchurch, for their valuable suggestions and guidance. I thank the Florida Geological Survey and Florida Department of Environmental Protection for providing personnel and equipment for field sampling. I especially thank Rick Copeland, Tom Greenhalgh and Harley Means of th e Florida Geological Survey and Rick Hicks of the Department of Environmental Protec tion for their assistance with this study. I thank the Suwannee River Water Management District for providing me the opportunity to work on one of the most unique an d wonderful systems in the world. I thank my wife for her support and encouragement during this journey.

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5 TABLE OF CONTENTS Page ACKNOWLEDGMENTS ...............................................................................................4 LIST OF TABLES ...........................................................................................................7 LIST OF FIGURES .........................................................................................................12 LIST OF ABBREVIATIONS ..........................................................................................19 ABSTRACT .....................................................................................................................2 2 CHAPTER 1 INTRODUCTION ...............................................................................................24 2 LITERATURE REVIEW ....................................................................................27 Overview of the Suwannee River Basin ..............................................................27 Location ............................................................................................................27 Hydrology .........................................................................................................27 Physiography.....................................................................................................29 Soils...................................................................................................................30 Hydrogeology ...................................................................................................33 Land Use Overview ..........................................................................................34 Water Quality Characteristics ...........................................................................35 Nutrients ...............................................................................................................37 Phosphorus ........................................................................................................37 Phosphorus cycle ........................................................................................38 Occurrence of phosphorus in groundwater .................................................39 Concerns with phosphorus ..........................................................................39 Water quality standards for phosphorus .....................................................40 Nitrogen ............................................................................................................40 Nitrogen cycle .............................................................................................41 Occurrence of nitrate-nitrogen ....................................................................42 Concerns with nitrate-nitrogen ...................................................................43 Water quality standards for nitrate-nitrogen ...............................................44 Water Quality Assessments ....................................................................................45 Groundwater Domain Delineation ..........................................................................49 3 COMPARISONS OF PRE AND POST OUTSTANDING FLORIDA WATER CONCENRATIONS, TRENDS AND RECENT OCCURRENCES OF TOTAL PHOSPHORUS AND NITRATENITROGEN CONCENTRATIONS ....................................................................63 Introduction ..........................................................................................................63 Materials and Methods .........................................................................................65

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6 Long Term Trend Analysis ...............................................................................65 Recent Distribution and Occurrenc es of Total Phosphorus and Nitrate-Nitrogen ................................................................................................65 Results and Discussion ........................................................................................66 Long Term Trend ..............................................................................................66 Comparison of Pre and Po st OFW Water Quality ............................................67 Anthropogenic Factors ......................................................................................68 Recent Distribution and Occurrenc es of Total Phosphorus and Nitrate-Nitrogen ................................................................................................71 Upper Floridan aquifer water quality ..........................................................71 Spring water quality ....................................................................................73 Surface water quality ..................................................................................74 Summary and Conclusions ..................................................................................76 4 NITRATE-NITROGEN LOADING FROM GROUND WATER TO SELECTED REACHES OF THE SUWA NNEE AND SANTA FE RIVERS ..107 Introduction ..........................................................................................................107 Materials and Methods .........................................................................................109 Results and Discussion ........................................................................................111 Middle Suwannee River Basin..........................................................................111 Lower Santa Fe River Basin .............................................................................115 Summary and Conclusions ..................................................................................119 5 GROUNDWATER DOMAIN DELI NEATION AND LANDUSE INFLUENCES ON GROUNDWATER QUALITY ...........................................146 Introduction ..........................................................................................................146 Materials and Methods .........................................................................................151 Results and Discussion ........................................................................................152 Summary and Conclusions ..................................................................................158 6 SYNTHESIS ........................................................................................................185 APPENDIX A HISTORICAL TOTAL PHOSPHOR US AND NITRATE-NITROGEN ...........189 B WATER QUALITY SUMMARY .......................................................................192 C SELECTED MIDDLE SUWANNEE SPRINGS ................................................234 D WATER QUALITY SUMMARY BY GROUNDWATER DOMAINS ............236 REFERENCE LIST .........................................................................................................253 BIOGRAPHICAL SKETCH ...........................................................................................262

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7 LIST OF TABLES Table Page 2-1 Reaches of the Suwannee River. ..............................................................52 2-2 National NO3-N concentrations in 383 U.S. Rivers. ..............................52 2-3 Tidal-freshwater water quality indices based on NO3-N concentration. ..........................................................................................52 3-1 Comparison of pre and post OF W concentrations of TP and NO3-N to OFW baseline concentrations of TP and NO3-N for the Suwannee River at Branford. ....................................................................................78 3-2 Comparison of baseline annual NO3-N load to water years 1998 to 2005 annual NO3-N load. .........................................................................78 3-3 Cross correlation of N fertilizer sales and annual median riverine NO3-N concentration for the Suwannee River at Branford. ....................79 3-4 Summary of NO3-N and TP concentrations in the upper Floridan aquifer for the Suwannee River Water Management District (2001 to 2006). ........................................................................................79 3-5 Summary of NO3-N and TP concentrations for the Springs by River Basin in the Suwannee Rive r Water Management District (1989 to 2006). ........................................................................................80 3-6 Summary of NO3-N and TP concentrations for each River Basin (1989 to 2006). ..............................................................................81 3-7 TP and NO3-N Loadings by Watersheds/Reach in the Suwannee River for water year 2005. ......................................................................82 4-1 Suwannee River and Santa Fe River se gments used in this study along with sampling dates and other pertinent information. ............................121 4-2 Middle Suwannee River Basin spring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the study reach.. ..............................122 4-3 Middle Suwannee River Basin NO3-N change profile 2000 and 2006. ..123 4-4 Lower Santa Fe River Basin NO3-N change profile 2001 and 2006. ......123

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8 Table Page 4-5 Lower Santa Fe Ri ver Basin refined NO3-N change profile for 2006. ....123 4-6 Lower Santa Fe River Basin spring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the study reach .....................................124 4-7 Discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the st udy reach for Lower Santa Fe River Basin springs in refined segments (October 10, 2006). ...........125 5-1 Principal component analysis showing significant components ..............159 5-2 Statistical summary for NO3-N and TP by groundwater domain. ..........160 5-3 1995 level 2 Florida Landuse Code for the Alapaha groundwater domain. ..............................................................................161 5-4 1995 level 2 Florida Landuse Code for the Aucilla groundwater domain. ..............................................................................162 5-5 1995 level 2 Florida Landuse Code for the Coastal groundwater domain. ..............................................................................163 5-6 1995 level 2 Florida Landuse Code for the Dixie groundwater domain. ..............................................................................164 5-7 1995 level 2 Florida Landuse Code for the Ichetucknee groundwater domain. ..............................................................................165 5-8 1995 level 2 Florida Landuse Code for the Santa Fe groundwater domain. ..............................................................................166 5-9 1995 level 2 Florida Landuse Code for the Steinhatchee groundwater domain. ..............................................................................167 5-10 1995 level 2 Florida Landuse Code for the Suwannee groundwater domain. ..............................................................................168 5-11 1995 level 2 Florida Landuse Code for the Waccasassa groundwater domain. ..............................................................................169 B-1 Summary of upper Floridan groundwater quality for the Suwannee River Water Management District (2001 to 2006). ................................192

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9 Table Page B-2 Summary of water quality parameters for the Springs of Aucilla River Basin (1989 to 2006). .....................................................................193 B-3 Summary of water quality paramete rs for the Springs of Coastal Rivers Basin (1989 to 2006). ...................................................................194 B-4 Summary of water quality parame ters for the Springs of Lower Suwannee River Basin (1989 to 2006). ...................................................195 B-5 Summary of water quality paramete rs for the Springs of Santa Fe River Basin (1989 to 2006). .....................................................................196 B-6 Summary of water quality parame ters for the Springs of Upper Suwannee River Basin (1989 to 2006). ...................................................197 B-7 Summary of water quality parameters for the Springs of Waccasassa River Basin (1989 to 2006). .....................................................................198 B-8 Summary of water quality parameters for the Springs of Withlacoochee River Basin (1989 to 2006). ............................................199 B-9 Summary of surfacewater quality parameters for the Alapaha River Basin (1989 to 2006). .....................................................................200 B-10 Summary of surfacewater quality parameters for the Aucilla River Basin (1989 to 2006). .....................................................................201 B-11 Summary of surfacewater quality pa rameters for the Coastal Rivers Basin (1989 to 2006). ...............................................................................202 B-12 Summary of surfacewater quality parameters for the Lower Suwannee River Basin (1989 to 2006). ...................................................203 B-13 Summary of surfacewater quality pa rameters for the Santa Fe River Basin (1989 to 2006). ...............................................................................204 B-14 Summary of surfacewater quality parameters for the Upper Suwannee River Basin (1989 to 2006). ...................................................205 B-15 Summary of surfacewater quality parameters for the Waccasassa River Basin (1989 to 2006). .....................................................................206 B-16 Summary of surfacewater quality parameters for the Withlacoochee River Basin (1989 to 2006). .....................................................................207

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10 Table Page B-17A TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 1998. .................................................................................208 B-17B TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 1999. .................................................................................208 B-17C TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 2000. .................................................................................209 B-17D TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 2001. .................................................................................209 B-17E TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 2002. .................................................................................210 B-17F TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 2003. .................................................................................210 B-17G TP and NO3-N loadings by watersheds/rea ch in the Suwannee River for water year 2004. .................................................................................211 D-1 Groundwater quality statistical summary by groundwater domain. ........236 D-2A. The Kruskal-Wallis Test for the groundwater domains differences using nine domains. .................................................................................244 D-2B. The Kruskal-Wallis Test for the groundwater domains differences using eight domains. ................................................................................244 D-2C. The Kruskal-Wallis Test for the groundwater domains differences using seven domains. ...............................................................................245 D-2D. The Kruskal-Wallis Test for the groundwater domains differences using six domains. ....................................................................................245 D-2E. The Kruskal-Wallis Test for the groundwater domains differences using five domains. ..................................................................................246 D-2F. The Kruskal-Wallis Test for the groundwater domains differences using four domains. ..................................................................................246 D-2G. The Kruskal-Wallis Test for the groundwater domains differences using three domains. ................................................................................247

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11 Table Page D-2H. The Kruskal-Wallis Test for the groundwater domains differences using two domains. ..................................................................................247

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12 LIST OF FIGURES Figure Page 1-1 Basins of the Suwannee River System. ..........................................................26 2-1 Physiography regions of the Suwann ee River Water Management District. ...53 2-2 High leaching soils in the Suwannee River Water Management District. ........54 2-3 Generalized geologic cro ss section of the region. ...........................................55 2-4 Confined and unconfined regions of the Floridan aquifer system. ..................56 2-5 Map showing the reaches of the Suwannee River in Florida. ..........................57 2-6 Plot of mean alkalinity (mg L-1 as CaCO3) in the five reaches of the Suwannee River in Florida. ..............................................................................58 2-7 Plot of mean color (PCU) in the five reaches of the Suwannee River in Florida. .........................................................................................................58 2-8 P cycle in soils. ................................................................................................59 2-9 N cycle in soils. ................................................................................................60 2-10 Nutrient loadings by watershed/re ach in the Suwannee River System for water year 1998. .........................................................................................61 2-11 Estimated N inputs for Suwannee County. ......................................................62 2-12 Estimated N inputs for Lafayette County. .......................................................62 3-1 Suwannee River Water Management District surfacewater quality monitoring network. .........................................................................................83 3-2 Suwannee River Water Management District groundw ater quality monitoring network. .........................................................................................84 3-3 Median TP for the Suwannee River at Branford with linear trend lines. ........85 3-4 TP concentration by water year for Suwannee River at Branford. Box represents 25th percentile, median, 75th percentile and whiskers represents the upper and lower observed value. .................................................................86 3-5 Median NO3-N for the Suwannee River at Branford with linear trend line. ...87

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13 Figure Page 3-6 NO3-N concentration by water year for Suwannee River at Branford. Box represents 25th percentile, median, 75th percentile and whiskers represents the upper and lower observed value. .................................................................88 3-7 Population for Lafayette and Su wannee counties, 1950 through 2004. ..........89 3-8 Median NO3-N concentration for the Suwannee River at Branford and population for Lafayette and Suwannee counties. .....................90 3-9 Median TP concentration for the Suwannee River at Branford and population for Lafayette and Suwannee counties. .....................91 3-10 Fertilizer sales data for Suwa nnee and Lafayette counties. .............................92 3-11 Median TP concentration for the Suwannee River at Branford and N fertilizer sale for Suwann ee and Lafayette counties. .......................................93 3-12 Median NO3-N concentration for the Suwannee River at Branford and N fertilizer sales for Suwannee and Lafayette counties. ..................................94 3-13 Median NO3-N concentration for the Suwannee River at Branford and N fertilizer sales and total crop acres for Suwannee and Lafayette counties. ...................................................................95 3-14 Median K concentration for the Suwannee River at Branford with linear trend line. ...............................................................................................96 3-15 Median K and median NO3-N concentrations for the Suwannee River at Branford. ............................................................................................97 3-16 Median K concentration for th e Suwannee River at Branford and K fertilizer sale for Suwa nnee and Lafayette counties. .............................98 3-17 Mean upper Floridan aquifer TP concentration contour map for water year 2006. ...............................................................................................99 3-18 Mean upper Floridan aquifer NO3-N concentration contour map for water year 2006. ...............................................................................................100 3-19 Mean upper Floridan aquifer K concentration contour map for water year 2006. ................................................................................................101 3-20 TP Loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005. ..........................................................................................102

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14 Figure Page 3-21 NO3-N Loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005. ..........................................................................................103 3-22 Annual TP loads and rainfall by water year for the Suwannee River. .............104 3-23 Annual NO3-N loads and rainfall by water ye ar for the Suwannee River. ......105 3-24 Suwannee River Basin loading by watershed/reach for water year 2005. ...............................................................................................106 4-1 Suwannee River Water Manageme nt District stations on the Suwannee River with aerial photography. .......................................................126 4-2 Suwannee River Water Manageme nt District stations on the Santa Fe River with aerial photography. ..........................................................127 4-3 Mean NO3-N and TP for Suwannee River Water Management District Suwannee River stations (1989 to 2006). ........................................................128 4-4 Mean NO3-N and TP for SRWMD Sant a Fe River stations (1989 to 2006). .................................................................................................129 4-5 Middle Suwannee River Basin samp ling points (July 21, 2000) for NO3-N profile ....................................................................................................130 4-6 Middle Suwannee River Basin (D owling Park to Branford) NO3-N profile on July 21, 2000. ...................................................................................131 4-7 NO3-N profile of the Middle Suwann ee River Basin (October 2000). ............132 4-8 NO3-N profile of Middle Suwannee River Basin (October 2000 and September 2006). .............................................................................................133 4-9 The relationship of discharge and NO3-N concentration for the Suwannee River at Branford (1989 to 2006). ....................................................................134 4-10 The relationship of specific conductance and discharge for the Suwannee River at Branford (1989 to 2006). .....................................................................135 4-11 The relationship of specific conductance and NO3-N concentration for the Suwannee River at Branford (1989 to 2006). ...................................................136 4-12 Middle Suwannee River Basin sampling poi nts and discharge cross-sections (October 2000 and September 2006). ..............................................................137

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15 Figure Page 4-13 Comparison of segment NO3-N load change per m of river in the Middle Suwannee River Basin (July 2000 and September 2006). ...............................138 4-14 Lower Santa Fe River Basin sa mpling points (June 7, 2000) for NO3-N profile. ..................................................................................................139 4-15 NO3-N profile of the Lower Santa Fe River Basin on June 7, 2000. ...............140 4-16 NO3-N profile of the Lower Santa Fe River Basin (September 2001 and October 2006). ...........................................................................................141 4-17 Lower Santa Fe River Basin segments for September 2001 NO3-N profile. ...142 4-18 Refined Lower Santa Fe River Basin segments for October 2006 NO3-N profile. ..................................................................................................143 4-19 Comparison of segment NO3-N load change per m of river in the Lower Santa Fe River Basin (September 2001 to October 2006). ..............................144 4-20 Refined segments NO3-N load change per m of ri ver in the Lower Santa Fe River Basin in October 2006. ...........................................................................145 5-1 Groundwater domains based on 1985 potentiometric surface. ........................170 5-2 Groundwater domains based on 1990 potentiometric surface. ........................171 5-3 Groundwater domains based on 1995 potentiometric surface .........................172 5-4 Groundwater domains based on 2002 potentiometric surface. ........................173 5-5 Groundwater domains based on 2005 potentiometric surface. ........................174 5-6 Principal component 1 contours fo r hydrochemical facies analysis .................175 5-7 Principal component 2 contours fo r hydrochemical facies analysis .................176 5-8 Refined groundwater domains based on composite potentiometric surfaces and hydrochemical facies analysis. ..................................................................177 5-9 Median groundwater TP concen tration by groundwater domains. ..................178 5-10 Median groundwater NO3-N concentration by gr oundwater domains. ...........179

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16 Figure Page 5-11 1995 level 2 Florida Landuse Code landuse/landcover for the Suwannee River Water Manage ment District. ..................................................................180 5-12 Median groundwater NO3-N concentration vers us percentage of groundwater domains in cr op and pasture lands. .............................................181 5-13 Median groundwater TP concentration versus percentage of groundwater basins in crop and pasture lands. ......................................................................182 5-14 Median groundwater NO3-N concentration and per centage of groundwater basins in crop and pasture lands. ......................................................................183 5-15 Landuses within crop and pasture land s code for the groundwater domains with elevated median NO3-N. ..........................................................................184 A-1 Median TP concentration for the Suwannee River at Branford. .......................189 A-2 Median NO3-N concentration for the Suwannee River at Branford. ................190 A-3 Median K concentration for th e Suwannee River at Branford. .......................191 B-1A Mean upper Floridan aquifer TP concentration contour map for water year 2001. ................................................................................................212 B-1B Mean upper Floridan aquifer TP concentration contour map for water year 2002. ................................................................................................213 B-1C Mean upper Floridan aquifer TP concentration contour map for water year 2003. ................................................................................................214 B-1D Mean upper Floridan aquifer TP concentration contour map for water year 2004. ................................................................................................215 B-1E Mean upper Floridan aquifer TP concentration contour map for water year 2005. ................................................................................................216 B-2A Mean upper Floridan aquifer NO3-N concentration contour map for water year 2001. ................................................................................................217 B-2B Mean upper Floridan aquifer NO3-N concentration contour map for water year 2002. ................................................................................................218 B-2C Mean upper Floridan aquifer NO3-N concentration contour map for water year 2003. ................................................................................................219

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17 Figure Page B-2D Mean upper Floridan aquifer NO3-N concentration contour map for water year 2004. ................................................................................................220 B-2E Mean upper Floridan aquifer NO3-N concentration contour map for water year 2005. ................................................................................................221 B-3A Mean upper Floridan aquifer K concentration contour map for water year 2001. ................................................................................................222 B-3B Mean upper Floridan aquifer K concentration contour map for water year 2002. ................................................................................................223 B-3C Mean upper Floridan aquifer K concentration contour map for water year 2003. ................................................................................................224 B-3D Mean upper Floridan aquifer K concentration contour map for water year 2004. ................................................................................................225 B-3E Mean upper Floridan aquifer K concentration contour map for water year 2005. ................................................................................................226 B-4A Suwannee River Basin loading by wa tershed/reach for water year 1998. ........227 B-4B Suwannee River Basin loading by wa tershed/reach for water year 1999. ........228 B-4C Suwannee River Basin loading by wa tershed/reach for water year 2000. ........229 B-4D Suwannee River Basin loading by wa tershed/reach for water year 2001. ........230 B-4E Suwannee River Basin loadings by watershed/reach for water year 2002. ......231 B-4F Suwannee River Basin loading by wa tershed/reach for water year 2003. ........232 B-4G Suwannee River Basin loading by wa tershed/reach for water year 2004. ........233 C-1 Plot of NO3-N versus K concentrations for spring SUW718971. ....................234 C-2 Plot of NO3-N versus K concentrations for spring SUW725971. ....................235 D-1 1985 potentiometric surface map for the Suwannee River Water Management District. ........................................................................................248 D-2 1990 potentiometric surface map for the Suwannee River Water Management District. ........................................................................................249

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18 Figure Page D-3 1995 potentiometric surface map for the Suwannee River Water Management District. ........................................................................................250 D-4 2002 potentiometric surface map for the Suwannee River Water Management District.. .......................................................................................251 D-5 2005 potentiometric surface map for the Suwannee River Water Management District. ........................................................................................252

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19 LIST OF ABBREVIATIONS ADCP Acoustic Doppler Current Profiler BMP best management practice C carbon C degrees Celsius CAFO confined animal feeding operation CFC chloroflurocarbons cfs cubic feet per second d day DACS Florida Department of Agri culture and Consumer Services DO dissolved oxygen DOC dissolved organic carbon EPA United States Environmental Protection Agency F.A.C. Florida Administrative Code FDEP Florida Department of Environmental Protection FDER Florida Department of Environmental Regulation FLUC Florida Land Use Code GPS global positioning system HRS Department of Health and Rehabilitative Services IFAS Institute of Food and Agricultural Sciences K potassium kg kilogram km kilometer

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20 L liter L s-1 liter per second LSRB Lower Suwannee River Basin LSFRB Lower Santa Fe River Basin m meter g g-1 micrograms per gram mg L-1 milligram per liter g L-1 micrograms per liter MLRA Major Land Resource Area msl mean sea level MSRB Middle Suwannee River Basin N nitrogen NAWQA National Water Quality Assessment NH4 + ammonium NO2 nitrite NO3 nitrate NO3-N nitrate-nitrogen NOx-N nitrate plus nitrite nitrogen NRCS Natural Resource Conservation Service OFW Outstanding Florida Water OM organic matter P phosphorus PCA principal component analysis

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21 PCU platinum cobalt unit PO4 3phosphate SRB Suwannee River Basin SRBNMWG Suwannee River Basin Nutr ient Management Working Group SRWMD Suwannee River Wate r Management District TDS total dissolved soilds TKN total Kjeldahl nitrogen TMDL Total Maximum Daily Load TOC Total organic carbon TP total phosphorus U.S. United States USDA United States Depa rtment of Agriculture USGS United States Geological Survey WARN Water Assessment Regional Network y year

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22 Abstract of Dissertation Pres ented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy INFLUENCES ON THE DISTRIBUTION AND OCCURRENCE OF NITRATE-NITROGEN AND TOTAL PHOSPHORUS IN THE WATER RESOURCES OF THE SUWANNEE RIVER WATER MANAGEMENT DISTRICT By H. David Hornsby December 2007 Chair: Donald Graetz Major: Soil and Water Science In Florida, the Suwannee River is highl y influenced by the interconnection with groundwater. This relationship affects the quality and quantity of water in the river. An increasing temporal trend in nitrate-nitrogen (NO3-N) concentration and a declining temporal trend for total phosphorus (TP) concentrations has been identified in the river. Loadings of NO3N were consistently highest in the Middle Su wannee River Basin (MSRB) and the Lower Santa Fe River Basin (LSFRB). The research objectives were to inde ntify changes in riverine TP and NO3-N concentrations and relate to anthropogenic influences, charac terize groundwater/surfacewater interaction in the MSRB and LSFRB and locate segment(s) with the greatest NO3-N load entering the river, delineate groundwater domai ns in the Suwannee River Water Management District (SRWMD) using potenti ometric surface maps and hydroc hemical facies analysis, and determine relationships of groundwater domain TP and NO3-N concentrations to domain landuse/landcover. The increasing temporal trend in NO3-N concentrations and dec lining temporal trend in TP concentrations are still pres ent in the river. The declinin g trend in TP is related to

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23 management of a phosphate mining discharge. The NO3-N concentration observed in the Suwannee River at Branford is likely related to fertilizer sales/use in Suwannee and Lafayette counties. The increase in NO3-N loading in the MSRB and LSFRB occurred over small segments of each river. The NO3-N load increases in the MSRB and LSFRB appear to be due to groundwater inputs based on riverine chemical signa ture and river discharg e. Eight groundwater domains were delineated from the SRWMD poten tiometric surface maps and were refined to nine domains using hydrochemical facies anal ysis. Groundwater domain landuse/landcover was related to observed grou ndwater domain TP and NO3-N concentrations. When crop and pasture land was greater than 12 % of the land area of the groundwater domain elevated groundwater NO3-N concentrations were observed. These landuses receive much of the fertilizer used in the basins. Groundwater domains with elevated NO3-N concentrations are adjacent to the MSRB and LSFRB. Groundwater domains with elevated NO3-N concentrations are affecting the surfacewater quality that receives discharge from these groundwat er domains and the most likely source of the NO3-N is fertilizer use in the groundwater domains.

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24 CHAPTER 1 INTRODUCTION The Suwannee River Basin (SRB) is shared by two states: Georgia and Florida (Figure 11). The SRB covers 9,950 square miles [25,770 km2] of land drained by the Suwannee, Alapaha, Withlacoochee, and Santa Fe rivers in Florid a and Georgia. The S RB in Florida covers 4,230 square miles [10,955 km2] (Katz and DeHan, 1996). The Suwann ee River is the State River of Florida. The Florida Legisl ature in 1979 designated the Su wannee River in Florida an Outstanding Florida Water which means the river ha s significant cultural a nd ecological value to the State of Florida. Also, the Suwannee River is one of the last rivers in the United States that flows unimpeded by dams, dikes, or levees and is the second largest discha rging river in Florida (FDEP, 2001). The SRB consists of three majo r tributaries: the With lacoochee River (and its tributary Little River), Alapaha River, and Sant a Fe River (Berndt, 1996) as shown in Figure 1-1. The SRB has been farmed since the 1700’s, and the present road patterns reflect historic travel routes. River and stream corridors and larger wetland areas have, for the most part, remained relatively undeveloped and provide exce llent wildlife habitat (Fernald and Purdum, 1998). National Wildlife Refuges managed by th e United States Fish and Wildlife Service occupy both the headwaters and delta of the Suwannee River. Agriculture constitutes most of the devel oped land uses within the SRB in Florida, including pine plantations, row crops, and pastur es. Irrigated acreage has increased considerably in the SRB over the last several decades as t echnologies have improved and market conditions have changed (Marella, 2004). The primary wate r source is ground water from the Floridan aquifer system in Florida (Fernald and Purdum 1998). Trends over th e last decad e indicate a general shift towards more inte nsive production of food and fora ge crops as well as animal husbandry. Agricultural crops a nd products from the SRB include dairy and poultry, fruits and

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25 vegetables, grains, pasture, hay, and forestry products. Forest ry, primarily pine plantations, covers large areas of the SRB and provides timb er and fiber for mills within and outside the SRB. In recent years, water quality data have indi cated an increasing temporal trend for nitratenitrogen (NO3-N) in the Suwannee River. The rate of increase is 0.02 mg N L-1 y-1 (Ham and Hatzell, 1996). Possible sources of the NO3-N in the SRB are atmospheric deposition, septic tanks, fertilizer, and animal waste (Andr ews, 1994). Data have shown that NO3-N loadings are consistently highest in the Middle Suwannee River and the Lower Santa Fe River basins. This Dissertation contributes the following: 1. An understanding of the changes in concentr ations of total phosphorus (TP) and NO3-N in the Suwannee River due to possi ble anthropogenic influences. 2. Summary of recent ground and surface water quality data in the Suwannee River Water Management District (SRWMD). 3. Characterization of groundwater/surfacewater interactions in the Middle Suwannee River Basin (MSRB) and the Lower Santa Fe Rive r Basin (LSFRB). This characterization located the segment (s) of the river where the greatest NO3-N load enters the river system from ground water. 4. Determination of the groundwater domains within the SRWMD using potentiometric surface maps and principal component anal ysis of groundwater quality. Groundwater domain TP and NO3-N concentrations were statistically evaluated to ensure that each groundwater domain was statistically diffe rent from each other and a summary of groundwater quality by groundwater domain was generated. 5. Landcover/Landuse was clipped to each groundwater domain and correlations will be run to determine relationship to groundwater domain TP and NO3-N concentrations and level 2 Florida Land Use Codes (FLUC) landuses.

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26 Figure 1-1. Basins of the Suwannee Ri ver System (Hornsby and Raulston, 2000).

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27 CHAPTER 2 LITERATURE REVIEW Overview of the Suwannee River Basin Location The Suwannee River Basin (SRB) is located within the Coastal Plain physiographic region of the southeastern U. S., extending from n ear Cordele, Georgia, to Cedar Key, Florida, in the Gulf of Mexico (Fernald and Purdum 1998). The Okefenokee Swamp contains the headwaters of both the Suwannee and St. Marys Rivers (Fernald and Purdum, 1998). The SRB covers part of South Georgia and North Florid a (Figure 1-1), and has at least 60 units of government with jurisdiction (Hornsby and Raul ston, 2000). Valdosta, Georgia is the largest city within the SRB, followed by Lake City, Flor ida. Interstate 75 traverses the length of the SRB; Interstate 10 crosses the southern third. Hydrology The SRB hydrology is highly varied in terms of flows, water quality, aquatic habitat, and related values. The SRB includes freshwater sw amp, small surfacewater streams, large rivers, extensive tidal salt marshes, and interior-drained karst areas with extensive spring discharge. The character of the Suwannee River changes dramatically as it progresses down stream, reflecting the geology, physiography and land cover of the region it drains (Fernald and Purdum, 1998). Surface drainage characteristics dominate the upper two-thirds of the SRB. The dendritic pattern of the stream drainage is also eviden ced by the forested stream corridors. Surface drainage exists where soils contain more clays and fine sediments that are more resistant to infiltration. Streams, lakes, and wetlands ar e more abundant in the upper Suwannee River, and in the upper Santa Fe River basins Water quality conditions in th ese areas reflect the dominant

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28 influence of surfacewater systems which contai n low dissolved minerals and generally acidic conditions due to low buffering (FDEP, 2001). In the southern third of the SRB, a relatively thin layer of highly porous sand overlies the Floridan aquifer system, and the Suwann ee River takes on more groundwater quality characteristics (Hornsby and Cery ak, 1999). Rainfall in these areas percolates directly to the aquifer. The relative absence of surfacewater features such as streams, lakes, and wetlands indicates areas where recharge to the aquifer is direct. The transition between these areas includes many stream-to-sink sub-basins, where surface stream flow is abruptly captured by sinkholes and is directed to the aquifer. This transition zone lies along a feature in Florida known as the Cody Escarpment or Cody Scarp (Fer nald and Purdum, 1998). These areas, as well as the numerous springs along the lower river reaches, act as points of inte raction between surface water and ground water (Scott et al., 2004). Water quality conditions in the Suwannee and it s tributaries reflect th e physical setting of the SRB. Areas dominated by surface drainage t ypically have more acidic water, higher levels of sediment and particulate matte r, and higher variability in flow regime. Downstream of White Springs, Florida, the Suwannee River receives in flow from over 200 known springs (Scott et al., 2004; Hornsby and Ceryak, 1998). The influx of ground water from the upper Floridan aquifer system buffers the acidity and darker color of th e surface water with relatively constant flow of clear, mineral-rich ground water which provides base flow to the Suwannee River (Hornsby and Ceryak, 1999). Base flow in a river system is a natural condition of ground water discharge to the river and is the primary source of flow in the system during low flow (Pittman et al., 1997). Ground water influence on water quality in the ri ver is more pronounced during low flow and in the river reaches having the greatest number of springs and the leas t tributary inflow (Hull et al.,

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29 1981). The upper Floridan aquifer will receive recharge from the Suwannee River when the surface water levels are above the adjacent aquife r potentiometric level. This results in the spring to estevelle, which is the cessation of di scharge due to the surf acewater head overcoming the groundwater head. This results in reverse flow of springs or surfacewater entering the aquifer. Physiography Hydrogeology within the SRB is directly related to the physiography. The SRB can be divided into three general physi ographic regions: Northern Highl ands, Gulf Coastal Lowlands, and River Valley Lowlands as shown in Figure 2-1 (White, 1970). The Northern Highlands region is mainly ch aracterized by altitude and thick, clayey strata that overlie the Floridan aquifer system The land surface throughout the area is greater than 100 feet (30.5 m) above mean sea level (m sl) and reaches heights up to 230 feet (70.1 m) msl (White, 1970; Hornsby and Ceryak, 1999; Fernald and Purdum, 1998). The area to the west and southwest is the Gulf Coastal Lowlands. The land surface of this area is less than 100 feet (30.5 m) msl and th e majority of the clayey sediments have been eroded away (White, 1970; Hornsby and Cerya k, 1999; Fernald and Purdum, 1998). Limestone is at or near land surface throughout the Gulf Coastal Lowlands. The most persistent topogra phic feature in the State of Fl orida is the Cody Scarp, which is the boundary between the Highlands and Lo wlands (Puri and Vernon, 1964; Hornsby and Ceryak, 1999; Fernald and Purdum, 1998). It is a very significan t feature as it pertains to hydrogeology of the SRB. Every river or stream (except the Suwannee Rive r) that originates in the Highlands disappears underground as it cros ses the Cody Scarp (White, 1970; Hornsby and Ceryak, 1999; Fernald and Purdum, 1998). The fe w streams that exist in the Gulf Coastal

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30 Lowlands have eroded downward into the upper Flor idan aquifer system and have intersected the unconfined upper Floridan aquifer. Base flow to Gulf Coastal Lowland streams is supplied by artesian spring flow from the uppe r Floridan aquifer system (Sco tt et al., 2002; Scott et al., 2004; Pittman et al., 1997). The third physiographic region is the River Valley Lowlands. River Valley Lowlands are erosional/depositional features formed by the rivers that originate in the Highlands and pass through the River Valley Lowlands to the Gulf of Mexico (White, 1970; Hornsby and Ceryak, 1999). Soils The Natural Resource Conservation Serv ice (NRCS) formerly known as the Soil Conservation Service (SCS), a branch of the Un ited States Department of Agriculture (USDA), has defined three major land resource areas (M LRAs) within the SRB in the Suwannee River Water Management District (SRWMD). The th ree MLRAs are Southern Coastal Plain, NorthCentral Florida Ridge, and Eastern Gulf Coas t Flatwoods (Soil Survey Staff, 1997). The Southern Coastal Plain’s soils are predominantly Udults. These soils are characterized as deep and have a thermic temperature regime, an udic moisture regime, a loamy or sandy surface layer. The North-Central Florida Ridge’s soils are pred ominantly Udults and Psamments. These soils are characterized by having a thermic temperature regime and an udic moisture regime. The soils range from well drained to poorly draine d and generally sandy. The predominant Eastern Coast Flatwood’s soils are Aquults, Aquepts, and Aquods. These soil s are characterized by having a thermic temperature regime and an aqui c moisture regime. The soils are generally sandy and poorly drained or very poorly drained (Soil Survey Staff, 1997) Nair et al. (2004) noted the sandy soils of the SRB in Florida have little ability to absorb phosphorus (P) and that

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31 many animal husbandry operations were appl ying P-rich lagoon effluent to permanent sprayfields. This application of P-rich lagoon effluent increase d the P loading to the sites and may result in P loss via surfacewater runoff or l eaching to ground water. Furthermore, Obreza and Means (2006) noted that the sandy soils of the SRB were vulnerable to nutrient and agrichemical leaching, especially under exce ssive rainfall or irrigation conditions. The Middle Suwannee River Basin (MSRB) is a sub-basin of the SRB which is located in Suwannee and Lafayette counties in Florida. Generally, soils in the MSRB are sandy well drained to excessively drained. For agricultu ral production, these soils present issues with irrigation and leaching of nutrients from the root zone (USDA, 1993). Furthermore, these soils have medium to high potential for nitrogen (N ) leaching to ground water. Most agricultural production in the MSRB occurs primarily on Enti sols and Ultisols (Obreza and Means, 2006). Entisols are soils that do not display evidence of pedogenic horizon development (Brady and Weil, 2000). Entisols are able to support any vege tation and occur in any climate. Entisols form in inert parent materials such as quartz sand or sl owly soluble rock such as limestone (Carlisle et al., 1985). The properties unique to Florida Entisols are a domi nance of mineral soil and an absence of distinct pedogenic horizons except fo r an ochric epipedon, an albic horizon, and a spodic or argillic diagnostic subsurface horizon that is below 80 inches[203 cm] (Collins, 2003). Ultisols occur in humid regions and formation is from weathering and leaching that results in subsurface horizons of illuvial accumulations, such as, quartz, kaolinite, and iron oxides (Brady and Weil, 2000; Soil Survey Staff, 2007). Ge nerally, Ultisols are acidic with nutrients concentrated within a few centimeter of the la nd surface and have a relatively low capacity to retain fertilizers (So il Survey Staff, 2007).

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32 Soil orders with high leachi ng potential in the SRWMD are shown in Figure 2-2. These soil orders include Ultisols, Spodos ols, Inceptisols and Entisols with Entisols being the majority of the high leaching soils. High leaching Ultis ols in the SRWMD are Apopka (loamy, siliceous, subactive, hyperthermic Grossa renic Paleudults) and Valdosta (s iliceous, thermic Psammentic Paleudults) [Houston et al., 1965; Carlisle, 1985 a nd Soil Survey Staff, 2007]. High leaching Spodosols are Cassia (sandy, siliceous, hypertherm ic Oxyaquic Alorthods ), Hurricane (sandy, siliceous, thermic Oxyaquic Alorthods), Ma ndarin (sandy, siliceous, thermic Oxyaquic Alorthods), and Ridgeland (sandy, siliceous, thermi c Oxyaquic Alorthods) [Soil Survey Staff, 2007]. High leaching Inceptisol are Fort Meade (siliceous, hyperthermic humic Psammentic Dystrudepts), Orlando (siliceous, hyperthermic humic Psammentic Dystrudepts), Pickney (sandy, siliceous, thermic Cumulic Humaquepts) and Placid (sandy, siliceous, hyperthermic typic Humaquepts). The high leaching Entisols ar e Adamsville (hyperthermic, uncoated aquic Quartzipsamments), Alaga (thermic, coated typi c Quartzipsamments), Alpin (thermic, coated Lamellic Quartzipsamments), Astatula (hyperthermic, uncoated typic Quartzipsamments), Bigbee (thermic, coated typic Quartzipsamments), Candler (hyperthermic, uncoated Lamellic Quartzipsamments), Chipley (thermic, coated aquic Quartzipsamments), Clara (siliceous, thermic spodic Psammaquents), Foxworth (the rmic, coated typic Quartzipsamments), Gainesville (hyperthermic, coated typic Quartz ipsamments), Kershaw (thermic, uncoated typic Quartzipsamments), Lake (hyperthermic, coated typic Quartzipsamments), Lakeland (thermic, coated typic Quartzipsamments), Orsino (hype rthermic, uncoated spodic Quartzipsamments), Ortega (thermic, uncoated typic Quartzipsa mments), Osier (siliceous, thermic typic Psammaquents), Ousley (thermic, uncoated aq uic Quartzipsamments), Paola (hyperthermic, uncoated spodic Quartzipsamments), Penney (the rmic, uncoated Lamellic Quartzipsamments),

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33 Pompano (siliceous, hyperthermic typic Psamma quents), Resota (thermic, coated spodic Quartzipsamments), Ridgewood (thermic, uncoa ted aquic Quartzipsamments), and Tavares (hyperthermic, uncoated typic Quartzipsamments ) [Houston et al., 1965; Carlisle, 1985 and Soil Survey Staff, 2007]. The dominant Entisols soils in the MSRB are Alpin and Penney (Figure 2-2). The Alpin series consists of very deep, excessively draine d, moderately rapidly perm eable soils on uplands and river terraces of the Coastal Pl ain. The soils formed in thick beds of sandy eolian or marine deposits. (Soil Survey Staff, 2007). The Penney series consists of very deep, excessively drained, rapidly permeable soils on uplands. The soils formed in thick beds of sandy eolian or marine deposits (Soil Survey Staff, 2007). These soils have leaching potential. Sabasan (2004) identified NO3-N concentrations in various landuse on Entisols, Ultisols, and Spodosols in the Santa Fe River Waters hed. For landuse pine plantations, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 0.05, 0.33 and 0.28 g N g-1of soil, respectively. For landuse improved pasture, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 0.51, 1.80 and 1.65 g N g-1of soil, respectively. For landuse crops, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 2.70, 2.60 and 0.56 g N g-1of soil, respectively. Hydrogeology A highly productive regional aquifer exists wi thin the SRB that is capable of producing thousands of gallons of water per minute to wells. This aquifer is referr ed to as the Floridan Aquifer system (Miller, 1997). The upper Floridan aquifer system is the primary source of drinking water and base flow in the SRB (FDEP, 2001). The Floridan aquifer system is made up of limestone and dolostone. Car bonate rock (limestone and/or dolostone) as much as 5,000 feet

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34 (1,524 m) thick exists in the subsurface of the SRB. These strata, which are primarily Tertiary in age, make up the Florida Platform. The Floridan aquifer system is found within these strata in the Florida Platform (Figure 2-3) and in similar strata in the Caro linas and portions of Alabama. The permeable portion of this carbonate-rock plat form ranges from about 600 feet (182.9 m) to 1,700 feet (518.2 m) in thickness (Miller, 1982). Water that recharges the Floridan aquifer system comes from rainfall and focused recharge through leaky sediments at the base of the upper aquifers, at the edge of the upper aquifers where the clayey base becomes discont inuous, or through sinkholes that penetrate into the aquifer system (Ceryak et al., 1983; Horn sby and Ceryak, 1999). There are two distinct regions of the upper Floridan a quifer within the SRB in Florid a: a confined region and an unconfined region (Figure 2-4). The confined re gions are where there is a layer of clay over limestone, thus reducing/retarding the recharge of rainwater and fostering surface water runoff. The unconfined regions are where limestone is at or near land surface and are recharged directly from percolating rainfall, since the only sedime nt overlying the aquifer is porous sand (Hornsby and Ceryak, 1999). These unconfined regions allo w for direct recharge of the upper Floridan aquifer and allows for the contamination of the upper Floridan aquifer by water-soluble contaminants such as nitrates (NO3 -). Land Use Overview The land use patterns that have evolved w ithin the SRB reflect the opportunities and constraints of the land. Most of the developed land uses in th e SRB historically have been located on the upland, better-drained regions. Th e SRB has been farmed since the 1700’s and the present road patterns reflect historic travel routes. River and stre am corridors and larger wetland areas have, for the most part, remained relatively undeveloped and provide excellent

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35 wildlife habitat (Fernald and Purdum, 1998). National Wildlife Refuges managed by the United States Fish and Wildlife Service bracket both the headwaters and de lta of the Suwannee River. Growth and development within the Florida side of the SRB has been steady since the 1960s, but at a relatively slower rate than other areas in Flor ida (Fernald and Purdum, 1998). Most of the urban development ha s occurred near the Interstate 75 corridor, and in proximity to cities and towns. The estimated population in 2006 in the SRB within Florida is 350,000 (K. Webster, 2007, Personal Communication). Growth projections for the SRB indicate a 13 to 15 % increase in the population over the co ming decade (Fernald and Purdum, 1998). Agriculture defines most of the developed land uses within the SRB in Florida, including pine plantations, row crops, and pastures. Irri gated acreage has increased considerably in the SRB over the last several decades as technolog ies have improved and market conditions have changed (Marella, 2004). Drinki ng water source is primarily ground water from the Floridan aquifer system in Florida (Fernald and Purdum 1998). Agriculture acreages within the SRB over the last decade indicate a declining trend, which indicates a general shift towards more intensive production of food, forage crops and animal husbandry on less acreage. Agricultural crops and products from the SRB include dair y and poultry, fruits and vegetables, grains, pasture, hay, and forestry products. Forestry, prim arily pine plantations, covers large areas of the SRB and provides timber and fiber for mills within and outside the SRB. Water Quality Characteristics The Suwannee River system’s hydrology and water chemistry is influenced by physiographic characteristics (FDER, 1985). The geologic and physiographic changes that the Suwannee River undergoes as it traverses through north central Florida results in dramatic longitudinal changes in water chemistry (Cerya k et al., 1983; FDER, 1985). The changes in

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36 these characteristics may best be described by recognizing six reaches of the Suwannee River in Florida, as shown in Figure 2-5 (Hornsby et al., 2 000). A description of the reaches is given in Table 2-1. Water chemistry in the Suwannee River cha nges in a unique way from upstream to downstream (Bass and Cox, 1985). Hornsby a nd Mattson (1998) used water chemistry and stream structure to define six distinct reaches of the Suwannee River; the upper river (Reaches 1 and 2) is a soft, acidic, blackwater stream, with waters of low minera l content and high color (Figures 2-6 and 2-7). As the river progresses downstream (Reaches 3, 4, 5 and 6), it receives increasing amounts of water from the upper Floridan aquifer, which change s river water quality to a clear, slightly colored, alkaline stream (F igures 2-6 and 2-7). These natural chemical gradients influence the ecology of the river in many ways. In terms of overall biological production, the upper river tends to be more o ligotrophic, while the lower river is more productive. Total organic carbon (TOC) concentrations ar e higher in the upper reaches of the river (Hornsby et al., 2000), largely due to the dissolved organic carbon (C) associated with the high water color. Nutrient concentrations (dissolved N and P) are low in the uppermost reach (Reach 1), generally near detection lim its of less than 0.05 mg N L-1 and 0.04 mg P L-1 (Hornsby et al., 2000). The low levels of nutrients in the upper reach contribute to its low biological productivity. Dissolved N and P concentratio ns both generally incr ease going downstream. Peak P levels are seen in Reach 2, partly due to the geology, as the ri ver crosses the exposed Hawthorn Group that contains hi gh levels of phosphate in the form of carbonate-fluorapatite (Maddox et al., 1992), and partly due to discha rges from phosphate mining and processing. Highest NO3-N levels are seen in the middle and lower reaches (Reaches 3,4,5 and 6), and a

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37 historical trend of increasing NO3-N has been identified in th e middle and Lower Suwannee and Lower Santa Fe rivers (Ham a nd Hatzell, 1996). Much of NO3-N increase comes from groundwater discharges via springs along the river corridor (Katz et al., 1999; Pittman et al., 1997). Areas of elevated NO3-N have been identified in the upper Floridan aquifer in these regions (Hornsby et al., 2005B). Sources of this N are di verse and includ e agricultural operations, sewage spray fields, areas with dense concentrations of septic tank drain fields, and stormwater runoff to sinkholes. The 2004 State Water Quality Assessment 305(b) Report prepared by the Florida Department of Environmental Protection (FDEP) indicates generally “good” water quality in the SRB. Portions of the lower ri ver and most of the estuary are designated as “impaired” and are candidates for Total Maximum Daily Load (TMDL) establishment. Po rtions of the upper Suwannee and Santa Fe sub-basins are indicat ed to be “potentially impaired”. These assessments appear to be based largely on low di ssolved oxygen (which is partly natural due to groundwater discharge), nutrients, and/or elevated fecal coliform levels. Nutrients For water quality concerns, the two nutrients th at receive the most a ttention in water are P and N. The most common forms of P and N that plants uptake are H2PO4 and HPO4 2for P and NO3 and NH4 + for N (Brady and Weil, 2000). Phosphorus Phosphorus is second only to N in its importa nce in the production of healthy plants and profitable yields (Brady and Weil, 2000). Phosphorus is needed for the production of adenosine triphosphate (ATP) that is the energy source for most biochemi cal process, a component of deoxyribonucleic acid (DNA) and ri bonucleic acid (RNA). Native soils are generally low in

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38 available P thus soil amendments have been used to promote crop yields (Havlin et al., 1999). Unfortunately, more P is often added to the so il than is removed by plant uptake (Brady and Weil, 2000). This results in excess P in the soil a nd allows for the movement of the P via erosion or leaching. Phosphorus cycle Phosphorus is a macronutrient for primary produ cers. The availability of P for biological uptake has little to no relationship to the total P (TP) content in soils (Havlin et al., 1999). Factors which control H2PO4 and HPO4 2in the soil solution are pH, adsorption, desorption, mineralization and immobilization, precipitation, dissolution, fer tilization, soil organic matter, leaching and plant uptake. The sources for P in the environment are fert ilizer, soil organic matter, primary minerals and secondary minerals. Secondary minerals ar e formed when P complexes with cations and precipitates out of the soil solution. Primary and secondary minerals can dissolve to supply the soil solution P. Soil organic matter is both a s ource and a sink of P. Soil organic matter can complex with P or the P can be incorporated in to the soil microbial mass. This is immobilization of P. The release of P into the soil solution by the soil organic matter is mineralized. Fertilization with P results in th e increase of soil solution P by increasing the amount of P in the soil, wh ich saturates the possible ad sorption sites in the soil. The pH of the soil solution determines the form (s) of P available. At low pH, between 2 and 6, H2PO4 is the domiant form while at higher pH, 8 to 12, HPO4 2is the domiant form. At pH 7.2 there are equal amounts of H2PO4 and HPO4 2in solution (Havlin et al., 1999). Adsorption of P is a process in which P in soil solution is removed and accumulated at the interface of the so il (minerals and clays) and solution. The adsorption of P reduces the

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39 availability of the P for plant up take. The reverse process, desorp tion, is the releas e of adsorbed P into the solution. The P cycle in soils is shown in Figure 2-8. However, the P cycle can be reduced to the following relationship (H avlin et al., 1999): Soil solution P labile P nonlabile P Soil solution P is the P which is dissolved in soil pore water. Labile P is the P that is readily available to the soil solution to replace P, which is removed by biological uptake. Nonlabile P is the P in the soil, which is not available to the soil solution due to chemical or biological immobilization (Havlin et al., 1999; Brady and Weil, 2000). Occurrence of phosphor us in groundwater Maddox et al. (1992) defined the backgr ound concentration of ortho-phosphate (H2PO4 -, HPO4 2and PO4 3-) in the upper Floridan aquifer to be less than 0.10 mg P L-1 while surface water within the SRWMD ranges in concentration of TP and ortho-phosphate from 0.001 to 26.6 mg P L-1 and 0.001 to 26.2 mg P L-1, respectively (Hornsby and Mattson, 1998). The P concentrations in the Suwannee River vary as the river traverses from the headwaters to the Gulf of Mexico. The high concentrations of P in the Suwannee Ri ver is observed in the upper river where the river comes in contact with the Hawthorne Group, a P bearing unit, and also, receives discharge from a phosphate mining operation. From the uppe r Suwannee River to Gulf of Mexico, the P concentrations decline in the river (Hornsby and Mattson, 1998). Concerns with phosphorus The primary concern with P is eutrophication of surface water bodies. The input of P into these surface waters results in increased bio-ac tivity, favoring organisms able to adapt to the environmental changes in the water. Thus, the bi o-diversity will be reduce d. Also, harmful algae

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40 such as blue green can produce toxins that can cause fish kills and prevent the water from being suitable for human consumption (Brady and Weil, 2000). Water quality standards for phosphorus Currently, there is no gro undwater standard for P (in any form) and no numeric surfacewater standard for P (in any form) for the St ate of Florida. Florid a Administrative Code (F.A.C.) 62-302.530 for surface water has a narrative standard for nutrients, which states, “that nutrients shall not cause an imba lance to flora or fauna”. Th e only surfacewater body with a numeric standard for P is the Everglad es which has a standard of 10 g P L-1 per Florida Administrative Code (F.A.C.) 62-302.540. The FDEP uses a screening concentrati on for total N and TP of 0.45 and 0.1 mg L-1, respectively (T. Greenhalgh, 2005, Personal Communication). The screening concentrations are based on total N and TP concentrations in su rfacewater bodies that will support a chlorophyll a concentration of 20 g L-1 (J. Hand, 2005, Personal Communication). These screening concentrations for total N and TP are used to determine impaired water bodies by nutrients. These impaired water bodies are reported bi annually to the United States Environmental Protection Agency (EPA) and are placed on the State’s TMDL list for development of TMDLs for nutrients. Nitrogen Nitrogen is the most commonly deficient nutrien t in crop production (Havlin et al., 1999). Therefore, most crops re quire the addition of N for optimum yield. Nitrogen is needed by organisms for the production of pr otein. The most mobile form of N in the environment is nitrate (NO3 -). Nitrate is complete ly soluble in water. The movement of nitrates in the environment can pose risks to humans and animal health as well as impact the quality of the e nvironment.

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41 Nitrogen cycle Nitrogen is a macronutrient for pr imary producers. The N cycle is shown in Figure 2-9. The four general steps in this cy cle are 1) N fixation, 2) ammonifi cation, 3) nitrification, and 4) denitrification (Havlin et al., 1999): Nitrogen fixation can be a biol ogical or chemical process. The biological process converts atmospheric nitrogen gas [N2(g)] to organic nitrogen (N) matter while chemical fixation can occur naturally by lighting in the atmosphere converting N2(g) to nitric acid (HNO3) or by man converting N2(g) to NH3, NH2 -, NO3 used in synthetic fertilizers. Ammonification is the decomposition of soil organic matter by soil organisms to release ammonium ion (NH4 +) from organic matter. The released NH4 + can then be used by nitrifying organisms in a process called nitrification if conditions are suitable or immobilized by soil organisms or available for plant uptake. Al so, in high pH in soils and waters, the NH4 + can volatize to NH3(g) or become fixed in a biologically una vailable form in some clay mineral lattices. Nitrification is the conversion of NH4 + to NO3 by a biological me diated reaction that oxidizes the N. The pro cess in the conversion NH4 + to NO3 is a two step reac tion. The first step is the conversion of NH4 + to NO2 -. Bacteria called nitrosomonas mediate this reaction. The second step is the conversion of NO2 to NO3 -. Bacteria called nitrobacter mediate this reaction. The rate limiting step is the conversion of NH4 + to NO2 -. Denitrification is the conversion of NO3 to gaseous forms of nitrogen (N2(g), N2O(g)). The process occurs under anaerobic c onditions. Denitrifying bacteria ( Pseudomonas, Baccillus and Paracoccus ) in anaerobic conditions ha ve the ability to use NO3 as the terminal electron

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42 acceptor in place of O2(g) for respiration. Through the biol ogical mediated reactions, N (in NO3 -) goes from an oxidation state of +5 to 0. The amount of decomposable organic matter (O M) strongly influences denitrification. The NO3 is used in place of O2(g) in the respiration process by the denitrifying bacteria. Thus, OM is the food source and the amount of C availa ble defines the amount of denitrification that will occur to produce energy for the denitrifying bacteria. Soil water content determines the am ount of denitrification by impeding O2(g) diffusion into the soil by the soil pore spaces being filled with water. Thus, water fills pore spaces and promotes anaerobic conditions by creating regi ons in the soil where the concentration O2(g) is reduced or O2(g) is removed from the system The process of denitrific ation will only occur when the concentration of O2(g) is too low to meet biological requirements for aerobic resp iration. However, in well aerated soils, denitrification can occur due to deve lopment of anaerobic microsites. Occurrence of nitrate-nitrogen Nitrate is a widespread contaminant of shallow ground water and the levels of contamination are increasing (Spalding and Exner, 1993). Nationally, Spal ding and Exner (1993) conducted an evaluation of the occurrence of NO3-N in groundwater. Th e percentage of wells sampled with NO3-N concentrations higher than the 10 mg N L-1 found in the foll owing states were: 18 % in Iowa, 27 % in Kansas, 17 % in Nebraska 3 % in North Carolina, Ohio, and Arkansas, 7 % of the wells sampled in Texas, 13 % in California, 25 % in Delawa re, 9 % in Pennsy lvania, 22 % in Washington, 20 % in Minnesota, and 37 % in South Dakota. Fu rthermore, the National Water Quality Assessment (NAW QA) program of the Un ited States Geological Survey (USGS) has assessed the water quality of aquifer systems that cover the water resources of greater than sixty

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43 percent of the population in the contiguous Unites States. Th e findings were that approximately fifteen percent of shallow grou ndwater sampled beneath agricu ltural and urban areas had NO3-N concentration above 10 mg N L-1 (Manassaram et al., 2006). The concentrations of NO3-N in groundwater are associated with source availability, regional environmental factors [i.e., rainfall, organic C, dissolved O2] (Madison and Brunett, 1985) and man-induced fact ors [i.e., agricultural activities] (Spalding and Exner, 1993). The NO3-N concentrations in the nation’s river are shown in Table 2-2. The percentiles were determined from 383 different rive rs through the United States. Maddox et al. (1992) defined the background concentration of NO3-N in the Floridan aquifer system to be 0.05 mg N L-1 while surface water within the SRWMD ranged in concentration of NO3-N from 0.05 to 4.8 mg N L-1 (Hornsby and Mattson, 1998). Concerns with nitrate-nitrogen Methemoglobinemia which affect s infants, is a result of NO3 being reduced to nitrite (NO2 -) in the gastrointestinal tract. The reduced species nitrite (NO2 -), then oxidizes the ferrous iron (Fe2+) in hemoglobin to ferric iron (Fe3+) which inhibits the hemoglobin fr om releasing oxyg en to the cells of the body (Kreitler, 1975). Th e cells of the body ar e thereby oxygen deprived, resulting in the blue color of the skin of the effected infa nt; hence, the name "blue baby" disease. Methemoglobinemia also affects animals (i.e., liv estock). In the rumen, the bacteria convert NO3 to NO2 when excess NO3 is introduced into the rumen and causes NO2 to build up. NO2 can be adsorbed through the oral and/ or GI tract into the blood and a ffects the hemoglob in similarly as in human (MPCAMDA, 1991). The result is methemoglobinemia in livestock. Another human health pr oblem associated with NO3-N is the carcinogenic properties of N compounds which are created in the digestive tract. The elevated concentrations NO3-N in drinking watger has been correlated to eith er mortality or incide nce of stomach cancer

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44 (MPCAMDA, 1991). Just like in methemoglobinemia, NO3 is reduced to NO2 in the gastrointestinal tract. The acidic conditions in th e gastrointestinal tract is conducive to the formation of N-nitros o compounds (MPCAMDA, 1991). Th e EPA has classified N-nitroso compounds as probable huma n carcinogens (EPA, 1991). Nitrogen also causes eutrophication in surface water where N is the limiting nutrient. The input of NO3-N into these surface waters results in incr eased bio-activity, favo ring organisms able to adapt to the environm ental changes in the wa ter (MPCAMDA, 1991). Thus, the bio-diversity will be reduced. In surface waters, nitrate provides the N, which is a macronutrient, needed by primary producers. In surface waters where N is the limiting nutrient, the additional N introduced can result in over production by the primary producers and result in a condition called eutrophication. The over production by primary producers generates increased biomass in a system which results in the depletion of av ailable oxygen in the system to organisms for respiration. Eutrophication results in the reduction of species in a water body and ultimately can result in a dead water body. Nutrients delivered by the Mississippi River have been shown to contribute to the “dead zone” in the Gulf of Mexico and nutrients (primarily P) are the main problem in Lake Okeechobee (Zagier, 2003; Hey, 2002). Water quality standards for nitrate-nitrogen There is a numeric groundwater standard for NO3-N of 10 mg N L-1 which is for the protection of human health. However, there is no numeric surface water standard for NO3-N in the State of Florida. The Florida Admini strative Code (F.A.C.) 62-302.530 for surface water narrative standard for nutrients st ates “that nutrients shall not cau se an imbalance to flora or

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45 fauna”. U.S. Department of Agriculture (1991) developed water quality indices for tidal and freshwater based on NO3-N concentration. The water quality i ndices are presented in Table 2-3. Water Quality Assessments In 1979, the FDEP identified the Middle Suwa nnee River Basin (MSRB) as one of five watersheds within the State of Florida for potential groundwat er contamination by nonpoint sources due to agricultural practices (FDEP, 1979). However, the ranking was based on professional judgment due to the paucity of groundwater data within the watershed. Furthermore, in Florida, ground water has few regul ations in place to protect it from nutrient contamination from non-point sources of pollution such as agriculture runoff (Hauserman, 2000). In the late 1980’s, a shift in agricultural pract ices occurred in dairy operations in the SRB in Florida, primarily in Suwannee and Lafayette counties. The number of dairy operations and the number of dairy cows increased. It was perceived that the dairy cow population was increasing in the SRB due to the dairy buyouts in the Lake Okeechobee Basin in south Florida and that the dairy operations from the Lake Ok eechobee Basin were shifting to the SRB. The dairy buyouts in the Okeechobee were designed to reduce surface runoff loadings of P, a macronutrient, to Lake Okeechobee which was impacting the water quality of the lake due to the lake being P limited. The loading of P was accel erating the eutrophication of the lake. This perceived increase in dairy cows populations resulted in concern am ong local public health officials as to the effects of the waste from the dairy operations in Suwannee and Lafayette counties would have on groundwater quality. Si nce the Floridan aquifer is unconfined in Suwannee and Lafayette counties, it is easily co ntaminated with water soluble contaminates, such as, NO3-N (E. Wilson, 2004, Personal Communication).

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46 The state health officials with the Florida Department of Health and Rehabilitative Services (HRS) started private well surveys ne ar dairy operations in Suwannee and Lafayette counties (these counties comprise a regi on known as the MSRB) in 1990 (E. Wilson, 2004, Personal Communication). These surveys revealed that 20 to 30 percent of the wells near dairy operations had NO3-N concentrations in excess of the St ate Drinking Water Standard of 10.0 mg N L-1. Some of the wells sampled by the HRS in the MSRB in 1990-92 had NO3-N concentrations in excess of 20 mg N L-1 (USDA, 1993). The NO3-N contamination in excess of the Drinking Water Standard was observed in ten wells located on dairy operations (HRS, 1992). At the same time, ambient monitoring for NO3-N in the surface water resources and springs in the MSRB indicated a statistically significant increasing trend (Ham 1996) while Mueller et al. (1995) identified increasi ng concentrations of NO3-N in the upper Floridan aquifer system in the same region. The results of these monitoring acti vities prompted the FDEP to start requiring industrial wastewater permits for any new da iry operations in the SRWMD in 1992 (E. Wilson, 2004, Personal Communication). Also, under the Clean Water Act the U. S. Environmental Protection Agency (EPA) in 2002 began regul ating through the state’s Department of Environmental Protection confined animal feedi ng operations (CAFO). A dairy is considered a confined animal feeding operations if it has more than 700 dairy cows. In the MSRB, the implementation of confined animal feeding opera tions regulation only affected seven of the dairies since the majority of the dairy opera tions had less than 700 dairy cows (D. Smith, 2004, Personal Communication). In 1993, the United States Department of Ag riculture – Soil Conservation Service (now known as the Natural Resource Conservation Servi ce) submitted a watershed protection plan and environmental assessment under the authority of the Watershed Protection and Flood Prevention

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47 Act and in accordance with the National Environmental Policy Act to Secretary of Agriculture (USDA, 1993). The objective of the pl an was to reduce the potential for NO3-N leaching to the Floridan aquifer from animal operations through the installation of best management practices (BMPs) in the MSRB. The watershed protectio n plan setup public law 566 (PL-566) projects that receive federal assistance wi th the implementation of projects that are consistence with the actions outlined in the plan. Furthermore, in 1996 the Florida Legisl ature provided line item funds to assist in the implem entation of the Soil Conservation Services Watershed Protection Plan. Federal and state funds are used to co st share the implementation of BMPs on animal operations to help prevent leaching of NO3-N in to the upper Floridan aquifer. A follow up study of private drinking water wells conducted in 1997 by the FDEP found that wells near animal husbandry operation were 29 percent more likely to have NO3-N concentrations greater than the Drinking Water Standard for NO3-N (Copeland et al., 1999). The EPA has found that nutrients are the leading cause of water quality impairment in estuaries and the second leading cause of water quality impairme nt in lakes and rivers (EPA, 1994). Also, the EPA defined the number one source of impairment to rivers and lakes are from agriculture and agriculture is the third source of impairment fo r estuaries (EPA, 1994). The SRWMD ambient monitoring identified the MSRB as the largest contributor of the NO3-N load to the Suwannee River. Figure 210 shows the loadings by sub-basins in the Suwannee River system. The highest percentage of the NO3-N loading is derived from the MSRB. In this region, ground water from the uppe r Floridan aquifer enters the Suwannee River via springs and seeps. The ground water provides the base flow to the Suwannee River in this region. Under base flow conditions, the flow in the Suwannee River doubles in volume from the top of the MSRB (near Dowling Park, Florida) to the bottom the MSRB (near Branford, Florida).

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48 In the MSRB, there are no tributaries to the river, thus, the increase in fl ow is directly due to ground water influx from the upper Florid an aquifer via springs and seeps. A series of studies added to the knowledge that NO3-N contamination of the upper Floridan aquifer was occurring and the NO3-N contamination of the upper Floridan aquifer was impacting the water quality of the springs along the Suwannee Rive r and the river itself. The average NO3-N concentration in the upper Floridan aquifer was observed to be 30 to 40 mg N L-1 under dairy lagoons and high in tensity areas, 30 mg N L-1 under spray fields which receive dairy effluent, 6.2 mg N L-1 on dairy pastures, and on average 4.25 mg N L-1 under property adjoining dairy farms (USDA, 1993; Andrews, 1994). Duri ng base flow in the MSRB, Pittman et al. (1997) observed a 160 per cent increase in the NO3-N concentration in the Middle Suwannee River (Dowling Park to Branford). Springs in the MSRB have NO3-N concentrations that range from 10 to 300 times greater than the background concentration for NO3-N of 0.05 mg N L-1 (Maddox et al., 1992; Scott et al., 2002, Scott et al., 2004, Katz et al., 1999, Berndt et al., 1998, Hornsby and Mattson, 1998; and Hornsby and Ceryak, 1999). Also, when the Suwannee River was compared to the Altamaha River, St. J ohns River, Satilla River, Ogeechee River, Withlacoochee River (South), and the Ochlockone e River, the Suwannee River had the highest in-stream TP and NO3-N load km- of basin of the seven rivers (Asbury and Oaksford, 1997). Based on N estimation from potential sources in the SRWMD, there are multiple sources of N in the MSRB with fertilizer bei ng the largest potential contribu tor, poultry the second largest potential contributor, and dairy cows the third largest potential contributors as shown in Figures 2-11 and 2-12 (Hornsby and Matt son, 1998). Furthermore, the Suwannee River and its estuary have been shown to be N limited (Quinlan, 2003 ). A study conducted by Katz et al. (1999 and 2001) showed that the mean age of the water discharging from the springs was between 12 and

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49 25 years old in the MSRB. This st udy indicates that the observed NO3-N concentration in the ground water, rivers and springs represents NO3-N that may have entered the aquifer under land uses that occurred 12 to 25 years ago and from mixed sources. All the sources of N within the MSRB (Suwannee and Lafayette counties) are anthropogenic. Thus, the NO3-N from the MSRB accounts for 45 percent of the annual NO3-N load for the Suwannee River for water year 1998 (F igure 2-10); there are multiple sources of N within the basin and the travel time within the upper Floridan aquifer is between 12 and 25 years (Katz et al., 1999). The FDEP classified the waters of the MS RB as being impaired due to nutrients, primarily NO3-N, in the FDEP Water Quality Assessmen t 305(b) Report to the U.S. EPA in 1998 (FDEP, 1998). The Water Qua lity Assessment 305(b) Report is required to be submitted to the EPA every two years by the State’s envi ronmental assessment agen cy under the authority of the Clean Water Act. The lis ting of the Suwannee River in th e 305(b) report resulted in the Suwannee River being listed on the FDEP, 2002 Sec tion 303(d) List of Impaired Waters for the development of TMDL. The listing of the Suwa nnee River on the 303(d) will result in FDEP allocation of pollutants (i.e., nitrates) to permitte es within the Florida portion of the SRB. Groundwater Domain Delineation Understanding the region/area from whic h ground water is derived aids in the management of the resource. Groundwater stud ies have used various techniques to define contributing areas (or basins) to the ground wa ter. The two commonly used methods are utilizing groundwater level or potentiometr ic surface and geochemical fingerprinting or hydrochemical facies. The first method util izes contours of potentiometric surface of groundwater levels. This method used ground wate r moving perpendicular to the contours and

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50 defines the basin at bend points in the potentiometric contour. J ones and Upchurch (1993) used this method to define a study area for the contributing groundwater domain to Lithia and Buckhorn springs. Davis (1996) used potentiomet ric surfaces to determine groundwater basins in North Central Florida and Southwest Georgia. The basins defined by Davis delineated the groundwater basins (spring sheds) for Spring Creek spring group, Wakulla spring, Saint Marks spring, and Wacissa spring group. Also, Upchurch et al. (2001) referenced this method for defining a preliminary groundwater domain (spr ingshed) for springs within the SRWMD. Furthermore, Upchurch et al. ( 2001) referenced the uses of geoc hemical fingerprinting to refine groundwater domains. Geochemical factor analysis (fingerprinting) has been used in the SRWMD to identify recharge areas within the upper Floridan aqui fer (Lawrence and Upchurch, 1982). From the factor analysis, four distinct chemical distin ct water masses were identified as well as the impacts of the quality of the recharge water enteri ng the upper Floridan aqui fer. Factor analysis was employed due to the combining of variables that are correlated into clusters in order of the amount of variance explained (Lawrence and Up church, 1978; Lawrence and Upchurch, 1982). Jones et al. (1996) used hydrochemi cal facies analysis (geochemical fingerprinting) to determine groundwater quality domains to Ra inbow Springs to ascertain dis tinctive water qua lity and relate the observed water quality within the domain to sp ecific spring vents within the Rainbow springs group. The hydrochemical facies placed a series of water quality analyses into a spatial context that allowed for patterns to be determined. Al so, hydrochemical facies analyses were used by Maddox et al. (1992) when determining the quality of waters within the Florida’s aquifers. Variations in NO3-N concentrations within the groundwat er domain of Rainbow Springs were due to anthropogenic sources such as i norganic fertilizer (J ones et al., 1996).

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51 In most published studies by geol ogists, the term factor analys is is used when the actual analysis is Principal Component Analysis (Dav is, 1973). Principal Component Analysis (PCA) is used to interpret the structure within the vari ance-covariance matrix of a multivariate data set (Davis, 1973). The PCA is a method that simp lifies a dataset (Lawrenc e and Upchurch, 1982). PCA is also called Karhunen-Loeve transform. Based on this literature review, additional ev aluation of water quality issues in the SRB are needed to define th e extent of nutrients, NO3-N and TP, and relations hips between the water resources, nutrients and possible sources of the nutrients. This dissertation will address the interaction of ground and surface water, extent and changes over time of nutrients, NO3-N and TP, in the water resources of the SRWMD and eval uate relationships of the possible sources of the nutrients, NO3-N and TP, with observed concentrations in the water resources with the goal of determining anthropoge nic factors effecting NO3-N and TP concentrations in the water resources.

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52 Table 2-1. Reaches of the Suwannee River (Hornsby et al., 2000). Reach Description 1 Upper River Blackwater 2 Cody Scarp Transitional 3 Middle River Calcareous 4 Lower River Calcareous 5 Tidal Riverine 6 Estuary (same as 5 with salinity) Table 2-2. National NO3-N concentrations in 383 U. S. Rivers (USDA, 1991). Percentile Concentrations 25t h 0.21 mg N L-1 50t h 0.40 mg N L-1 75t h 0.89 mg N L-1 Table 2-3. Tidal-fres hwater water quality indices based on NO3-N concentration (USDA, 1991). Condition Nitrate-Nitrogen (mg N L-1) Healthy and High Quality < 0.6 Fair 0.6 to 1.0 Fair to Poor 1.0 to 1.8 Poor > 1.8 Note: For higher salinity levels N is more limiting and optimum N concentrations are much lower than 0.6 mg N L-1

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53 Figure 2-1. Physiography regions of the Suwannee River Water Management District (Hornsby and Ceryak, 1999).

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54 LegendSoil Component ADAMSVILLE ALAGA ALPIN APOPKA ARENTS ASTATULA BIGBEE CANDLER CASSIA CHIPLEY CLARA ELECTRA VARIANT FORT MEADE FORT MEADE VARIANT FOXWORTH GAINESVILLE HURRICANE KERSHAW KUREB LAKE LAKELAND MANDARIN ORLANDO ORSINO ORTEGA OSIER OTELA OUSLEY PAOLA PENNEY PICKNEY PITS PLACID POMPANO PSAMMAQUENTS QUARTZIPSAMMENTS RESOTA RIDGELAND RIDGEWOOD TAVARES UDORTHENTS VALDOSTA Figure 2-2. High leaching soils in the Su wannee River Water Management District.

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55 Figure 2-3. Generalized geologic cross section of the region (modified from Ceryak et al., 1983).

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56 Floridan Unconfined Floridan Confined/Semi-confined County Boundaries District Boundary 02040Miles NNOTE: This map was prepared for informational purposes and does not conform to National Map Accuracy Standards. No attempt has been made to establish or locate specific jurisdictional boundaries of either federal, state, or local agencies. Figure 2-4. Confined and unconfined regions of the Floridan aquifer system (Hornsby and Ceryak, 1999).

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57 Figure 2-5. Map showing the reaches of the Su wannee River in Florid a (Hornsby et al., 2000). Reach 6

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58 0.00 20.00 40.00 60.00 80.00 100.00 120.00S UW0 1 0 S UW0 4 0 S UW0 7 0 SUW080 SUW100 SUW120 SUW130 S U W 1 40 S U W 1 50 S U W 1 60 S U W 2 4 0mg/L as CaCO3 Reach 1 Reach 2 Reach 3 Reach 4 Reach 5 Figure 2-6. Plot of mean alkalinity (mg L-1 as CaCO3) in the five reaches of the Suwannee River in Florida (Hornsby et al., 2000). 0 50 100 150 200 250 300 350 400 450SU W 010 SUW0 4 0 SU W 070 SUW0 8 0 S UW 100 SUW1 2 0 S UW 130 SUW1 4 0 S UW 150 SUW1 6 0 S UW 240PCU Reach 1 Reach 2 Reach 3 Reach 4 Reach 5 Figure 2-7. Plot of mean color (PCU) in the five reaches of the Suwannee River in Florida (Hornsby et al., 2000).

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59 Figure 2-8. P cycle in soils. Nonlabile PLabile PP inputsP loss Solution P H2PO4 -HPO4 2Primary Minerals Secondary Minerals Soil Organic Matter Adsorbed P Plant and animal residues Fertilizer Soil Organic Matter Leaching Erosion Plant uptake Dissolution Precipitation Dissolution Desorption Adsorption Immobilization Mineralization

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60 Figure 2-9. N cycle in soils. Processes InputsLosses Plant and animal residues N fixation Plant uptake NH3 N2O, NO, N2 Leaching Soil organic matter NH4 + N02 N03 NH4 + Fixation on clays Mineralization Immobilization MineralizationN i t r i f i c a t i o nDenitrification Volatilization Fertilizer

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61 Figure 2-10. Nutrient loadings by watershed/reach in the Suwannee River System for water year 1998 (Hornsby and Mattson, 1998).

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62 Beef Cows 5.8% Beef Cows 5.8% Beef Cows 5.8% Dairy Cows 5.4% Dairy Cows 5.4% Poultry 34.1% Poultry Poultry 34.1% People 1.0% People 1.0% 1.0% Fertilizer 48.9% Fertilizer Fertilizer 48.9% Atmospheric 4.8% Atmospheric 4.8%Estimated Nitrogen Inputs Estimated Nitrogen InputsSuwannee County Suwannee CountyTotal 28,992,636 pounds of N Figure 2-11. Estimated N inputs for Su wannee County (Hornsby and Mattson, 1998). Estimated Nitrogen Inputs Estimated Nitrogen InputsLafayette County Lafayette CountyTotal 13,819,763 pounds of N Beef Cows 3.6% Beef Cows 3.6% Dairy Cows 18.3% Dairy Cows 18.3% Poultry 31.1% Poultry 31.1% People 0.5% People 0.5% Fertilizer 38.7% Fertilizer 38.7% Atmospheric 7.9% Atmospheric 7.9% Figure 2-12. Estimated N inputs for Lafa yette County (Hornsby and Mattson, 1998).

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63 CHAPTER 3 COMPARISONS OF PRE AND POST OUTSTANDING FLORIDA WATER CONCENTRATIONS, TRENDS AND RECENT OCCURRENCES OF NITRATENITROGEN AND TOTAL PHOSPHORUS Introduction The Florida Legislature in 1979 designat ed the Suwannee River in Florida an Outstanding Florida Water (OFW) which means th e River has significant cultural and ecological value to the State of Florida. The Florida De partment of Environmenta l Protection (FDEP) was directed by Florida Statues Chap ter 403.061 (27) which states “Est ablish rules which provide for a special category of water bodies within the Stat e, to be referred to as Outstanding Florida Waters, which water bodies shall be worthy of special protection because of their natural attributes. Nothing in this subs ection shall affect any existing ru les of the department.” Thus, the FDEP developed a rule 62-302.700 Florida Administrative Code (F .A.C.). Rule 62-302.700 (1) F.A.C. states “It shall be the Department policy to afford the highest protection to Outstanding Florida Waters and Outstanding Na tional Resource Waters. No degradation of water quality, other than that a llowed in subsections 62-4.242(2) and (3), F.A.C., is to be permitted in Outstanding Florida Waters and Outstanding National Resource Waters, respectively, not withstanding any other Departme nt rules that allow wa ter quality lowering.” This rule focuses on point source discharges in to an OFW. Furthermore, rule 62-302.700 (8) F.A.C. establishes the baseline definition for wa ter bodies designated OFWs, as stated in the following: “For each Outstanding Florida Wa ter listed under subsection 62-302.700(9), F.A.C., the last day of the baseline year for defining the existing ambient water quality (paragraph 624.242(2)(c), F.A.C.) is March 1, 1979, unless otherwise indicated. Where applicable, Outstanding Florida Water boundary expansions are indicated by date(s ) following “as mod.” under subsection 62-302.700(9), F.A.C. For each Outstanding Florida Water boundary which

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64 expanded subsequent to the original date of designation, the baseline year for the entire Outstanding Florida Water, including the e xpansion, remains March 1, 1979, unless otherwise indicated.” The Suwannee River falls in the init ial induction into the OFW status; therefore, the last day of the baseline year is March 1, 1979. The Suwannee River at Branford, Florida, has been monitored for water quality analytes by the United States Geological Survey (USG S) since 1954 and the Suwannee River Water Management District (SRWMD) since 1989. Conc urrently, with water quality monitoring, the USGS monitors daily discharge for the Suwa nnee River at Branford (station number 02320500) since 1931 to present. Due to the paucity of hi storical data for the Santa Fe River only the Suwannee River at Branford will be discussed in this Chapter for long trend analysis and comparisons to pre-OFW, baseline, and post-OF W concentrations of total phosphorus (TP) and nitrate-nitrogen (NO3-N). The SRWMD Water Assessment Regional ne twork (WARN) has 67 surface water quality stations (47 river and 20 spring stations ) and 251groundwater quality stations as shown in Figures 3-1 and 3-2, respectively (Hornsby et al., 2005C). The WARN data will be used to determine the recent distribution and occurrences of TP and NO3-N in the SRWMD. The WARN surfacewater quality stations have a peri od of record of sixteen years (Hornsby et al., 2005A) and the WARN groundwater qua lity stations have a period of record of six years (Hornsby et al., 2005B). The WA RN surfacewater quality monitoring was started in 1989 while the WARN groundwater quality monitoring was star ted in 2000. The WARN water quality data provides a dataset that has been collected and an alyzed in a consistent manner. This reduces variation in the data due to collec tion and analyzed method differences.

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65 The objectives of this chap ter are to analyze and interp ret changes in the TP and NO3-N concentrations in the Suwannee River at Br anford from pre-OFW conditions to post-OFW conditions by combining several data sets, re late possible anthropogenic factors to observed changes, and determine the recent occurrences of TP and NO3-N in surface water, springs and ground water in the upper Florid an aquifer within the SRWMD using WARN data. Materials and Methods Long Term Trend Analysis Data was collected from the USGS for th e station on the Suwannee River at Branford, Florida and the SRWMD. The USGS has been m onitoring water quality at this site since 1954. The USGS data contains NO3-N and potassium (K) concentrations from 1954 to 1989 and TP concentration from 1971 to 1989. The SRWMD data contains NO3-N, K, and TP data from 1989 to 2006 for the Suwannee River at Branford. The data from the USGS and the SRWMD were combined to form a time series (or period of record) from 1954 to 2006. Period of record graphs were produced for TP, K, and NO3-N. The period of record for NO3-N, K and TP were analyzed for linear correla tion. Post-OFW median water year values for NO3-N and TP were compared to median pre-OFW values using a Mann-Whitney test. The anthropogenic factors, such as, fertilizer sales, crop acreages, a nd population, were gathered for the period of record for correla tion with riverine TP and NO3-N concentrations. Recent Distribution and Occurrences of To tal Phosphorus and Nitrate-Nitrogen The SRWMD WARN data was analyzed usi ng MiniTab to generate descriptive statistics (mean, standa rd deviation, median, 25th percentile, 75th percentile) for ground water (upper Floridan aquifer and springs) and su rfacewater quality. Surface water was further subdivided by river basin. Annual mean upper Florid an aquifer concentrati ons contours of TP

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66 and NO3-N were generated using Surfer with the kr iging option with linear interpolation and zero nugget. Annual surfacewater basin loading was determin ed using water quality data collected by the SRWMD, under my supervision, and discharge volume collected by the USGS and SRWMD. Loads for TP and NO3-N were calculated by sub-basin. Results and Discussion Long Term Trends The median annual TP concentration in the Su wannee River at Branford for the period of record (1971 to 2006) ranged from 0.13 to 0.34 mg P L-1 as shown in Appendix A, Figure A-1. Based on the data, there was an increasing tre nd from 1971 to 1985 and a declining trend starting in 1986 in the Suwannee River at Branford for TP as seen in Figure 3-3. The TP concentrations dropped in water years 1985 and 1986 and have continued to d ecline. The range of TP concentrations observed by water year is shown in Figure 3-4. This drop in TP concentration in 1985-1986 and the declining trend is associated with the regulation of a poi nt source discharge for phosphate mining operations in northern Colu mbia and eastern Hamilton counties (J. Owens, 1998. Personal Communication). Also, the variati ons in the riverine co ncentrations observed have been reduced since 1986 due to regulation of the point source. The Suwannee River has a background concentration of TP of 0.3 mg L-1 due to the river coming into contact with the Hawthorne Group that contains high levels of P (FDER, 1985). Thus, the TP concentration in the Suwannee River is decreasi ng due to better management practices by the phosphate mining operation. The median annual NO3-N concentrations in the Suwannee River at Branford for the period of record (1954 to 2006) ranged from 0.14 to 1.21 mg N L-1 as shown in Appendix A,

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67 Figure A-2. Based on the data, th ere is an increasing trend in the Suwannee River at Branford for NO3-N (Figure 3-5). Ham and Hatzell (1996 ) documented this increasing trend for NO3-N for the period of 1954 to 1995 for the Suwannee River at Branford. Recent data (1996 to 2006) indicates that the increasing trend is still present. The range of NO3-N concentrations observed by water year is shown in Figure 3-6. Comparison of Pre and Post OFW Water Quality The OFW language in F.A.C. establishes 1979 as the baseline year for water quality for the Suwannee River and that the water quality should not degrade from the baseline water quality. Changes in water quality in the Suwa nnee River can be determined by comparing the water quality of a point in time to the water qua lity during the baseline year. Using the water quality data prior to and includ ing the baseline year defines th e pre-OFW and water quality data after the baseline year defined the post -OFW. A comparison of annual median NO3-N and TP concentrations to 1979, the year the River was de signated an OFW are given in Table 3-1. The baseline annual median concentrations for NO3-N and TP are 0.50 mg N L-1 and 0.235 mg P L-1, respectively; and post-OFW annual median concentrations for NO3-N and TP are 0.72 mg N L-1 and 0.152 mg P L-1, respectively. The comparison of base line to post-OFW concentration shows a decreasing trend at greater than the 99.9 % c onfidence level for TP and a increasing trend at greater than the 99.9 % confidence level for NO3-N. Also, a comparison of water years 1954 to 1979 or pre-OFW designation me dian concentrations of NO3-N and TP of 0.14 mg N L-1 and 0.21 mg P L-1, respectively; and water years 1979 to 2006 or post-OFW designation annual median concentrations of NO3-N and TP of 0.72 mg N L-1 and 0.152 mg P L-1, respectively, yielded similar results to the preOFW to the post-OFW. The annual NO3-N loads for 1979 and 1998 to 2005 (post-OFW) are presented in Table 3-2. The annual NO3-N load for 1979 was

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68 3,548,981 kg N yr-1 while the annual NO3-N load for water year 2005 was 6,197,855 kg N yr-1. This shows an approximately 75 pe rcent increase in the annual NO3-N load for the Suwannee River to the Gulf of Mexico from 1979 to 2005 and is indicative of th e increasing trend in NO3N concentrations in the river. Anthropogenic Factors The counties adjacent to the Suwannee Rive r at Branford are Suwannee and Lafayette. The reach of the Suwannee River that borders Suwa nnee and Lafayette countie s receives little to no surface water inputs due to the internal draina ge of the counties; however, the River picks up flow from groundwater discharge via springs a nd seeps in the riverbed during base flow conditions. This pickup in flow from groundwater inputs can al most double the volume in the River from upstream to down stream under certa in flow conditions (T. Mirti, 2003, Personal Communication). Data has show n that the reach of the Suwannee River, also known as the Middle Suwannee River Basin (M SRB), bordering Suwannee and Lafayette counties has the largest increase in NO3-N concentration than any other subbasin in the Suwannee River system and the NO3-N was associated with flow conditions that are dominated by groundwater inputs (Hornsby et al., 2005A). The population began increasing between 1970 to 1980 for Suwannee and Lafayette counties (Figure 3-7). The combined populatio ns for Suwannee and Lafayette counties were plotted against annual median NO3-N and TP concentrations for the Suwannee River at Branford as shown in Figures 3-8 and 3-9, respectiv ely. The plot of population versus NO3-N concentrations in the Suwannee River at Branfo rd shows as population increases so does the riverine NO3-N concentration. The increase in riverine NO3-N concentration associated with the increase in population may be due to increase d densities of onsite domestic systems (septic

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69 tanks) and/or increased use of fertilizers asso ciated with improved pasture and agricultural production. Based on the data for TP, there is an inverse relationship with TP concentration and population; however, this is a spurious correla tion because the concentration of TP in the Suwannee River is dominated by the mini ng discharge in the upper River. Fertilizer sales data (N, K, P) for Suwannee and Lafayette counties from 1941 to 2006 are shown in Figure 3-10. Florida Department of Agriculture an d Consumer Services (DACS) Fertilizer sales data represents the sale and use of fertiliz er within a county (W. Cox, 1997, Personal Communication). Florida Department of Agriculture and Consumer Services tracks the sales and the designation of N fe rtilizers in the State as re quired by Chapter 576.041(7), Florida Statues. Reports on fertilizer sales and des tination county are reporte d to DACS on a monthly basis as required by Chapter 576, Florida Statues. Thus, DACS can generate annual reports by county that represents the fertilizer sales as well as fertilizer applied in each county within the State. Figure 3-11 presents the annual medi an TP concentration in the Suwannee River at Branford and P sales for 1971 to 2006. There is no correlation with sales data and riverine TP concentrations. Based on the P sales data, a shar p increase in P sales occurred in 1998 and has remained well above historic sales data from 197 1 to 1998. The increase in P sales that occurred in 1998 maybe attributed to reapplication of P to crops during the growin g season due to El Nio conditions; however, this is not the case for 1999 to 2006. The departure from historical sales data is most likely associated with a change in the DACS methodology fo r the collection of P sales data. A possible reason fo r the P sales remaining above th e historical le vel since 1998 may be a result of a change in reporting format that occurred in 1994 which the fertilizer dealers submit to DACS (W. Cox, 2007, Personal Communi cation). Furthermore, since 1998, DACS does not compile the fertilizer sales data or deve lop the annual fertilizer sales report. Florida

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70 Department of Agriculture and Consumer Serv ices now contracts the data management and development of the annual report of fertilizer sales to the Un iversity of Kentucky (D. Terry, 2007, Personal Communication). Theref ore, the potential exists that the historical P sales data have been under reported. Figure 3-12 presents the annual median NO3-N concentrations in the Suwannee River at Branford and N sales for 1954 to 2006. There was a linear increasing trend in fertilizer sales and riverine NO3-N concentrations from 1954 to 1982. From 1982 to 1992, sales data indicates dramatic fluc tuations in N sales; however, the sales were lower than the time period from1954 to 1982. The riverine NO3-N concentrations began dropping in 1988 and shows similar fluctuations as the sales data. This drop in riverine concentr ations reflects the drop in total crop acres, primarily co rn acreage, in Suwannee and La fayette counties as shown in Figure 3-13. In 1998, a spike in sales for N was re ported similar to the spike of P in 1998. Also, Figure 3-13 shows that from 1960 to 1999 N fertilizer sales data tracked the total crop acres in Suwannee and Lafayette counties; however, since 1988, N fertilizer sales data has diverted from the total cropped acres indicating th at more fertilizer is being a pplied per acre than in the period 1960 to 1988. The correlation of the N fertilizer sales and riverine NO3-N concentration was analyzed using Minitab time series analysis with cross correlation. Based on a cross correlation of N fertilizer sales and riverine NO3-N concentration, there is a one to six year time lag between the relationship of N sale s data and the observed riverine NO3-N concentrations (Table 3-3). This time lag or reside nce time in sales data and riverine NO3-N concentrations is most likely a result of rainfa ll and the path from the application through the upper Floridan aquifer to river via springs and s eeps in the riverbed. The variati on in rainfall from year to year greatly influences the rate at which NO3-N will be leached from the root zone and vadose zone and reach the underlying aquifer. Furthermore, th e residence time is related to tortuosity of the

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71 flow path and aquifer properties, such as, h ead, porosity and transmissivity (Maddox et al., 1992). The annual median potassium (K) concentrations in the Suwannee at Branford were plotted for water years1954 to 2006 in Appendix A, Figure A-3. An increasing trend for riverine K was observed (Figure 3-14). The trend for K was similar to the trend observed for NO3-N. The riverine annual median for K and NO3-N were plotted form 1954 to 2006 in Figure 3-15. Figure 3-16 presents the annual median K concentr ations in the Suwannee River at Branford and K sales for 1954 to 2006. The K sales data show s that prior to 1998 the amount of K sold in Suwannee and Lafayette counties was less than 100,000 kg y-1; however, in 1998 a spike in sales occurred, sales for 1998 were ~500,000 kg and since 1998 have ranged between 225,000 to 300,000 kg. The increases in 1998 for K also occurred for P and N. This was possibly due the heavy rainfall in the spring of 1998 that was generated by a strong El Nio. The heavy springtime rains result in leaching events and fa rmers reapplied fertilizer to replace the leached nutrients. As with P and N, the reported K sales have been greater than historical levels since 1998. This might be attributed to a change in re porting format in 1994 that the fertilizer dealers submit to DACS and different data manageme nt and report format developed by DACS contractor, the University of Kentuc ky (W. Cox, 2007, Person al Communication) Recent Distribution and Occurrences of To tal Phosphorus and Nitrate-Nitrogen Upper Floridan aquifer water quality Background concentrations for TP and NO3-N in the upper Floridan aquifer is < 0.1 mg P L-1 and <0.05 mg N L-1, respectively (Maddox et al., 1992). The mean upper Floridan aquifer concentrations for TP and NO3-N are 0.219 mg P L-1 and 0.94 mg N L-1, respectively (Table 34). These concentrations (2001-2006) are th ree times above background and 23 times above

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72 background concentrations for TP and NO3-N, respectively. Annual mean distributions for water years 2001 to 2005 of TP, NO3-N, and K in the upper Floridan a quifer are presented in Appendix B, Figures B-1A to B-1E, B-2A to B-2E, and B-3A to B-3E, respectively. The annual mean distribution for water year 2006 for TP, NO3-N, and K are presented in Figures 3-17, 3-18, and 3-19, respectively. Lower TP concentrations are observed in the regions where the upper Floridan aquifer is confined while the higher concentrations were observed in the unconfined regions of the upper Floridan aquifer (Figure 3-17). Since the unconf ined region receives recharge almost directly from rainfall events, the pH of the recharge water is still slightly acidic; thus, mobilizing TP. Thus, the distribution of TP in the upper Floridan aquifer seems to be controlled by whether the upper Floridan aquife r is confined or unconf ined. The highest NO3-N concentrations were observed in the unconfined regions of the uppe r Floridan aquifer; while, the lowest NO3-N concentrations are observe d in the confined regions of the upper Floridan aquifer (Figure 3-18). Nitrogen applied to the land surf ace in the unconfined re gions leached into the upper Floridan aquifer when recharge events occur. Thus, NO3-N concentrations seem to be controlled by both geology and land use prac tices. The mean upper Floridan aquifer concentration for K was 1.23 mg K L-1 compared to the background concentration of 1.1 mg K L-1. The concentration of K observed in the up per Floridan aquifer has no relationship to geology (Figure 3-19). Both the unconfined and c onfined regions have similar concentrations. There are regions within the unconfined upper Floridan aquifer that show K depletion that may correlate to zones where the ground water is discharging (i.e., conduct flow) and possibly represents a groundwater basin. A summary of all collected water quality parameters for the upper Floridan aquifer is presented in Appendix B, Table B-1 a nd contour concentrations for TP, NO3-N, and K are

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73 graphically presented in Appendix B, Figures B-1A to B-1E for TP, Figures B-2A to B-2E for NO3-N, and Figures B-3A to B-3E for K. Spring water quality Spring water quality data are presented by sp ecific river basin. The mean TP for the springs of Aucilla River Basin is 0.053 mg P L-1, for the springs of Coastal Rivers Basin is 0.075 mg P L-1, for the springs of Lower Suwannee River Basin (LSRB) is 0.051 mg P L-1, for the springs of Santa Fe River Basin is 0.083 mg P L-1, for the springs of Upper Suwannee River Basin is 0.102 mg P L-1, for the springs of Waccasassa River Basin is 0.045 mg P L-1, and the springs of Withlacoochee River Basin is 0.054 mg P L-1 (Table 3-5). The TP observed in the springs reflect the concentrati ons of TP observed in the upper Floridan aquifer which supplies water to the springs. Springs in the unconfined regions of the upper Florid an aquifer have higher TP concentrations than the sp rings in the confined region. The mean NO3-N for springs of the Aucilla River Basin is 0.16 mg N L-1, for the springs of Coastal Rivers Basin is 0.05 mg N L-1, for the springs of LSRB is 3.01 mg N L-1, for the springs of Santa Fe River Basin is 0.90 mg N L-1, for the springs of Upper Suwannee River Basin is 0.40 mg N L-1, for the springs of Waccasassa River Basin is 0.43 mg N L-1, and the springs of Withlacoochee River Basin is 1.34 mg N L-1 (Table 3-5). Similarly, to TP, the NO3-N concentrations in the springs are a reflection of the concentrations in the upper Floridan aquifer. The unconfined regions of the upper Floridan aq uifer are producing springs with the highest concentrations of NO3-N. The unconfined regions of th e upper Floridan are subject to contamination by water soluble contaminants, such as NO3-N. A summary of all collected water quality para meters for the springs of Aucilla River Basin is presented in Appendix B, Table B-2, for th e springs of Coastal Rive rs Basin is presented

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74 in Appendix B, Table B-3, for the springs of LS RB is presented in Appendix B, Table B-4, for the springs of Santa Fe River Basin is presente d in Appendix B, Table B-5, for the springs of Upper Suwannee River Basin is presented in Appendix B, Table B-6, for the springs of Waccasassa River Basin is presented in A ppendix B, Table B-7, and the springs of Withlacoochee River Basin is presen ted in Appendix B, Table B-8. Surface water quality The mean TP for the Alapaha River Basin is 0.127 mg P L-1, for the Aucilla River Basin is 0.026 mg P L-1, for the Coastal Rivers Basin is 0.169 mg P L-1, for the LSRB is 0.115 mg P L-1, for the Santa Fe River Basin is 0.151 mg P L-1, for the Upper Suwannee River Basin is 0.253 mg P L-1, for the Waccasassa River Basin is 0.075 mg P L-1, and the Withlacoochee River Basin is 0.137 mg P L-1 (Table 3-6). The exception of the Upper Suwannee River Basin which is influenced by a point discharge and geological formation, the TP concentration seems to be influenced by geological formation. The mean NO3-N for the Alapaha River Basin is 0.48 mg N L-1, for the Aucilla River Basin is 0.05 mg N L-1, for the Coastal Rivers Basin is 0.07 mg N L-1, for the LSRB is 0.57 mg N L-1, for the Santa Fe River Basin is 0.34 mg N L-1, for the Upper Suwannee River Basin is 0.15 mg N L-1, for the Waccasassa River Basin is 0.10 mg N L-1, and the Withlacoochee River Basin is 0.39 mg N L-1 (Table 3-6). The riverine NO3-N concentration seems to be influenced by the NO3-N concentrations in the ground water of the upper Floridan aqui fer adjacent to the rivers. A summary of all collected water quality parameters for the Alapaha River Basin is presented in Appendix B, Table B-9, for the Auci lla River Basin is presented in Appendix B, Table B-10, for the Coastal Rivers Basin is pr esented in Appendix B, Table B-11, for the LSRB is presented in Appendix B, Table B-12, for the Santa Fe River Basin is presented in Appendix

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75 B, Table B-13, for the Upper Suwannee River Basi n is presented in Appendix B, Table B-14, for the Waccasassa River Basin is presented in Appendix B, Table B-15, and the Withlacoochee River Basin is presented in Appendix B, Table B-16. Annual TP and NO3-N loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005 are presented in Figures 3-20 and 3-21, respectively. Asbury and Oaksford (1997) comparison of the Suwannee Ri ver to the Altamaha River, St Johns River, Satilla River, Ogeechee River, Withlacoochee River (South), and the Ochlockonee River, showed the Suwannee River had the highest in-stream TP and NO3-N load km- of basin of the seven rivers. Quinlan (2003) demonstrated that the Suwann ee River and its estuary are N limited. Thus, increases in NO3-N loads in the Suwannee River and the estuary will increase the potential for eutrophication. Figures 3-22 a nd 3-23 present the TP and NO3-N for water years 1998 to 2005 with annual rainfall. The TP loads increased wi th increased rainfall. This is likely due to surfacewater runoff from the headwater in the Ok efenokee Swamp that lowers the pH and results in leaching of P from the Hawthorne Group and other sites where P is bound. The NO3-N loads increases with rainfall is most lik ely due to the flushing of the NO3-N from the soil profile into the upper Floridan aquifer that is connected to the rivers. Based on the regionalization of the SRB developed by Hornsby and Mattson (1998), th e mainstem of the Suwannee and Santa Fe rivers are subdivided into six and two reaches, re spectively. Annual TP loads for the sub-basins of the SRB for each water year from 1998 to 2004 ar e presented in Appendix B, Tables B-17A to B-17F and graphically presented in Appendix B, Figures B-4A to B-4G. The annual TP and NO3-N loads for the sub-basins of the SRB for wa ter year 2005 are presented in Table 3-7 and graphically presented in Figure 324. The sub-basin that contribut ed the largest percentage of the TP load is Reach 1 of the Suwannee Rive r, followed by the Alapaha and Withlacoochee

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76 rivers for water years 1998 to 2005. This is th e region where the Suwannee River intersects the Hawthorne Group and where a phosphate mining opera tion discharges to the Suwannee River. The sub-basin that contributed the largest percentage of the NO3-N load is Reach 3 of the Suwannee River, followed by Reach 2 of the Santa Fe River for water years 1998 to 2005. Summary and Conclusions The observed concentrations of TP and NO3-N in the Suwannee River at Branford has significantly (>95% confidence level) changed sin ce its designation as an Outstanding Florida Water in 1979. The annual median TP concentra tions in the Suwannee River have significantly decreased from 0.235 mg P L-1 in water year 1979 to 0.148 mg P L-1 in water year 2006. The decrease in the annual median TP concentra tion in the Suwannee River that started in 1985 coincides with the increased regulation of a phosphate mining operation in Hamilton and Columbia counties. The annual median NO3-N concentrations in the Suwannee River have significantly increa sed from 0.50 mg N L-1 in water year 1979 to 1.21 mg N L-1 in water year 2006. There is an observed time lag between the sales data and riverine NO3-N concentrations of one to six years. The increasing trend for NO3-N in the Suwannee River is supported by the increased use of inorganic ferti lizer. Therefore, anthropogenic f actors are driving the changes in water quality for TP and NO3-N from pre-OFW to pos t-OFW concentrations. The mean upper Floridan aquifer concentrations for TP and NO3-N are three times above background and 23 times above background concentr ations, respectively, as defined by Maddox et al (1992). Surfacewater NO3-N concentrations reflect the u pper Floridan aquifer groundwater concentrations for NO3-N in the adjacent surfac ewater basin. Surfacewater basin concentrations of TP are driven by geological formations, point sources and surface runoff. While, surfacewater basins with low concentrations of NO3-N in the upper Floridan aqui fer have low concentrations

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77 of NO3-N observed in the surface wa ter and surfacewater basins w ith high concentrations of NO3-N in the upper Floridan aquifer have high concentrations of NO3-N observed in the surface water. The basin with the highest percentage load of TP is Reach 1 of the Suwannee River. This is a region of the Suwannee River where a point source discharges and where the River comes in contact with a P bearing Hawthorne Group. The ba sins with the highest percentage loads of NO3-N is Reach 3 of the Suwannee River and Reach 2 of the Santa Fe River. These are regions that have high concentrations of NO3-N in the upper Floridan a quifer and the Suwannee and Santa Fe rivers receives ground wa ter from numerous springs a nd riverbed seeps during base flow conditions. Thus, ground water from the uppe r Floridan aquifer plays a major role on the quality of surface water in regions where the River intersects the top of the upper Floridan aquifer.

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78 Table 3-1. Comparison of pre and pos t OFW concentrations of TP and NO3-N to OFW baseline concentrations of TP and NO3-N for the Suwannee River at Branford. Water Year Median NO3-N (mg N L-1) Trend Significant Median TP (mg P L-1) Trend Significant 1954 to 1979 (pre OFW) 0.14 0.21 1979 to 2006 (post-OFW) 0.72 increasing <0.0001 0.152 decreasing<0.0001 1979 (Baseline) 0.50 0.235 Annual water year comparis on to Baseline 1998 0.49 Neutral 0.6474 0.109 decreasing<0.0001 1999 1.05 increasing <0.0001 0.118 decreasing<0.0001 2000 0.835 increasing 0.0001 0.129 decreasing<0.0001 2001 0.680 increasing 0.0346 0.123 decreasing<0.0001 2002 0.875 increasing 0.0003 0.216 decreasing 0.0215 2003 0.595 increasing 0.6711 0.160 decreasing<0.0001 2004 0.97 increasing 0.0051 0.167 decreasing<0.0001 2005 0.43 decreasing0.3218 0.153 decreasing<0.0001 2006 1.21 increasing 0.0040 0.151 decreasing<0.0001 Table 3-2. Comparison of OFW baseline annual NO3-N load to water years 1998 to 2005 annual NO3-N load. Water Year Annual NO3-N Load (kg N yr-1) Departure from Baseline Mean Discharge [cfs/L s-1)] 1979 3,548,981 Baseline 8,657(245,139) 1998 6,402,033 Greater than 15,476(438,232) 1999 4,270,788 Greater than 6,415(181,653) 2000 2,358,000 Less than 3,406(96,447) 2001 2,356,146 Less than 5,339(151,183) 2002 2,674,080 Less than 3,275(92,738) 2003 4,036,590 Greater than 10,088(285,660) 2004 4,789,350 Greater than 6,467(183,125) 2005 6,197,855 Greater than 16,310(461,848)

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79 Table 3-3. Cross correlation of N ferti lizer sales and annual median riverine NO3-N concentration for the Suwannee River at Branford. Lag time (years) Cross correlation function -8 -0.0596 -7 -0.0567 -6 0.0228 -5 0.0719 -4 0.1256 -3 0.2065 -2 0.2917 -1 0.4014 0 0.4312 1 0.5200 2 0.5547 3 0.5456 4 0.5540 5 0.4681 6 0.5090 7 0.4028 8 0.3469 Table 3-4. Summary of NO3-N and TP concentrations in the upper Floridan aquifer for the Suwannee River Water Management District (2001 to 2006). Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Minimum Maximum NO3-N mg L-1 0.94 2.73 0.00 0.17 1.00 0.000 52.0 TP mg L-1 0.219 1.558 0.000 0.07 0.156 0.000 45.0

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80 Table 3-5. Summary of NO3-N and TP concentrations for the Sp rings by River Basin (1989 to 2006). Basin Parameter Mean Standard Deviation 25th PercentileMedian 75th PercentileMinimumMaximum Units Aucilla NO3-N mg L-1 0.17 0.14 0.05 0.13 0.26 0.00 0.46 Aucilla TP mg L-1 0.054 0.053 0.036 0.043 0.056 0.009 0.319 Coastal NO3-N mg L-1 0.05 0.07 0.02 0.03 0.05 0.00 0.38 Coastal TP mg L-1 0.075 0.020 0.068 0.072 0.078 0.047 0.128 Lower Suwannee NO3-N mg L-1 3.01 3.11 1.30 1.91 3.45 0.00 21.80 Lower Suwannee TP mg L-1 0.051 0.031 0.032 0.047 0.064 0.004 0.430 Santa Fe NO3-N mg L-1 0.91 1.60 0.39 0.58 1.01 0.00 26.00 Santa Fe TP mg L-1 0.084 0.058 0.048 0.077 0.101 0.004 0.820 Upper Suwannee NO3-N mg L-1 0.40 0.40 0.02 0.29 0.70 0.00 1.91 Upper Suwannee TP mg L-1 0.102 0.046 0.060 0.111 0.136 0.004 0.220 Waccasassa NO3-N mg L-1 0.44 0.25 0.42 0.43 0.65 0.03 0.65 Waccasassa TP mg L-1 0.046 0.006 0.044 0.046 0.048 0.039 0.053 Withlacoochee NO3-N mg L-1 1.35 0.35 1.17 1.40 1.58 0.27 1.94 Withlacoochee TP mg L-1 0.054 0.016 0.044 0.050 0.060 0.040 0.140

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81 Table 3-6. Summary of NO3-N and TP concentrations for each River Basin in the Suwannee River Water Management District (1989 to 2006). Basin Parameter Mean Standard Deviation 25th PercentileMedian 75th PercentileMinimumMaximum Units Alapaha NO3-N mg L-1 0.48 0.44 0.14 0.31 0.72 0.00 2.00 Alapaha TP mg L-1 0.191 0.097 0.110 0.180 0.250 0.041 0.567 Aucilla NO3-N mg L-1 0.05 0.05 0.01 0.03 0.07 0.00 0.44 Aucilla TP mg L-1 0.054 0.027 0.037 0.048 0.070 0.011 0.150 Coastal NO3-N mg L-1 0.07 0.11 0.02 0.05 0.06 0.00 0.71 Coastal TP mg L-1 0.285 0.707 0.054 0.091 0.139 0.010 9.600 Lower Suwannee NO3-N mg L-1 0.57 0.33 0.31 0.56 0.81 0.00 2.44 Lower Suwannee TP mg L-1 0.161 0.094 0.111 0.140 0.181 0.004 1.320 Santa Fe NO3-N mg L-1 0.34 0.32 0.07 0.26 0.56 0.00 4.80 Santa Fe TP mg L-1 0.204 0.368 0.080 0.124 0.210 0.001 6.000 Upper Suwannee NO3-N mg L-1 0.15 0.31 0.03 0.05 0.20 0.00 8.04 Upper Suwannee TP mg L-1 0.299 0.535 0.100 0.168 0.280 0.004 8.900 Waccasassa NO3-N mg L-1 0.10 0.09 0.02 0.09 0.16 0.00 0.49 Waccasassa TP mg L-1 0.075 0.036 0.050 0.068 0.098 0.023 0.350 Withlacoochee NO3-N mg L-1 0.39 0.28 0.20 0.32 0.51 0.00 2.36 Withlacoochee TP mg L-1 0.137 0.098 0.093 0.115 0.147 0.010 1.100

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82 Table 3-7. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2005. Contributing Basin Area (mi) Annual Load Contribution (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 41,589.9 0.7% 340,891.6 14.6% Alapaha River 1,801 155,304.6 2.5% 297,750.6 12.7% Withlacoochee River 2,382 1,166,049.5 18.8% 507,256.9 21.7% Withlacoochee GA 2,118 441,407.9 7.1% 340,207.0 14.5% Withlacoochee – FL 264 724,641.6 11.7% 167,049.8 7.1% Suwannee River Reach 2 443 208,815.9 3.4% 748,258.8 31.9% Suwannee River Reach 3 824 2,362,408.1 38.1% 201,830.1 8.6% Santa Fe River Reach 1 820 48,107.4 0.8% 237,689.3 10.1% Santa Fe River Reach 2 564 1,133,998.0 18.3% 145,558.5 6.2% Suwannee River Reach 4 342 -421,452.7 -6.8% -106,884.5 -4.6% Suwannee River Reaches 5 & 6 344 1,503,034.7 24.3% -29,667.8 -1.3% Total 9,950 6,197,855.5 100% 2,342,683.5 100.0%

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83 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H# # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # *Legend# *River Station! HSpring Station Figure 3-1. Suwannee River Water Management Di strict surfacewater quality monitoring network.

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84 # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # #* # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # *# # # # # # # # # # # # # # # # # # # # # / / / / / / / / / / / / / / / / / / / / / / / / / / / / / /" / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / /" / / / / / / / / / / / / /Legend" /Trend Well# *Status Well Figure 3-2. Suwannee River Water Management District groundwat er quality monitoring network.

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85 Figure 3-3. Median TP for the Suwannee Rive r at Branford with linear trend lines.

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86 Water yearTotal P (mg/L) 2 0 0 6 2 0 0 5 2 0 0 4 2 0 0 3 2 0 0 2 2 0 0 1 2 0 0 0 1 9 9 9 1 9 9 8 1 9 9 7 1 9 9 6 1 9 9 5 1 9 9 4 1 9 9 3 1 9 9 2 1 9 9 1 1 9 9 0 1 9 8 9 1 9 8 8 1 9 8 7 1 9 8 6 1 9 8 5 1 9 8 4 1 9 8 3 1 9 8 2 19 8 1 1 9 8 0 1 9 7 9 1 9 7 8 1 9 7 7 1 9 7 6 1 9 7 5 1 9 7 4 1 9 7 3 1 9 7 2 1 9 7 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Figure 3-4. TP concentration by water year for Suwannee River at Branford. Box represents 25th percentile, median, 75th percentile and whiskers represents the upper and lower observed value.

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87 y = 0.0177x + 0.0504 R2 = 0.6839 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.401 954 1956 1 9 58 1960 1 9 62 1 9 68 1970 1 9 72 1 97 4 1976 1 9 78 1980 1982 1 9 84 1986 1 9 88 1 99 0 1992 1 9 94 1996 1998 2 0 00 2002 2 0 04 2 0 06Median NOx-N (mg/L) Figure 3-5. Median NO3-N for the Suwannee River at Branford with linear trend line.

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88 Water YearNOx-N (mg/L) 2 0 0 6 2 0 0 5 2 0 0 4 2 0 0 3 2 0 0 2 2 0 0 1 2 0 0 0 1 9 9 9 1 9 9 8 1 9 9 7 1 9 9 6 1 9 9 5 1 9 9 4 1 9 9 3 1 9 9 2 1 9 9 1 1 9 9 0 1 9 8 9 1 9 8 8 1 9 8 7 1 9 8 6 1 9 8 5 1 9 8 4 1 9 8 3 1 9 8 21 9 8 1 1 9 8 0 1 9 7 9 1 9 7 8 1 9 7 7 1 9 7 6 1 9 7 5 1 9 7 4 1 9 7 3 1 9 7 2 1 9 7 1 1 9 7 0 1 9 6 9 1 9 6 8 1 9 6 7 1 9 6 2 1 9 6 1 1 9 6 0 1 9 5 9 1 9 5 8 1 9 5 7 1 9 5 6 1 9 5 5 1 9 5 4 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Figure 3-6. NO3-N concentration by water year for Suwann ee River at Branford. Box represents 25th percentile, median, 75th percentile and whiskers represents the upper and lower observed value.

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89 0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000 1950196019701980199020002004Population Lafayette Suwannee Figure 3-7. Population for Lafaye tte and Suwannee Counties, 1950 th rough 2004 (BEBR, 2001; BEBR, 2004).

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90 0 0.2 0.4 0.6 0.8 1 1.2 1.41 9 5 0 1 9 5 2 1 9 5 4 1 9 5 6 1 9 5 8 1 9 6 0 1 9 6 2 1 9 6 4 1 9 6 6 1 9 6 8 1 9 7 0 1 9 7 2 1 9 7 4 1 9 7 6 1 9 7 8 1 9 8 0 1 9 8 2 1 9 8 4 1 9 8 6 1 9 8 8 1 9 9 0 1 9 9 2 1 9 9 4 1 9 9 6 1 9 9 8 20 0 0 2 0 0 2 2 0 0 4 2 0 0 6Median NOx-N (mg/L)0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000 45,000 50,000Population Median NOx-N Suwannee and Lafayette Counties Population Figure 3-8. Median NO3-N concentration for the Suwannee River at Branfo rd and population for Lafayette and Suwannee counties (BEBR, 2001; BEBR, 2004).

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91 0 0.05 0.1 0.15 0.2 0.25 0.3 0.351970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006Water YearTotal P (mg/L)0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000 45,000 50,000Population Total P Population Figure 3-9. Median TP concen tration for the Suwannee River at Branford a nd population for Lafayette and Suwannee counties (BEBR, 2001; BEBR, 2004).

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92 0 1,000,000 2,000,000 3,000,000 4,000,000 5,000,000 6,000,000 7,000,000 8,000,0001 94 4 1946 1 9 48 1 9 50 1952 1 9 54 1 9 56 1958 1 9 60 1 9 62 1964 1 9 66 1 9 68 1970 1 9 72 1 9 74 1976 1978 1 9 80 1982 1 9 84 1 9 86 1988 1990 1 9 92 1994 1996 1 9 98 2 000 2 0 02 2 0 04N Fertilizer Sales (kg)0 100,000 200,000 300,000 400,000 500,000 600,000 700,000 800,000 900,000P or K Fertilizer Sales (kg) N P K Figure 3-10. Fertilizer sales data for Suwannee and Lafayette counties.

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93 0 0.05 0.1 0.15 0.2 0.25 0.3 0.351971 1972 1 97 3 19 7 4 1975 1976 1 97 7 19 7 8 1979 1980 1981 1 98 2 19 8 3 1984 1985 1 98 6 19 8 7 1988 1989 1 990 19 9 1 19 9 2 1993 1 994 1 99 5 19 9 6 1997 1998 1 99 9 20 0 0 2001 2002 2003 20 0 4 2005 2006Median P (mg/L)0 100,000 200,000 300,000 400,000 500,000 600,000 700,000 800,000 900,000Fertilizer sales (kg of P) Median total P Phosphorus sales for Suwanneee and Lafayette counties Figure 3-11. Median TP concentration for the Suwannee River at Branford and N fertilizer sale for Suwannee and Lafayette count ies.

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94 0 0.2 0.4 0.6 0.8 1 1.21954 1956 19 5 8 19 6 0 1 96 2 1 96 4 1966 1968 1970 1972 19 7 4 19 7 6 1 97 8 1 98 0 1 98 2 1984 1986 1988 1990 19 9 2 19 9 4 1 99 6 1 99 8 2000 2002 2004 2006median NOx-N (mg/L)0 1,000,000 2,000,000 3,000,000 4,000,000 5,000,000 6,000,000 7,000,000 8,000,000Fertilizer Sales (kg) median Nox-N N Fertilizer Suwannee & Lafayette counties Figure 3-12. Median NO3-N concentration for the Suwannee River at Branford and N fertilizer sales for Suwannee and Lafayette counties.

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95 0 0.2 0.4 0.6 0.8 1 1.2 1.41 96 0 1 96 2 1964 1 9 66 1 9 68 1 97 0 1 97 2 1 97 4 1976 1 9 78 1 98 0 1 98 2 1 98 4 198 6 1988 1 9 90 1 99 2 1 99 4 1 99 6 1998 2 0 00 2 0 02 2 00 4 2 00 6Median NOx-N (mg N/L)0 20,000 40,000 60,000 80,000 100,000 120,000 Median Nox-N Total Crops (acres) N Fertilizer (* 100 kg) Figure 3-13. Median NO3-N concentration for the Suwannee River at Branfo rd and N fertilizer sales and total crop acres for Suwannee and Lafayette counties.

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96 y = 0.0195x + 0.2723 R2 = 0.7482 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.81954 1956 1958 1960 1962 19 6 7 1969 1971 1973 1975 19 7 7 1979 1981 1983 1985 19 8 7 1989 1991 1993 1995 19 9 7 1999 2001 2 00 3 2005Water YearMedian K (mg/L) Figure 3-14. Median K concentration for the Suwa nnee River at Branford with linear trend line.

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97 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.81 9 54 1956 1 9 58 1960 1 9 62 1 9 67 1 969 1 9 71 1973 1 97 5 1 9 77 1979 1 9 81 1983 1 9 85 1 9 87 1 989 1 9 91 1993 1 9 95 1997 1 999 2 0 01 2003 2 0 05Water YearConcentration (mg/L) Median K Median Nox-N Figure 3-15. Median K and median NO3-N concentrations for the Su wannee River at Branford.

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98 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.81954 1956 1 95 8 19 6 0 19 6 2 1964 1966 1968 1 97 0 1 97 2 19 7 4 19 7 6 1978 1980 1 982 1 98 4 19 8 6 19 8 8 1990 1992 1994 1 99 6 1 99 8 20 0 0 20 0 2 2004 2006Median K (mg/L)0 100,000 200,000 300,000 400,000 500,000 600,000Fertilizer Sales (kg) Median K K sales Suwannee and Lafayette counties Figure 3-16. Median K concentration for th e Suwannee River at Branford and K fertiliz er sale for Suwannee and Lafayette counti es.

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99 Mean Total Phosphorus Concentration (mg/L) October 2005 to September 2006TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Confined Floridan Figure 3-17. Mean upper Floridan aquifer TP concentration contour map for water year 2006.

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100 Mean Nitrate-Nitrogen Concentration (mg/L) October 2005 to September 2006 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.50 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Confined Floridan Figure 3-18. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2006.

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101 Mean Potassium Concentration (mg/L) October 2005 to September 2006K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.2 1.425 2.65 5.1 10 40 50 Confined Floridan Figure 3-19. Mean upper Floridan aquifer K c oncentration contour ma p for water year 2006.

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102 0 5 10 15 20 25 30 35 40 1990199119921993199419951996199719981999200020012002200320042005 Water YearTotal Phosphorus (100,000 kg/yr) Figure 3-20. TP loads for the Suwannee River to the Gulf of Mexico for water years 1990 to 2005.

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103 0 1 2 3 4 5 6 7 1990199119921993199419951996199719981999200020012002200320042005 Water YearNitrate-N Loads (1,000,000 kg/yr) Figure 3-21. NO3-N loads for the Suwannee River to the Gu lf of Mexico for water years 1990 to 2005.

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104 0 5 10 15 20 25 19981999200020012002200320042005Annual TP load (100,000 kg of P)0 20 40 60 80 100 120 140 160 180 200Annual Rainfall (cm) TP Load Rainfall Figure 3-22. Annual TP loads and rainfall by water year for the Suwannee River.

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105 0 1 2 3 4 5 6 7 19981999200020012002200320042005 Water YearAnnual NOx-N Load (1,000,000 kg)0 20 40 60 80 100 120 140 160 180 200Annual Rainfall (cm) Nox-N Load Rainfall Figure 3-23. Annual NO3-N loads and rainfall by water year for the Suwannee River.

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106 Figure 3-24. Suwannee River Basin loadi ng by watershed/reach for water year 2005.

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107 CHAPTER 4 NITROGEN LOADING FROM GROUD WATER TO SELECTED REACHES OF THE SUWANNEE AND SANTA FE RIVERS Introduction Ground water can either contribute positively to river flow through riverbed inflows and spring discharge or negatively by river water se epage through the riverbed and reverse spring discharge, depending on hydrologi c conditions (Winter et al., 1998; Dingman, 2002). Hornsby et al. (2004) demonstrated that the Suwannee River has reaches that receive ground water from the upper Floridan aquifer and reaches which lose surface flow to the aquifer. Water loss from the Suwannee River to the upper Floridan aquifer occurs when the stage of the river is higher than the adjacent groundwater levels This results in a cessation of flow from the springs along the Suwannee River and reverses flow or estevell e, which results in focus recharge. The river has incised into the top of the upper Floridan aqui fer in the lower reaches of the Suwannee River. Under base flow conditions, the Suwannee River stage is lower than the adjacent groundwater levels in the upper Florida aquifer. This re sults in the ground water discharging through the springs and seeps along the riverbed. The numer ous springs and the amount of ground water that discharges to the river indicat e the interaction of the Suwannee River and the upper Floridan aquifer (Hull et al., 1981). The Middle Suwannee River Basin (MSRB) has karstic geology and the region is internally drained. The internal drainage results in karst features, such as sinkholes that capture the surface water from streams. The result is th at surface waters, such as streams, do not flow for long distances and are directly connected to the underlying upper Floridan aquifer. In some cases, surfacewater features, such as Rose Creek in the Lower Santa Fe River Basin (LSFRB),

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108 that are captured by sinkholes have been shown to be directly connected by conduits in the upper Floridan aquifer to springs within the surfacewater basin (FDEP, 2000). The Lower Suwannee and the Lower Santa Fe Rivers and their associated springs flows depend on the groundwater levels in the cont iguous upper Floridan aquifer (Grubbs and Crandall, 2007). This interaction of the gr ound water and surface water results in the ground water having dramatic impacts of the surfacewater quality of the rivers (Hull et al., 1981). Pittman et al. (1997) conducted a study of a 33 mile (53 km ) reach of the MSRB (Dowling Park to Branford), that was divided into an upstream and downstream segment, to assess the impact of groundwater discharge on the quantity and quality of water in the Suwannee River. The study was conducted under base flow conditions. The objective of the study was to determine whether the measured springs and other groundwater inflows and NO3-N contributions were similar in each segmen t. They found that 11 % of the 3,700 kg N d-1 of NO3N load in the study area was from the upstrea m segment and 89 % was from the downstream segment. Furthermore, in the upstream segmen t, the four springs accounted for 92 % of the 350 cubic feet per second (cfs) [9,911 L s-1] flow pickup with the re maining 8 % consisting of riverbed seepage; while, the downstream segment the springs accounted for 41 % of the 600 cfs (16,990 L s-1) flow pickup and the remaining 59 % flow pickup was associated with riverbed seepage. The Suwannee River Water Management Dist rict (SRWMD) monitoring stations on the Suwannee and Santa Fe rivers are shown in Figur es 4-1 and 4-2, respectively. Data from the monitoring network for the period 1989 to 2006 has shown an increasing trend for NO3-N concentrations in the Suwannee and Santa Fe rivers as they traverse from their headwaters to

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109 downstream. The increase in the NO3-N concentrations is associat ed with regions of the river that receive ground water inputs. The largest increase in NO3-N concentration in the SRB occurred between Dowling Park and Branford (MSRB), a 60.8 kilometer (km) segmen t of SRB (Figure 4-3). The largest increase in NO3-N concentration occurred in the Santa Fe River between US 441 and State Road 47 (Figure 4-4). To date, no study has identified the exact ar ea within the MSRB or the LSFRB where the NO3-N load is entering the river system from the groundwater system. This study will expand on the work of Pittman at al. (1997) and the SRWMD monitoring program by sampling the Suwannee River in the MSRB on 1.6 km segments fr om Dowling Park to Branford. Also, this study will be expanded to include the LSFRB (Riv er Rise to the conflu ence with the Suwannee River). The initial sampling will identify the river segment where NO3-N concentrations currently increase in the rivers. The sampling in crement lengths will be decreased and in-stream discharge measurements of th e river and discharge measurement for the springs will be conducted to define the segment or segm ents with the greatest increase in NO3-N load. The results of this study will identify the se gment(s) and springs within MSRB and LSFRB associated with groundwater inputs that are contributing to the increase in NO3-N loads in the surface water and qualitatively rela te adjacent landuse to the segment(s) with the greatest increase in NO3-N loads. Materials and Methods Water quality sampling and discharge m easurements were performed over an approximately 61 km stretch of the Middle Su wannee River from Dowling Park, Florida, downstream to Branford, Florida on July 21 and 22, 2000; and an approximately 42 km stretch of

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110 the Lower Santa Fe River, from its re-emergence in River Rise State Park to its confluence with the Suwannee River on June 7, 2000. Measurements were made on subsequent sampling dates on selected segments of the above reaches as in dicated in Table 4-1. Sampling locations were chosen at intervals not exceeding 2.2 km and at all inflow points (i.e., springs). The distance between locations was determin ed using a global positioning system (GPS) where the path between points was nearly stra ight. Where the curvature of the river made straight-line distan ces difficult to determine, a combination of a USGS topographic map for the area, a 1:24,000 scale mileage template, and site recognition of mapped feat ures were used. GPS points were collected in 1983 No rth American Datum (NAD83) and differentially corrected to provide a 3-5 meter (m) accuracy range to ensure sampling locations. Vertical-axis meter discharge measurements (i.e., Price AA and Pygmy current meters) were conducted in springs, such that, no partial section contained more than five percent of the flow from the spring; conseque ntly, approximately 25 partial sections were used at each measurement (Buchanan and Somers, 1969). The two-point method (velocity measurements at the 0.2 and 0.8 tenths depths) was used primarily fo r velocity measurement in a partial section. The six-tenths method, is where the velocity meter is placed six-tenths of the total depth from the surface of the water being measured, was employed as necessary and appropriate to instrument capabilities, velocity profile char acteristics, and the partial secti on depth. Data obtained from the spring discharge measurements included the spring name, date of measurement, beginning and ending times of measurement, beginning and endi ng reference water level measurements, width of measurement, total cross-sectional area, mean velocity, and discharge. Discharge measurements were conducted on the river us ing Teledyne Workhorse Rio Grande Acoustic Doppler Current Profiler (ADCP) and were performed by the FDEP. Discharge measurements

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111 were performed using the ADCP following the gui delines established in ADCP manuals by RD Instruments. The discharge measurements with the ADCP included five cross-sectional traverses of the stream. The discharge from each trav erses were sum and a mean was calculated to determine the discharge. For springs discharging less than one cfs (28.3 L s-1), field estimates were made. Water chemistry samples were collected in mid channel and at a depth of 0.5 m while spring samples were collected as ne ar as possible to the spring ve nt. Samples were preserved in accordance with FDEP Standard Operating Proc edures (011/01) and analyzed using EPA methods (EPA, 1983). Results and Discussion Middle Suwannee River Basin (MSRB) The MSRB was sampled from Dowling Park to Branford at 1.6 km intervals for NO3-N on July 21 and 22, 2000 (Figure 4-5). The NO3-N concentration incr eased from 0.32 mg N L-1 at Dowling Park to 0.52 mg N L-1 at Branford (Figure 4-6). The highest rate of increase in NO3-N concentration in the river was observed over a 12 .8-km stretch sampling points 19 to 28 (circled area on Figure 4-6). The NO3-N concentrations in the springs in the MSRB for July 21 and 22, 2000, ranged from 0.02 to 13.8 mg N L-1 (Table 4-2). The flow increased from 1,030 cfs (29,166 L s-1) at Dowling Park to 1,480 cfs (41,908 L s-1) at Branford. The springs accounted for 277 cfs (7,844 L s-1) of the flow increase or 62 % at low flow conditions (Table 4-2) Since, there are no surfacewater inflow points in this stretch of th e river; the increase not accounted for by measured springs is presumably due to groundwate r inputs through the riverbed. The NO3-N load increased by 1,080 kg N d-1 from Dowling Park to Branford and the springs in the reach accounted for approximately 1,080 kg N d-1 or 100 % of the load increase (Table 4-2). This

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112 indicates that the NO3-N concentration in the adjacent upper Floridan aqui fer is greater than the NO3-N concentration in the Suwannee River. Ba sed on the loading increase, the concentration of NO3-N in the upper Floridan aquifer is 2 to 30 tim es that of the concentration observed in the Suwannee River. Pittman et al. (1997) study consisted of three river sites which had discharge gages (Suwannee River near Dowling Park, FL station number 301259083143700, Suwannee River at Luraville, FL station number 02320000, and Suwann ee River at Branford, FL station number 02320500) and three springs in the upstream segmen t and eight (8) springs in the downstream segment. The study area (Dowling Park to Br anford) was divided into an upstream segment (Dowling Park to Luraville) and a down stream segment (Luraville to Branford) The study concluded that 11 % of the 3,700 kg N d-1 of NO3-N load in the study area was from the upstream segment and 89 % was from the downstr eam segment. Furthermore, the study found that in the upstream segment the four sp rings accounted for 92 % of the 350 cfs (9,911 L s-1) flow pickup with the remaini ng eight percent consisting of riverbed seepage; while, the downstream segment the springs accounted for 41 % of the 600 cfs (16,990 L s-1) flow pickup and the remaining 59 % flow pickup was associated with riverbed seepage. The findings of the July 2000 sampling confirmed the findings of Pittma n et al. (1997) that the major of flow and NO3-N increase occurred in the MSRB below Luravi lle gage. This indicates that there is a consistent supply of ground water and NO3-N entering the MSRB below Luraville gage. Additional samplings were conducted from Luraville to Branford on October 24, 2000 and September 19, 2006. This river segment cove rs the area where the greatest increases in NO3-N were observed in the July 2000 sampling ev ent (Figure 4-5). In the MSRB on October 24, 2000, the highest rate of increase in NO3-N concentration in the river was observed over a

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113 4.8 km stretch (Figure 4-7). The September 19, 2006 sampling yielded similar results (Figure 48). Since there are no surfacewater inflow points in this stretch of the river, the increase not accounted by measured springs is presumably due to groundwater inputs through the riverbed. The NO3-N concentration increased from 0.61 mg N L-1 at Luraville to 1.07 mg N L-1 at Branford on October 24, 2000 and 0.70 mg N L-1 at Luraville to 1.10 mg N L-1 at Branford on September 19, 2006 (Figure 4-8). The increase in riverine NO3-N concentration is associated with the increase in groundwater discharge. Fi gure 4-9 shows an invers e relationship of river discharge and NO3-N concentration in the Suwannee Rive r at Branford. Thus, as the flow decreases the NO3-N concentration increases. Also, as gr ound water enters th e river system, the specific conductance of the river increases. Typi cally, surface water has specific conductance of less than 100 ohms cm-1; while ground water has specific c onductance generally greater than 250 ohms cm-1. As discharge increases the specific conductance in the Suwannee River at Branford decreases (Figure 4-10). This is a re sult of the stage of the river overcoming the groundwater head. The hydraulic gradient in the upper Floridan aquifer is toward the Suwannee River during low flow conditions and away from the river during high flow conditions (Hirten, 1996). Hirten (1996) identified th at the impacts of the high rive r stage on the potentiometric surface during high flow conditions extended outward from the river for approximately 3 km. As the specific conductance in the Suwannee River at Branford increases so does the NO3-N concentration in the rive r (Figure 4-11). The increase in grou ndwater discharge is a result of the river stage beginning lower in 2006 than 2000; thus, allowing more groundwater into the river. Since discharge was measured in the river at six locations (as indicated by the red lines in Figure 4-12), it is possible to calculate loading for each segment (Table 4-3). The load change for each segment was calculated by subtracting the upstream segment load from the load for the

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114 given segment. The highest NO3-N load change per m of river for both the 2000 and 2006 sampling events were observed in segment 3 (Figure 4-13). The major landuse adjacent to segment 3 is row crops on the Suwannee County side. On the Lafayette County side of segment 3, animal husbandry operations and improved pasture are the major landuses. The recommended University of Florida, Institute of Foods and Agricultural Science (IFAS) recommend N fertilizer rates for typical crops, corn, potatoes and watermelon, grown in the MSRB are 200 lb acre-1 (222 kg hectare-1), 200 lb acre-1 ( 222 kg hectare-1) and 150 lb acre-1 (168 kg hectare-1), respectively (Hochmuth and Hanlon, 2000). For hay, the IFAS recommendation for N is 80 lb acre-1 (89 kg hectare-1) in the spring and 80 lb acre-1 (89 kg hectare-1) following each cutting except for the fina l fall cutting (Mylavarapu et al., 2007). Generally, hay fields are cut four times per year (M. Randall, 2004, Pers onal Communication). Thus, hay fields may receive 320 lb acre-1 (359 kg hectare-1) based on IFAS recommended rates. While, IFAS N fertilizer recommendation for improved pasture range between 50 lb acre-1 (56 kg N hectare-1) and up to 160 lb acre-1 (179 kg N hectare-1) [Mylavarapu et al., 2007]. The landuses are occurring primarily on Alpin and Penney soils. Both soils are Entisols. The Alpin series consists of very deep, excessively draine d, moderately rapidly perm eable soils on uplands and river terraces of the Coastal Pl ain. The soils formed in thick beds of sandy eolian or marine deposits. (Soil Survey Staff, 2007). The Penney series consists of very deep, excessively drained, rapidly permeable soils on uplands. The soils formed in thick beds of sandy eolian or marine deposits (Soil Survey Staff, 2007). Thes e landuse uses are occurring over the unconfined Floridan aquifer on Entisols (Alpin and Penne y) which have high le aching potential. The contributions of the springs for Oct ober 2000 and September 2006 are given in Table 4-2. Also, Table 4-2 presents the discharge, NO3-N loading and percent of NO3-N load increase

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115 in the segment that the spring discharges. The NO3-N concentration of the springs ranged from 0.09 to 18.6 mg N L-1 in 2000 and 0.33 to 15.0 mg N L-1 in 2006. The two springs (SUW718971 and SUW725971) with the highest NO3-N concentrations discharge in segment 3. These two third magnitude springs were sampled by Katz et al. (1999 an d 2001) and yielded NO3-N concentrations of 29 and 38 mg N L-1 for SUW718971 and SUW725971, respectively. Katz et al. (1999) used isotopic ratios of 14N and 15N to determine the source of the NO3-N in the spring water from springs SUW718971 and SUW725971. Katz et al. (1999) findings showed that the NO3-N was from an inorganic source. Also, Katz et al. (1999) used ch lorofluorocarbons (CFC) to date the spring water from springs SU W718971 and SUW725971. The findings of the age dating were that the youngest water had a mean age of less than nine years reported by Katz et al. (1999). This corresponds with the observed time lag in Chapter 3 of fertilizer sales data and riverine NO3-N concentration of one to six years. Also, the Florida Department of Environmental Protection (FDEP) on an every other week schedule from March 15, 2000 to January 10, 2001 sampled these two sp rings (SUW718971 and SUW725971) for NO3-N and K (T. Greenhalgh, 2005, Personal Communication) The springs SUW718971 and SUW725971 show a clear linear relationship between the concentration of NO3-N and K, which indicates an inorganic (fertilizer) source as shown in Appendi x C, Figures C-1 and C-2, respectively. There is a major agricultural operation (row crop) w ithin 1.6 km of these springs. Based on the findings that inorganic fertilizer is correlated to the increasing NO3-N trend in the Suwannee River at Branford (Chapter 3), th e activities that occur adjacent to segment 3 (Figure 4-12) of the MSRB should be investigated.

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116 Lower Santa Fe River Basin (LSFRB) The LSFRB begins at River Rise, which is wh ere the Santa Fe River re-emerges from the upper Floridan aquifer after traveling approximately 3.2 km underground from River Sink. River Sink is located in O’Leno State Park and is a karst feature, which captures the entire Santa Fe River during all but extremely high flow cond itions. The LSFRB has 58 identified spring and six siphons (Hornsby and Ceryak, 1998). Thus, the LSFRB is highly connected to the upper Floridan aquifer. This connection with the upper Floridan aquifer has impacts on the water quality and quantity of the LSFRB. Unlike the springs in the MSRB, the springs in LSFRB do not typically reverse flow or estevelle. Due to the morphology of the rive r system, the surface stage cannot overcome the head in the upper Floridan aquife r. Also, should the river overcome the groundwater head at a spring vent, the groundwater pressure is relieved by discharging from kars t features within the floodplain. Thus, the observed decrease in riverine NO3-N concentrations in high flow conditions is related to dilution of ground water by surface water not by excluding the ground water from the surface water, as is the case for the MSRB. On June 7, 2000, the LSFRB was sampled on 1.6 km intervals for NO3-N (Figure 4-14). There was little discharge at River Rise due to the drought conditions and limited flow in the upper Santa Fe River. This crea ted a base flow condition that wa s virtually all ground water with little surface water inputs from the upper Santa Fe River. This allowed for the sampling of the LSFRB to determine the impacts of groundwater discharge on the NO3-N concentration in the river. The highest ra te of increase in NO3-N concentration in the LSFRB was observed over a 4.8 km stretch (Figure 4-15). The NO3-N concentration incr eased from 0.09 mg N L-1 at the Santa Fe Rise to 0.88 mg N L-1 near Fort White, with the co ncentration decreasing to the

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117 confluence with the Suwannee River. Ground wa ter inputs accounted for 100 % of the flow increase. The NO3-N concentrations in the springs in the LSFRB for June 7, 2000, ranged from 0.11 to 4.8 mg N L-1. Based on the sampling results from June 2000 sampling event, the sampling intervals were reduced and the sampling reach of the LS FRB was reduced to the Santa Fe River above Rum Island to the USGS gage near Fort White and the sampling was conducted on September 5, 2001 and October 10, 2006. In the LSFRB, the highest rate of increase in NO3-N concentration in the river was observed over a 0.3 km stretch (Figure 4-16) for September 5, 2001 and October 10, 2006. The NO3-N concentration increased from 0.28 mg N L-1 above Rum Island to 0.79 mg N L-1 near Fort White on September 5, 2001 and 0.26 mg N L-1 above Rum Island to 0.82 mg N L-1 near Fort White on October 10, 2006. As the cas e for the MSRB, the flow in the Santa Fe River was lower in 2006 than 2000. This results in less dilution of ground water by surface water in 2006 than 2000. Also, the percentage of flow increase in the river from the springs was greater in 2006 than 2000. Therefore, the riverine NO3-N concentration increased due to less quantity of the receiving surface water to dilute the NO3-N concentration in the groundwater that was discharge into the surfacewater system. Since discharge was measured in the river at three transects (as indicated by the red lines in Figure 4-17) on September 5, 2001 and at se ven transects on Octobe r 10, 2006 (as indicated by the red lines in Figure 4-18), it is possible to calculate load ing for each segment (Tables 4-4 and 4-5). The set of transects used in 2006 in corporated the three transects for 2001 by adding additional transects between the 2001 transects to better define the NO3-N inputs. A comparison of 2001 to 2006 loading increase per m of river is shown in Table 4-4 and Figure 4-19. The greatest increase in NO3-N loads change per m of river was observed in segment 1 for 2001 and

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118 2006 when the sampling reach was divided into three segments. The refined seven segments for 2006 segments indicated that segment 4 as the highest NO3-N load change per m of river for 2006 sampling events (Table 4-5 and Figure 4-20). The discharge contribution of the springs for September 5, 2001 and October 10, 2006 ar e given in Table 4-6. The NO3-N concentration of the springs ranged from 0.55 to 1.59 mg N L-1 in 2001 (Table 4-6) and 0.27 to 1.9 mg N L-1 in 2006 (Table 4-6). Segment 1 (for the 3 segmen t sampling) and segment 4 (for the 7 segment sampling) had the highest increase in NO3-N loads and contain the lotu s of springs known as the Devil’s complex. Based on the 2006 sampling, the NO3-N load is associated with the Devil’s complex that consists of two first magnit ude springs (Devil’s Ear and July). The landuses adjacent to segments 1 in 2001 and 4 in 2006 are improved pasture, recreational park, and low dens ity residential. These landuse uses are occurring over the unconfined Floridan aquifer on Entisols (Lakeland and Penney) with high leaching potential. Sabasan (2004) identified NO3-N concentrations in various landuse on Entisols, Ultisols, and Spodosols in the Santa Fe River Watershe d. For landuse improved pasture, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 0.51, 1.80 and 1.65 g N g-1of soil, respectively. The Entisols which are in landuse improve pasture have lower soil NO3-N due to the leaching of the NO3-N. And where these Entisols are over the unconfined Floridan aquifer there is potential for leaching of NO3-N into the upper Floridan aquifer. Katz et al. (1999) sampled the July and Ginnie Springs for 15N and 14N. The result of Katz’s study indicated that the NO3-N was from an inorganic source (i .e., fertilizer). As with the MSRB springs, the springs in the LSFRB in the segment where the NO3-N load in the river increases are discharging NO3-N whose source is inor ganic fertilizer.

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119 Summary and Conclusions The regions of the Middle Suwannee and Lo wer Santa Fe rivers where the greatest increase in NO3-N concentrations occur are relatively sma ll segments of studied river reach. The greatest increase in NO3-N load occurs in segment 3 of the MSRB, which is 3,408 m of river channel, and Segment 4 of the LSFRB, which is 425 m of river channel. The NO3-N is moving into the surfacewater system via ground water th rough springs and seeps in the riverbed during base flow conditions. The soils adjacent to thes e segments are Entisols that have high leaching potential. Furthermore, the upper Floridan aquife r is unconfined in these regions. The coupling of the upper Floridan aquifer being unconfined an d overlain by soil with high leaching potential with landuses that are adding NO3-N via fertilizer crea tes the potential for contamination of the upper Floridan aquifer and ultimately the Suwannee and Santa Fe river which receive base flow from the upper Floridan aquifer by the NO3-N. Two springs sampled in segment 3 of th e MSRB, where the highest increase in NO3-N loading occurred, showed a linear relationship with K and NO3-N. Also, these two springs were sampled by the USGS for NO3-N sourcing and age dating. The result from the USGS sampling showed the NO3-N source as inorganic and the age of the water was less than nine years (Katz et al., 1999) which is similar to the results observed in the lag time between fertilizer sales and riverine NO3-N concentrations in the Suwannee River at Branford in Chapter 3. Furthermore, for the Suwannee River at Branford, this confirms that fertilizer is the major component of the observed increasing NO3-N trend in the Suwannee River at Br anford (see Chapter 3). Segment 4 of the LSFRB springs was also sampled by Katz et al. (1999). The resu lts indicated that the major springs in segment 4 were discharging NO3-N that was primarily fro m inorganic fertilizer. The MSRB and LSFRB showed increased NO3-N concentrations from 2000-2001 to 2006

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120 sampling events. This indicates that the NO3-N loading from the gr ound water to the surface water is increasing for the studied areas of the Suwannee and Santa Fe rivers and the NO3-N is primarily from inorganic fertiliz er. Thus, understanding of fertili zer use and contribution areas to the upper Floridan aquifer, which supplies th e water to segment 3 of the MSRB and segment 4 of the LSFRB, is needed to fo cus management activities.

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121 Table 4-1. Suwannee River and Sa nta Fe River segments used in this study along with sampling dates and other pertinent information. River Segment Sampling Date Comments Middle Suwannee River Basin Dowling Park to Branford See Figure 4-5 for locations. July 21-22, 2000 Water samples and discharge measurements taken at 1.6 km intervals and at all identified springs of 61 km river segment. Luraville to Branford See Figure 4-12 for locations. October 24, 2000 Water samples and discharge measurements taken at the segment (34 km) of the river showing high NO3-N input. Samples were taken at irregular intervals ranging from 2 km down to 0.7 km. The sampling interval was based on the previous sampling event (i.e., in the segments with the greatest NO3-N increase the interval was reduced). Luraville to Branford September 19, 2006 Repeat of the October 24, 2000 sampling. Lower Santa Fe River Basin River Rise State Park to confluence with the Suwannee River. See Figure 4-14 for locations. July 7, 2000 Water samples and discharge measurements taken at 1.6 km intervals of 42 km river segment and at all identif ied springs. Above Rum Island spring to USGS discharge gage near Fort White. See Figure 417 for locations. September 5, 2001 Water samples taken at 0.3 km intervals of 5.4 km river segment and at all iden tified springs. Discharge measurements were taken at 3 transects and all flowing springs. River Rise State Park to confluence with the Suwannee River. See Figure 4-18 for locations. October 10, 2006 Water samples taken at 0.3 km intervals of 5.4 km river segment and at all iden tified springs. Discharge measurements were taken at 7 transects and all flowing springs.

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122 Table 4-2. Middle Suwannee Ri ver Basin spring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N load and contribution of the total NO3-N load increase in the study reach. River Segment Spring Discharge[cfs/( L s-1)) NO3-N (mg L-1) NO3-N Load (kg d-1) NO3-N Load change (%) 2000 2006 2000 2006 2000 2006 2000 2006 1 LAF924971 15(425) 12(340) 3.05 4.9 111 143 2.43 4.09 Telford 38(1,076) 25(708) 1.93 2.7 175 163 3.84 4.69 Running 49(1,388) 45(1,274) 2.32 2.3 275 251 6.02 7.21 2 LAF919972 1.5(43) 2(57) 1.36 2.00 4.95 9.71 0.11 0.28 Bathtub 6(170) 3(85) 1.34 1.4 19.5 10.2 0.43 0.29 Convict 2.3(65) 3(85) 7.9 9.4 44.5 68.4 0.98 1.96 SUW919971 4(113) 7(198) 0.52 0.56 5.05 9.51 0.11 0.27 Suwannee Blue 18(510) 3.6(102) 6.5 3.6 282 79.1 6.19 2.27 3 SUW718971 8(226) 5(226) 18.6 14 361 169 7.92 4.87 SUW725971 5(142) 4(142) 16.6 15 201 145 4.42 4.18 4 Mearson 62.4(1,767) 55(1,557) 2.13 2.1 323 280 7.07 8.04 5 LAF718972 15(425) 15(425) 2.18 1.3 79.4 47.3 1.74 1.36 Troy 111.9(3,169) 87.4(2,475) 2.05 2.2 557 467 12.21 13.39 LAF1024001 0.5(14) 1(28) 0.12 0.33 0.15 0.80 0.00 0.02 6 Ruth 10.9(309) 1.6(45) 5.5 4.7 145 18.5 3.19 0.53 Little River 63.7(1,804) 51(1,444) 1.12 1.2 173 149 3.80 4.26 LAF93971 0.5(14) 0(0) 0.09 Dry 0.11 Dry <0.01 Dry LAF718971 15(425) 8(226) 1.1 0.44 40.0 8.54 0.88 0.25

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123 Table 4-3. Middle Suwannee River Basin NO3-N change profile 2000 and 2006. MSRB River Segment NO3-N Load change (kg d-1) NO3-N Load change per meter of river (kg d-1 m-1) Segment (m) 2000 2006 2000 2006 1 6,361 284 1,043 0.045 0.164 2 6,220 903 494 0.145 0.079 3 3,408 1,663 937 0.488 0.275 4 5,152 523 98 0.101 0.019 5 5,477 995 403 0.182 0.074 6 7,502 192 510 0.026 0.068 Table 4-4. Lower Sant a Fe River Basin NO3-N change profile 2001 and 2006. LSFR River Segment NO3-N Load change (kg d-1) NO3-N Load change per meter of river Segment (m) 2001 2006 2001 2006 1 2,171 894.6 1,171.0 0.412 0.539 2 2,127 309.2 108.2 0.145 0.051 3 813.8 -725.9 22.0 -0.892 0.027 Table 4-5. Lower Santa Fe River Basin refined NO3-N change profile for 2006. LSFR River Segment NO3-N Load change (kg d-1) NO3-N Load change per meter of river Segment (m) 2006 2006 1 914.5 -20.5 -0.022 2 351.2 176.9 0.504 3 481.0 -20.2 -0.042 4 424.7 1,034.8 2.437 5 1,141 188.7 0.165 6 985.9 -80.5 -0.082 7 813.8 22.0 0.027

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124 Table 4-6. Lower Santa Fe River Basin sp ring comparison 2000 to 2006 of discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the study reach. River Segment Springs Discharge [cfs/( L s-1)] NO3-N (mg L-1) NO3-N Load (kg d-1) % NO3-N Load change 2001 2006 2001 2006 2001 2006 2001 2006 1 Rum Island 30(850) 14.3(405) 1.06 1.5 77.2 52.2 16.2 4.01 Blue 50(1,416)14.1(399) 1.59 1.9 193 64.9 40.6 4.99 2 July 75(2,124)70(1,982) 1.28 1.6 233 271.8 49.0 20.89 Devil’s Ear 100(2,831)ns 1.37 ns 332 ns 70.0 ns 3 Ginnie 40(1,133)13.5(382) 1.24 1.3 120 42.7 25.3 3.28 Dogwood 15(425) 5.2(146) 0.86 0.79 31.3 10.1 6.59 0.77 Sawdust 7(198) 4(113) 0.82 0.78 13.9 7.57 2.93 0.58 Twin 15(425) 2.5(71) 0.55 0.27 20.0 1.61 4.21 0.12 ns = no sample

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125 Table 4-7. Discharge, NO3-N concentration, NO3-N Load and contribution of the total NO3-N load increase in the study reach for Lower Santa Fe River Basin springs in refined segments (October 10, 2006). River Segments Springs Discharge [cfs/ L s-1)] NO3-N (mg L-1) NO3-N Load (kg d-1) % NO3-N Load change 1 Rum Island 14.3(405) 1.5 52.2 4.01 Blue 14.1(399) 1.9 64.9 4.99 2 No springs 3 No springs 4 July 70(1,982) 1.6 271.8 20.9 5 Ginnie 13.5(382) 1.3 42.7 3.28 Dogwood 5.2(147) 0.79 10.0 0.77 Sawdust 4(113) 0.78 7.57 0.58 Twin 2.5(71) 0.27 1.61 0.12 6 No springs 7 No springs

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126 $ T $ T $ T $ T $ T $ T $ T $ T $ T $ TEllaville Dowling Park Luraville Branford Suwannee Springs W hite Springs S.R at SR 6 Rock Bluff W ilcox SR above Gopher River N Figure 4-1. Suwannee River Water Mana gement District stations on the Su wannee River with aerial photography.

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127 # # # # # # S u w a n n e e R i v e rBrooker Worthing Springs O'Leno US 441 S.R. 47 US 129 Figure 4-2. Suwannee River Water Manage ment District stations on the Sant a Fe River with aerial photography.

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128 00.10.20.30.40.50.60.70.8 S.R. at Gopher R. Wilcox Rock Bluff Branford Luraville Dowling Park Ellaville S.R. above Withla. Suw. Springs White Springs S.R. at SR6 Concentration (mg/L) NOx-N Total P Geor g ia Gulf of Mexico Figure 4-3. Mean NO3-N and TP for Suwannee River Water Management District Suwannee River stations (1989 to 2006).

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129 00.10.20.30.40.50.60.70.8 SFR at US 129 SFR at SR 47 SFR at US 441 O'leno Worhtington Springs Brooker Concentration (mg/L) Total P NOx-NSuwannee River Figure 4-4. Mean NO3-N and TP for Suwannee River Water Management District Santa Fe Rive r stations (1989 to 2006).

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130 O O O O O O O O O O O O O O O O O O O O O O O O# # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # *# # # # # # # # # # *9 8 7 6 5 4 3 2 1 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 Legend# *River Station! OSpring StationMayo Luraville Dowling Park Branford Figure 4-5. Middle Suwannee River Basi n sampling points (July 21, 2000) for NO3-N profile. N ote: y ellow river stations indicate g reatest increase in [ NO 3 N]

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131 Figure 4-6. Middle Suwannee River Ba sin (Dowling Park to Branford) NO3-N profile on July 21, 2000. 0 0.1 0.2 0.3 0.4 0.5 0.6 12345678910111213141516171819202122232425262728293031323334353637 Sampling PointNOx-N (mg/L) Dowling Park Luraville Branford N ote: circle re p resents the y ellow river stations on Fi g ure 4-5

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132 Figure 4-7. NO3-N profile of the Middle Suwann ee River Basin (October 2000). 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05 1.10 12345678910111213141516171819202122 Sampling PointsNOx-N (mg/L) Luraville Branford N ote: Circle re p resents se g ment 3 in Fi g ures 4-8 and 4-12.

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133 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1234567891011121314151617181920Sampling PointsNOx-N (mg/L) 2000 2006 Segment 123456Figure 4-8. NO3-N profiles of Middle Suwannee River Basin (October 2000 and September 2006). N ote: Se g ments are dis p la y ed on Fi g ure 4-12

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134 Figure 4-9. The relationship of discharge and NO3-N concentration for the Suwannee River at Branford (1989 to 2006).

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135 Figure 4-10. The relationship of specifi c conductance and discharge for the Suwa nnee River at Branford (1989 to 2006).

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136 Figure 4-11. The relationship of specific conductance and NO3-N concentration for the Suwannee River at Branford (1989 to 2006).

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137 O O O O O O O O O O O O O O O O O O# # # # # # # # # # # # # # # # # # # # # # 1 2 3 4 5 6 Legend# *River Station! OSpring StationMayo Luraville Dowling Park Branford1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Figure 4-12. Middle Suwannee River Basin sampling points and discharge cross-sectio ns [segments] (October 2000 and September 2006).

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138 0 0.1 0.2 0.3 0.4 0.5 0.6 123456Change in NOx N Load per m of river channel (kg/d/m)Segment 2000 2006 Figure 4-13. Comparison of segment NO3-N load change per m of river in the Middle Suwannee River Basin (October 2000 and September 2006).

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139 Figure 4-14. Lower Santa Fe River Ba sin sampling points (June 7, 2000) for NO3-N profile. N ote: Yellow river sta t ions indicate g reatest increase in [ NO 3 N]

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140 Figure 4-15. NO3-N profile of the Lower Sant a Fe River Basin on June 7, 2000. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1234567891011121314151617181920212223242526272829 Sampling PointsNOx-N (mg/L)Near Fort White Near High Springs N ote: Circle re p resents the y ellow river stations on Fi g ure 4-14

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141 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 123456789101112131415161718192021 SegmentNOx-N (mg/L) 2001 2006 2001 Segment123 2006 Se g ment123 4 567 Figure 4-16. NO3-N profile of the Lower Santa Fe Rive r Basin (September 2001 and October 2006). N ote: Se g ments are dis p la y ed on Fi g ures 4-17 and 4-18.

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142 O O O O O# # # # # # # # # # # # # # # # # # # # Legend# *River! OSpring1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 1 2 3 Figure 4-17. Lower Santa Fe River Basin segments for September 2001 NO3-N profile.

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143 O O O O O# # # # # # # # # # # # # # # # # # # # Legend# *River! OSpring1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 1 2 3 4 5 6 7 Figure 4-18. Refined Lower Santa Fe Ri ver Basin segments for October 2006 NO3-N profile.

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144 1 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 123Change in NOx N Load per m of river (kg/d/m)Segment 2001 2006 Figure 4-19. Comparison of segment NO3-N load change per m of river in the Lower Santa Fe River Basin (September 2001 to October 2006).

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145 0.5 0 0.5 1 1.5 2 2.5 3 1234567Change in NOx N Load per m of river (kg/d/m)Segment Figure 4-20. Refined segments NO3-N load change per m of ri ver in the Lower Santa Fe River Basin in October 2006.

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146 CHAPTER 5 GROUNDWATER DOMAIN DELINEATION AND LANDUSE INFLUENCES ON GROUNDWATER QUALITY Introduction A Chinese proverb states “When you drink th e water, remember the spring”. This statement is a good way to think about the influe nces of human activitie s on the land surface and the ultimate impacts to the ground water beneath the landuse. The springs ar e the sentinels of the Floridan aquifer’s overall status with respect to water quality. The geologic conditions in the Suwannee River Water Management District (SRW MD) are karstic which means that there are interconnections of surface and ground water. Th e landuse can be reflected in the ground water of the underlying Floridan aquifer. Also, agricu ltural activities and other landuses have impaired the quality of springs by contributing large quanti ties of nutrients to groundwater recharge in parts of the world (Katz et al ., 2001; Dietrich and Hebert, 1997; Focazio et al., 1998; Burg and Heaton, 1998; Buzek et al., 1998). The SRWMD operates the Water Assessment Regional Network (WARN) which has 181 wells monitored monthly for groundwater levels (Hornsby et al., 2005C). Also, the WARN network monitors 251 groundwater quality statio ns. About half of the WARN groundwater quality stations were randomly located and the re maining wells were placed to define regional trends (Upchurch and Goodwin, 2000). Also, ap proximately every five years the SRWMD and the United States Geological Survey (USGS) collect groundwater levels from approximately 1,000 wells to develop a potentiom etric surface map of the Floridan aquifer in the SRWMD. Groundwater domains can be approximated using potentiometric surface(s) of the aquifer or by using computer model(s) to simulate th e groundwater domain (Sco tt et al., 2004). The approximation of a groundwater domain is dete rmined by using potentiometric surface(s) to

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147 delineate groundwater divides and assumes that groundwater movement is perpendicular to the potentiometric surface isopleths (Freeze and Cherry, 1979). Groundwater flow modeling provides a valu able tool in under standing the hydrologic system, assessing the needs for additional data and information, and providing water managers a means to determine effects of changing hydrologic conditions (Planert, 2007). Groundwater computer models are mathematical representations of an aquifer and have been used to simulate groundwater flow and solute tran sport (Fetter, 1988). Most co mputer models for groundwater quality assumes a source of a water quality constitu ent and models transport rates, reactions and flow paths within the aquifer system. These tr ansport models use theoretical leaching and uptake coefficients to simulate observe d conditions. Thus, computer models are useful for conceptual understanding of the groundwater system. The computer model MODFLOW simulates an aquifer system by assuming that the aquifer has saturated flow, Darcy’s Law applies, and constant groundwater density within the aquifer (USGS, 1997). MODFLOW has been used to characterize the regional groundwater flow of the SRWMD (Planert, 2007; Grubbs and Crandall, 2007). Also, Davis (1996) used MODFLOW to assist in the deline ating capture zones of well fiel ds in the Woodville Karst plain areas of the panhandle of Florida. Shoemaker et al. (2004) to identify areas cont ributing recharge to the springs in northcentral Florida used groundwater flow models. The results yielded springshed and time based capture zones. Also, springsheds of Silver and Rainbow Springs in Marion County, Florida, were developed using two different flow models by indentified areas of groundwater that could be expected to reach the springs in 10 and 100 years (WRA and SDII, 2005). The identified land

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148 area associated with the groundw ater was classified a Spring Protection Zone for land use planning and management. Other studies try to relate observed isotopic nitrogen (N) ratios in NO3-N to the source of the NO3-N and the landuse that possibly can be associated with the observed isotopic composition. Gormly and Spalding (1979) collected ground water samples from Buffalo, Hall and Merrick counties in the Central Plat te Region of Nebraska and comp ared the isotopic values of the ground water samples to those of potential NO3-N sources. The potential sources were inorganic fertilizer, soil or ganic N and animal waste with 15N ranges of -2.1 to +1.9 ‰, +5.9 to +9.0 ‰ and +10.0 to +18.0 ‰, respectively. The ground water in the Centra l Platte Region during 1976-1977 had 183 of 256 ground water sa mples in excess of 10 mg N L-1 of NO3-N. The study indicated that the primary source of NO3-N contamination in the ground water was due to fertilizers and a small fraction of the sa mples indicated NO3-N contamination due to animal waste. Samples for which the source could not be identified were assumed to be a combination of tw o or more sources of contamination. Kreitler and Browning (1983) used N isot ope analyses in grou nd water samples from Cretaceous Edwards aquifer in Texas, U.S.A. and Pleistocene Ironshore Formation on Grand Cayman Island, West Indies. Both aq uifers are carbonate aquifers. The 15N classification ranges used were -2.0 to +1.9 ‰ (inorgan ic fertilizer), +2.0 to +8 ‰ (soil cultivation without fertilizer) and +10.1 to +22.0 ‰ (animal waste). The ground water samples from Cretaceous Edwards aquifer had 15N values that ranged from +1.9 to +10.0 ‰; while, the sample from Pleistocene Ironshore Formation had 15N values that ranged fr om +18 to 23.9 ‰. Cr etaceous Edwards aquifer 15N values indicate fertilizer and mineralization of soil organic ma tter as the sources of the NO3-N in the

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149 ground water; while, Plei stocene Ironshore Formation 15N values indicates animal wastes as the source of NO3-N contamination in the ground water. Flipse and Bonner (1985) used isotop ic ratios for the identification of NO3-N in the ground water under fertilized fields. Two sites were used. Site one was a potato farm where the fertilizer applied had an average 15N value of 0.2 ‰ and the NO3-N had an average 15N value of +6.2 ‰. Site two was a golf cour se where the fertilizer applied had an average 15N value of -5.9 ‰ and the NO3-N had an average 15N value of +6.5 ‰. Th e difference between the 15N of the fertilizer and the 15N of the NO3-N was possibly due to th e isotopic fractionation in the volatile loss of NH3 during (or after) application of ammonium fertilizer. The 15N values are consistent with characteristic range determined for NO3-N resulting from agricultura l operations (non-animal waste). Kreitler (1975) used 15N/14N ratios of groundwater NO3-N to determine the source(s) of NO3-N. 15N value ranges were -3 to +2 ‰ (inorganic fertilizer), +2 to +8 ‰ (unfertilized cultivated fields) and +10 to +20 ‰ (animal waste) From the isotop ic ratios of NO3 -, the source of NO3-N indicates a mixed source of NO3-N (mean 15N value +6.8 ‰). Due to the age of the water in the aquifer, the 15N value is representative of older land use pattern where agri culture was widely practiced and both i norganic fertilizer and manure were used. Mytyk and Delfino (2004) reviewed a 50-year period of record for NO3-N concentrations in the Ocklawaha Basin and linked changes to landuse based on isotopic composition. While Katz et al. (2001) used isotopic composition of NO3-N and age dating techniques from collected spring water to link landuse within the basin and estimate travel times. Isotopic studies were able to show relative co mposition of the sources of N in the form of NO3-N. However, the potential sources of N for the isotopic st udies were inorganic, organic or mixed.

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150 In hydrochemical studies, classification on the basis of water quality serves the purpose of identification of repr esentative clusters (hydrochemical f acies) of samples that reflect the processes generating the natura l variability found in hydrochemi cal parameters (Guler and Thyne, 2004). The use of hydrochemical facies was demonstrated by Back (1961), Back and Hanshaw (1965), Morgan and Winner (1962), Seaber (1962), Jones et al (1996), and Maddox et al. (1992) to indicate distinct regions of ground water which contain similar composition of cations and anions. The use of hydrochemical f acies analysis depends on pattern recognition. Methods for defining and displayi ng hydrochemical facies patterns range from the use of Piper diagrams, Stiff diagrams, and star diagrams to statistical methods, such as fuzzy c-mean clustering or factor analysis or principal compon ent analysis (Kwansirikul et al., 2005; Guler and Thyne, 2004; Lawrence and Upchur ch, 1982). Lawrence and Upc hurch (1982) used factor analysis to delineate regions of similar groundw ater quality in Northern Suwannee County. For small data sets, graphical methods are usef ul to display the relative patterns among hydrochemical facies; while, for large data sets, stat istical techniques are used to filter the data set and identify patterns. This study will identify groundwater domains based on potentiometric surface maps from 1985, 1990, 1995, 2002, and 2005. Hydrochemical facies analysis will be used to refine the groundwater domains determined from the potentiom etric surface data. Water quality statistics of the upper Floridan aquifer water will be de termined for each groundwater domain. Then each groundwater domain will be related to the observed groundwater domain median TP and NO3-N concentrations to percent of the groundwater do main in specific level 2 Florida Landuse Code (FLUC). This study will provide an examina tion of relationships of groundwater quality and land uses on a groundwater domain wide analysis.

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151 Materials and Methods The groundwater domains for potentiom etric surface maps from 1985, 1990, 1995, 2002 and 2005 were approximated by using the methods outlined by Freeze and Cherry (1979) and Upchurch et al. (2001). Principal component s analysis (PCA) of the WARN groundwater quality monitoring well data was used to conf irm and refine the groundwater domains which were delineated from the potentiometric surfaces The PCA used potassium (K), sodium (Na), magnesium (Mg), calcium (Ca), chloride (Cl), sulfate (SO4 2-) and NO3-N to cluster samples according to the hydrochemical facies, or geoche mical fingerprints, of the groundwater domains within the upper Floridan aquifer (Back, 1961; Lawrence and Upchurch, 1982). The PCA used Eigen analysis that created a correlation matrix for the components. The resulting component scores were imported into Surfer and contour ed using the kriging option with a linear interpolation and zero nugget. The resulting contours were importe d into ArcGIS. In ArcGIS, the groundwater domains from delineated potentio metric surface data were overlaid with the component score contours to deline ate the final groundwater domains. The WARN well coverage was clipped to groundwater domains. Mean, standard deviation, median, 25th percentile, 75th percentile, maximum, a nd minimum for groundwater quality were generated for each gr oundwater domain. The median NO3-N and TP were compared using a series of Kruskal-Wallis tests (Ott and Longnecker, 2001) to ensure that each basin was statistically different at the 95% confidence level. The 1995 landuse/landcover (SRWMD, 1997) coverage for the SRWMD was clipped to the groundwater domains using ArcGIS. The hectar es of basin in landuse/landcover at level 2 Florida landuse codes (FLUCs) were determined for each groundwater domain. The median

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152 groundwater domain concentrations of TP and NO3-N were correlated to each of the level 2 Florida landuse codes. Results and Discussion The potentiometric surface maps fo r SRWMD for 1985, 1990, 1995, 2002 and 2005 are presented in Appendix D, Figures D-1 through D-5. Figures 5-1 to 5-5 pr esent the groundwater domains based on the potentiometric surface maps for 1985, 1990, 1995, 2002 and 2005, respectively. In the 1985 groundwater domains, a east-west domain was not delineated in the center of Taylor County due to the groundwater withdrawals in th e region causing an artificial bend in the potentiometric surface. Th e groundwater domains for 1985, 1990, 1995, 2002 and 2005 potentiometric surface maps were overlaid and the maximum extent of each basin was used to determine the composite potentiome tric surface groundwater domains. The PCA revealed two distinct water types based on water quality parameters potassium (K), sodium (Na), magnesium (Mg), calci um (Ca), chloride (Cl), sulfate (SO4), and NO3-N. The PCA yielded two principal components that we re significant and accounted for 77.8 % of the total variability (Table 5-1) Principal component 1 includes K, Na, Mg, Cl, and SO4, which are positively correlated Figure 5-6 shows the component contours for principal component 1. The higher contours are associated with the regions of the upper Floridan aquifer that has a confining unit. Principal component 1 represents geologic al influences on recharge and weathering of the Hawthorne Group. Therefore, principal component 1 represents the confined Floridan aquifer. Principal component 2 includes Ca and NO3-N, which are negatively correlated. Figure 5-7 shows the component contours for principal component 2. The higher component contours indicate recharge or surfacewater influences. The region in the southwest corner of Dixie County indicates water quality that is different from the surrounding ground water. This resulted

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153 in the delineation of a ninth groundwater domain. The difference in the groundwater quality in southwest Dixie County may be associated with sand/limestone mining. Principal component 2 represents more rapid recharge of the upper \Floridan through karst features. Therefore, principal component 2 represents the unconfined Floridan aquifer. The results from the composite potentiometric surface groundwater domains yielded eight distinct groundwater domains. The eight potentiometric surface groundwater domains were coupled with the component contours. The component contours were used to confirm that the potentiometric surface groundwater domains did not contain water quality differences. The component contours for principal component 2 identified two groundwater domains in Dixie County instead of one groundwater domain as iden tified from the potentiometric surface. This resulted in the delineation of a ninth groundw ater domain, Dixie, which is the smallest groundwater domain delineated in the SRWM D. The potentiometric surface groundwater domain most likely did not account for the ninth ba sin due to the resolution of the potentiometric surface and the density of wells in the region used to create the potentiometric surface maps. The refined groundwater domains were adjusted to include the additional basin identified from the component contours. The refined groundwater domains map for the SRWMD are shown in Figure 5-10. Names were assigned to the ground water domains based on their relationship to surfacewater features (Alapaha, Aucilla, Coasta l, Dixie, Ichetucknee, Santa Fe, Suwannee, Steinhatchee, and Waccasassa). The statistical summary by groundwater domain for NO3-N and TP are presented in Table 5-2. A statistical summary for the period of record of the remaining groundwater quality parameters from the WARN network (tempera ture, specific conductance, pH, DO, turbidity,

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154 TDS, alkalinity, TOC, DOC, K, Na, Mg, Ca, Cl, F, SO4 2-, Fe, TKN, NH4 +-N) is presented in Appendix D, Table D-1. A series of Kruskal-Wallis tests we re conducted on the median TP and NO3-N concentrations to show that each groundwater doma in was statistically different at the 95 percent confidence level (Appendix D, Tables D-2A to D-2H). The median TP and NO3-N concentrations for each of the groundwater domains were examined. The first test included all nine basins. The model was found to be signi ficant at the 95 % c onfidence level. The groundwater domain with the highest concentrati ons was removed and the remaining basins were analyzed using the Kruskal-Wallis test. This process was continued until all the basins were determined to be statistically different at the 95 % confidence level for TP and NO3-N. These results provide a method for evaluating the groundwater conditions for TP and NO3-N on a regional scale. Figure 5-9 shows the median TP concentration with Kruskal-Wallis statistical separation for each groundwater domain. The groundwater do main with the highest TP concentration was the Waccasassa. Waccasassa groundwater TP ma y be associated with the weathering of carbonate-hydroxylapatite [Ca5(PO4•CO3)3•(OH)] in the Waccasassa Flats (Maddox et al., 1992). Carbonate-hydroxylapatite is the mineral produc ed by precipitation of phosphate which was liberated by weathering of carbonate-fluorapatite [Ca5(PO4•CO3)3•F] under acidic conditions. The precipitation of carbonate-hyd roxylapatite occurs when the phosphate rich water encounters an alkaline environment, such as the uppe r Floridan aquifer (Maddox et al., 1992). Furthermore, the groundwater domains closest to the Gulf of Mexico had the highest TP concentrations in the SRWMD. The possible sour ces of the P are organic rich recharge water containing P or leaching from the geological formations providing P as the acidic water is

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155 recharging to the upper Floridan aquifer. The groundwater doma ins adjacent to the Gulf of Mexico have large areas of swamps which are groundwater discharge zones. The swamps result from low lying topography and in some case, overl ying clayey sands and the high potentiometric surface which results in surficial waters being una ble to infiltrate into the ground (Arthur, 1991). The surface water conditions in these swamps re sult in an acidic environment, largely due to organic acids, in which P may be dissolved in the water column or su spended with organic material. As the water in the swamps move to th e edge of the swamps wh ich have karst features which can provide recharge points into the unde rlying upper Floridan aquifer. The ortho-P fraction of the TP will precipitate when it comes in contact with the al kaline water of the upper Floridan aquifer (Maddox et al., 1992). The organic P fraction of TP may precipitate or remain suspended or dissolved. Lawrence and Upchurch (1982) demonstrated that recharge water containing P could maintain the P in solution for several kilometers within karst features, such as conduits in the upper Floridan aquifer, due to the lack of contact with lim estone. Also, Lawrence and Upchurch (1982) noted that the weathering of apatite minerals from the Hawthorn Group introduced phosphate into surface and ground wate r. Erosion of the Hawthorn Group in the Highlands during various sea level stands a nd deposition of the erosion products from the Hawthorn Group within the groundwater domains ad jacent to the Gulf of Mexico may account for the P bearing materials with in the groundwater domains. Figure 5-10 shows the median NO3-N concentration with Kruskal-Wallis statistical separation for each groundwater domain. The groundwater domain with the highest median NO3-N concentration was the Santa Fe. Three gr oundwater domains, Santa Fe, Ichetucknee, and Suwannee, had elevated NO3-N concentrations. The elevated NO3-N is due to anthropogenic factors, such as atmospheric deposition, septic tanks, wastewater spray fi elds, or fertilization

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156 (Andrews, 1994). Also, there are no known natural sources of NO3-N in the upper Floridan aquifer. Katz et al. (1999) sampled springs within Santa Fe, Ichetucknee, and Suwannee groundwater domains. Nitrate-nitrogen in tw o springs in the Suwa nnee groundwater domain with NO3-N concentrations gr eater than 10 mg L-1 was from an inorgani c source; while other springs had mixed or organic source signatures based on the 15N/14N isotopic ratio. The results for the Santa Fe groundwater domain yiel ded that one spring (GIL917971) with NO3-N concentrations greater than 10 mg N L-1 was from a mixed source; while other springs had inorganic or organic source signatures. Only one spring was sampled in the Ichetucknee groundwater domain and it had an inorganic signature. Furtherm ore, the limitation of using 15N/14N ratio is potential sources are limited to inorganic, organic and mixed and that it cannot be traced to a specific landuse practice on a specific site. The groundwater domains, as shown in Fi gure 5-8, were used to clip the 1995 landuse/landcover (Figure 5-11) to determin e the landuse/landcover for each groundwater domain. The 1995 landuse/landcover coverage is the best ava ilable source of landuse data available at the time of this study. Level 2 FLUC landuse/landcove r for each groundwater domain is presented in Table 5-3 to 5-11. The single largest landus e/landcover for all the groundwater domains is tree plantations, which co nfirms the rural nature of the SRWMD. The percentage of each level 2 FLUC landuse/landcover was correlated to the median groundwater domain concentrations of TP and NO3-N. The only level 2 FLUC landuse/landcover with a correlation was crop and pasture land to NO3-N (Figure 5-12). No correlation was observed for TP for crop and pastur e land landuse/landcover (Figure 5-13) or any other landuse/landcover, which sugge sts that either TP is not in fluenced by landuse/landcover at this time or the ortho-P component of TP is precipitated in the upper Floridan aquifer, so

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157 concentration in the groundwater is a result of the chemical equilibrium. Figure 5-14 shows the median groundwater domain NO3-N and the percentage of the domain in crop and pasture land. Based on the correlation of median NO3-N concentrations and percen t of the basin in level 2 FLUC crop and pasture land landuse/ landcover there are elevated NO3-N concentrations in the upper Floridan aquifer within th e groundwater domain when th e groundwater domain has greater than 12 percent of the groundwater domain in crop and pasture land landuse/landcover. The Santa Fe groundwater domain has the highest median NO3-N concentration and the highest percentage of the domain in crop and pastur e land landuse/landcover followed by the Suwannee and Ichetucknee (Figure 5-14). The landuse crop and pasture land in Santa Fe, Suwannee and Ichetucknee domains are occurring over the unco nfined Floridan aquifer on primarily Entisols with high leaching potential. Sabasan (2004) identified NO3-N concentrations in various landuse on Entisols, Ultisols, and Spodosols in the Sa nta Fe River Watershed. For landuse improved pasture, the NO3-N concentrations for Entisols, Ultisols, and Spodosols were 0.51, 1.80 and 1.65 g N g-1of soil, respectively. The Entisols which are in landuse improved pasture have lower soil NO3-N due to the le aching of the NO3-N. Furthermore, where these Entisols are over the unconfined Floridan aquifer there is potential for leaching of NO3-N into the upper Floridan aquifer. For the Santa Fe, Suwannee and Ic hetucknee groundwater dom ain, the level 2 FLUC crop and pasture land landuse/landcover is co mposed of improved pasture, row crop and woodland pasture. The improved pasture makes up greater than 65 percent of the level 2 FLUC crop and pasture land landuse/landcover as shown in Figure 5-15. Also, hay fields are classified as improved pasture in the level 2 FLUC system which receives applications of N fertilizers.

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158 Summary and Conclusions There are nine distinct groundwater domain s in the upper Floridan aquifer within the SRWMD based on groundwater levels (potentiom etric surface) and groundwater quality. The Santa Fe, Ichetucknee and Suwannee groundwat er domains have the highest median NO3-N concentrations of the groundwater domains within the SRWMD. Va riation in the concentrations of TP is most likely due to geological properties of the upper Floridan aqui fer while the variation in the concentrations of NO3-N is due to anthropogenic factor s, such as, fertilizer use in the groundwater domain. Median concentrations of TP and NO3-N was related to various level 2 FLUC landuse/landcover classes in each groundwater do main. The only correlation was observed for crop and pasture land for groundwater domain NO3-N concentration. Based on the observed relationship in the SRWMD, when the percenta ge of a groundwater domain is greater than 12 percent crop and pasture land, the gro undwater domain will have elevated NO3-N concentrations. The landuse crop and pasture land in Santa Fe, Suwannee and Ichetucknee domains are occurring over the unconfined Floridan aquifer on primar ily Entisols with high leaching potential. The major component of the level 2 FLUC crop and pasture land class is improved pasture. Furthermore, improved pasture can also be fields for the production of hay that can receive N fertilizer to maximize hay crop yields a nd protein content. Thus this study identified for the SRWMD a direct relati onship tool for determining wh en a groundwater domain may be impacted by NO3-N concentrations in the upper Florid an aquifer by landuse crop and pasture lands.

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159 Table 5-1. Principal component analys is showing significant components. Variable Units Principal Com ponent 1Principal Component 2 Sodium mg L-1 0.463 -0.099 Chloride mg L-1 0.461 -0.099 Potassium mg L-1 0.456 -0.065 Sulfate mg L-1 0.421 0.061 Magnesium mg L-1 0.419 0.043 Calcium mg L-1 0.112 0.654 Nitrate-nitrogen mg L-1 0.006 0.737 Eigenvalue 4.418 1.030 Accounted percent of variability 63.1 14.7

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160 Table 5-2. Statistical summary for NO3-N and TP by groundwater domain. Variable Units Basin Mean Standard Deviation 25t h Percentile Median 75t h Percentile Mi nimum Maximum NO3-N mg L-1 Alapaha 0.18 0.56 0.00 0.01 0.09 0.00 3.94 Aucilla 0.62 1.12 0.01 0.03 0.62 0.00 4.16 Coastal 0.09 0.17 0.00 0.02 0.11 0.00 1.05 Dixie 0.02 0.02 0.00 0.02 0.03 0.00 0.07 Ichetucknee 0.62 1.74 0.01 0.25 0.73 0.00 27.20 Santa Fe 1.41 1.73 0.02 1.21 1.62 0.00 10.60 Steinhatchee 0.03 0.09 0.00 0.01 0.03 0.00 0.73 Suwannee 1.32 3.56 0.00 0.31 1.31 0.00 52.0 Waccasassa 0.01 0.02 0.00 0.01 0.01 0.00 0.09 TP mg L-1 Alapaha 0.087 0.087 0.040 0.070 0.109 0.000 0.598 Aucilla 0.325 0.545 0.050 0.133 0.480 0.000 4.870 Coastal 0.258 0.228 0.081 0.151 0.522 0.000 0.814 Dixie 0.028 0.019 0.010 0.030 0.042 0.000 0.056 Ichetucknee 0.144 0.359 0.035 0.053 0.100 0.000 3.640 Santa Fe 0.102 0.204 0.040 0.055 0.105 0.000 2.240 Steinhatchee 1.005 3.936 0.040 0.068 0.461 0.000 25.000 Suwannee 0.248 1.781 0.044 0.070 0.145 0.000 45.000 Waccasassa 0.195 0.037 0.189 0.196 0.209 0.078 0.303

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161 Table 5-3. 1995 level 2 Florida Landuse Code for the Alapaha groundwater domain. Land Cover Hectares Tree Plantations 160,459 Wetland Forested 30,762 Crop and Pasture Land 26,808 Wetland Coniferous 17,515 Wetland Hardwood 8,353 Upland Hardwood 5,145 Extractive 3,167 Streams and Waterways 929 Freshwater or Salt Marshes 625 Upland Coniferous 332 Industrial 314 Residential, Medium Density 310 Residential, Low Density 272 Utilities 232 Commercial and Services 229 Transportation 96 Recreational 57 Animal Feeding Operation 40 Specialty Farms 20 Nurseries and Vineyards 8.3 Residential, High density 8.0 Disturbed land 7.8 Major Springs 1.2

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162 Table 5-4. 1995 level 2 Florida Landuse Code for the Aucilla groundwater domain. Land Cover Hectares Tree Plantations 105,890 Wetland Forested 105,017 Embayments opening directly in to the Gulf of Mexico 40,470 Crop and Pasture Land 31,021 Wetland Coniferous 13,049 Wetland Hardwood 7,478 Freshwater or Salt Marshes 4,266 Upland Hardwood 4,097 Upland Coniferous 663 Utilities 533 Residential, Low Density 414 Extractive 393 Residential, Medium Density 326 Nurseries and Vineyards 244 Streams and Waterways 198 Commercial and Services 184 Transportation 173 Recreational 107 Industrial 93.0 Specialty Farms 37.1 Disturbed land 20.5 Animal Feeding Operation 17.9 Open Land 15.0 Residential, High density 9.78 Non-Vegetated Wetland 6.49 Major Springs 4.64 Oyster Bars 0.91

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163 Table 5-5. 1995 level 2 Florida Landuse Code for the Coastal groundwater domain. Land Cover Hectares Embayments opening directly in to the Gulf of Mexico 145,729 Tree Plantations 117,688 Freshwater or Salt Marshes 10,068 Wetland Forested 9,375 Wetland Coniferous 9,072 Crop and Pasture Land 4,216 Wetland Hardwood 3,386 Upland Hardwood 1,164 Residential, Low Density 808 Utilities 755 Upland Coniferous 586 Residential, Medium Density 484 Industrial 380 Commercial and Services 231 Non-Vegetated Wetland 176 Extractive 79.1 Streams and Waterways 68.2 Recreational 50.8 Coastal Scrub 48.9 Open Land 29.6 Animal Feeding Operations 27.5 Embayments not opening directly into the Gulf of Mexico 20.4 Residential, High Density 14.6 Major Springs 1.51 Disturbed Land 0.95

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164 Table 5-6. 1995 level 2 Florida Landuse Code for the Dixie groundwater domain. Land Cover Hectares Embayments opening directly in to the Gulf of Mexico 105,241 Tree Plantations 22,006 Freshwater or Salt Marshes 6,613 Wetland Forested 5,076 Wetland Coniferous 1,135 Residential, Low Density 341 Crop and Pasture Land 230 Non-Vegetated Wetland 206 Residential, Medium Density 196 Upland Hardwood 108 Commercial and Services 66.9 Wetland Hardwood 50.8 Embayments not opening directly into the Gulf of Mexico 41.5 Recreational 12.2 Upland Coniferous 10.3 Coastal Scrub 7.22 Open Land 3.16 Residential, High Density 1.97 Disturbed land 1.37 Utilities 1.17

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165 Table 5-7. 1995 level 2 Florida Landuse Code for the Ichetucknee groundwater domain. Land Cover Hectares Tree Plantations 276,578 Crop and Pasture Land 66,861 Wetland Forested 40,965 Upland Hardwood 19,916. Wetland Coniferous 13,968 Upland Coniferous 10,089 Wetland Hardwood 3,726 Residential, Low Density 3,292 Residential, Medium Density 1,754 Utilities 1,040 Commercial and Services 716 Extractive 390 Recreational 339 Freshwater or Salt Marshes 319 Nurseries and Vineyards 250 Industrial 247 Streams and Waterway 224 Disturbed land 214 Transportation 199 Animal Feeding Operations 173 Open Land 142 Residential, High Density 113 Specialty Farms 69.7 Tree Crops 30.3 Palmetto Prairies 19.3 Major Springs 1.47

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166 Table 5-8. 1995 level 2 Florida Landuse Code for the Santa Fe groundwater domain. Land Cover Hectares Tree Plantations 86,217 Crop and Pasture Land 68,046 Upland Hardwood 28,252 Wetland Forested 18,924 Residential, Medium Density 6,726 Residential, Low Density 6,465 Wetland Coniferous 5,033 Upland Coniferous 2,460 Freshwater or Salt Marshes 2,221 Wetland Hardwood 1,755 Commercial and Services 1,495 Utilities 1,353 Residential, High Density 1,142 Recreational 902 Extractive 718 Industrial 509 Transportation 499 Specialty Farms 449 Nurseries and Vineyards 307 Open Land 263 Streams and Waterway 176 Disturbed Land 60.8 Animal Feeding Operations 60.0 Tree Crops 12.8 Major Springs 1.81

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167 Table 5-9. 1995 level 2 Florida Landuse Code for the Steinhatchee groundwater domain. Land Cover Hectares Tree Plantations 166,446 Embayments opening directly in to the Gulf of Mexico 105,222 Wetland Forested 62,042 Wetland Coniferous 11,709 Freshwater or Salt Marshes 4,706 Wetland Hardwood 2,440 Upland Hardwood 797 Crop and Pasture Land 443 Residential, Low Density 407 Non-Vegetated Wetland 318 Residential, Medium Density 184 Upland Coniferous 99.1 Streams and Waterways 97.6 Commercial and Services 20.7 Embayments not opening directly into the Gulf of Mexico 18.9 Recreational 16.5 Industrial 9.68 Disturbed land 5.95 Open Land 3.90 Coastal Scrub 2.45 Utilities 1.56 Extractive 1.52 Major Springs 0.34

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168 Table 5-10 1995 level 2 Florida Landuse Code for the Suwannee groundwater domain. Land Cover Hectares Tree Plantations 283,108 Crop and Pasture Land 145,374 Upland Hardwood 90,396 Wetland Forested 86,362 Residential, Low Density 31,182 Wetland Coniferous 26,164 Wetland Hardwood 15,387 Open Land 9,153 Shrub and Brush Land 7,468 Upland Coniferous 4,340 Lakes 4,020 Other Open Lands 3,340 Streams and Waterway 3,299 Residential, Medium Density 1,698 Non-Vegetated Wetlands 1,082 ODC Institutional (Education, religious, health, military) 1,080 Commercial and Services 1,035 Extractive 965 Reservoirs 934 Tree Crops 929 Specialty Farms 737 Nurseries and Vineyards 687 Animal Feeding Operations 668 Industrial 360 Residential, High Density 106 Disturbed Lands 81.4 Major Springs 12.9 Bays and Estuaries 8.07

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169 Table 5-11. 1995 level 2 Florida Landuse Code for the Waccasassa groundwater domain. Land Cover Hectares Embayments opening directly in to the Gulf of Mexico 105,233 Tree Plantations 57,782 Wetland Forested 12,706 Crop and Pasture Land 10,060 Upland Hardwood 7,647 Freshwater or Salt Marshes 7,443 Upland Coniferous 3,013 Wetland Hardwood 2,305 Wetland Coniferous 1,759 Extractive 473 Nurseries and Vineyards 242 Residential, Low Density 207 Utilities 46.3 Commercial and Services 34.9 Recreational 23.9 Specialty Farms 22.9 Streams and Waterway 12.9 Open Land 8.25 Embayments not opening directly into the Gulf of Mexico 7.87 Coastal Scrub 7.64 Palmetto Prairies 5.31 Residential, Medium Density 2.81 Residential, High Density 1.45 Disturbed Land 0.70

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170 60 70 80 20 50 30 40 50 40 50 30 20 10 10 20 30 40 50 60 70 80 040Miles N Figure 5-1. Groundwater domians based on 1985 poten tiometric surface (Rosenau and Meadows, 1986). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

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171 3 04 02 01 06 07 09 05 08 05 07 05 06 08 0 040Miles N Figure 5-2. Groundwater domains based on 199 0 potentiometric surface (Meadows, 1991). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

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172 2 01 05 03 08 06 04 07 01 07 06 08 06 05 04 05 04 08 03 04 06 06 05 05 04 07 0 040Miles N Figure 5-3. Groundwater domains based on 1995 potentiometric surface (Mahon et al., 1997). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

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173 1 04 02 08 05 07 06 03 02 04 04 03 05 02 05 07 07 05 04 004 05 05 06 07 07 06 08 06 02 0 040Miles N Figure 5-4. Groundwater domains based on 2002 potentiometric su rface (SRWMD, 2002). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

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174 4 03 01 05 02 06 07 08 09 0007 08 02 08 005 06 06 08 06 0 1 05 06 07 09 08 04 002 03 02 002 04 06 06 08 02 05 07 08 08 006 08 02 01 05 06 07 09 08 04 002 03 02 002 04 06 06 08 02 05 07 08 08 006 08 02 0 Figure 5-5. Groundwater domains based on 2005 potentiometric su rface (SRWMD, 2005). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

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175 -2 0 2 4 6 8 10Component Contours Figure 5-6. Principal component 1 cont ours for hydrochemical facies analysis.

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176 -6 -4 -3 -2 0 2 4Component Contours Figure 5-7. Principal component 2 cont ours for hydrochemical facies analysis.

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177 Aucilla Suwannee Alapaha Ichetucknee Santa Fe Waccasassa Dixie Steinhatchee Coastal 040Miles N Figure 5-8. Refined groundwater domains ba sed on composite potentiometric surfaces ba sins and hydrochemical facies analysis.

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178 0 0.05 0.1 0.15 0.2 0.25 AlapahaAucillaCoastalDixieIchetuckneeSanta FeSteinhatcheeSuwanneeWaccasassaMedian Total Phosphorus (mg/L) A B C D E F G H I Figure 5-9. Median groundwater TP c oncentration by groundwater domains. ( Different letters indicated significant difference at 0.05 confidence level.

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179 0 0.2 0.4 0.6 0.8 1 1.2 1.4 AlapahaAucillaCoastalDixieIchetuckneeSanta FeSteinhatcheeSuwanneeWaccasassaMedian NOx-N (mg/L) A B C D EF GH I Figure 5-10. Median groundwater NO3-N concentration by groundwater domains. Different letters indicated significant difference at 0.05 confidence level.

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180 Land Cover Residential, Low Density Residential, Medium Density Residential, High Density Commercial and Services Industrial Extractive Institutional Recreational Open Land Crop and Pasture Land Tree Crops Animal Feeding Operations Nurseries and Vineyards Specialty Farms Other Open Lands (Rural) Shrub and Brushland Upland Coniferous Forest Upland Hardwood Forests Upland Hardwood Forests Tree Plantations Streams and Waterways Lakes Reservoirs Bays and Estuaries Major Springs Wetland Hardwood Forests Wetland Coniferous Forests Wetland Forested Mixed Freshwater or Salt Marshes Non-Vegetated Wetlands Cut Over Wetlands Disturbed Lands Transportation Utilities County Boundaries 040Miles N Figure 5-11. 1995 level 2 Florida Landuse Code landuse/landcover for the Suwann ee River Water Management District.

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181 y = 4.3078Ln(x) + 24.076 R2 = 0.7326 0 5 10 15 20 25 30 35 00.20.40.60.811.21.4 median NOx-N (mg/L)Percentage of Crop and Pasture Land Figure 5-12. Median groundwater NO3-N concentration versus per centage of groundwater domains in crop and pasture lands.

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182 0 5 10 15 20 25 30 35 00.050.10.150.20.25 Median Total P (mg/L)Percentage of Basin in Crop and Pasture Lands Figure 5-13. Median groundwater TP concentration versus pe rcentage of groundwater domains in crop and pasture lands.

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183 0 5 10 15 20 25 30 35 AlapahaAucillaCoastalDixieIchetuckneeSa nta FeSteinhatcheeSuwannneeWaccasassaPercent of Basin in Crop and Pasture Lands0 0.2 0.4 0.6 0.8 1 1.2 1.4Median NOx-N (mg/L) Landuse NOx-N Figure 5-14. Median groundwater NO3-N concentration and percen tage of groundwater domains in crop and pasture lands.

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184 0 10 20 30 40 50 60 70 80 90 100 IchetuckneeSanta FeSuwannee% of Crop and Pasture Land Improved Pasture Row Crop Woodland Pasture Figure 5-15. Landuses within crop and pasture lands code for the groundwate r domains with elevated median NO3-N.

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185 CHAPTER 6 SYNTHESIS The station on the Suwannee River at Branford is a sentinel or integrator station for the Suwannee River. This station has been monitored for water quality since 1954. Total phosphorus (TP) concentration ha s significantly (>99.9% confidence level) declined since the river was designated an Outstanding Florida Wa ter (OFW) in 1979. The decrease in the TP concentrations that started in 1985 coincides with increased regulation of a phosphate mining operation in Hamilton and Columbia counties. Nitrate-nitrogen (NO3-N) concentrations have significantly increased since its designation as an OFW in 1979. Also, there was an observed increasing trend for potassium (K). The increases in NO3-N and K concentrations suggest a fertilizer signature. There was an observed time lag between N fertilizer sales data for Suwannee and Lafayette countie s and riverine NO3-N concentrations of one to six years. This increasing trend is supported by the increa sed use of inorganic fertilizer in Suwannee and Lafayette counties. This suggests that the NO3-N concentration observed at the Branford station was likely related to fertilizer use in the groundwater domains that f eed ground water to the Suwannee River via the numerous springs and seeps in the Middle Suwannee River Basin (MSRB). The MSRB was consistently the highest contributor of the annual NO3-N load from water years 1998 to 2005 and reach 1 of the Suwannee River was cons istently the highest contributor of the annual TP load from water years 1998 to 2004 excluding 2005 when it was the third largest contributor. The range of the annual NO3-N loading for the MSRB was 29.3 to 46.9 percent of the annual NO3-N load for the entire Suwannee River Basi n (SRB) from 1998 to 2005. The range of the annual TP loading for reach 1 of the Suwannee River was 14.6 to 100 percent of the annual TP load for the entire SRB from 1998 to 2005. This suggests that anthropogeni c factors are driving the changes in water quality from pre-OFW to post-OFW conditions for TP and NO3-N.

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186 The current mean upper Floridan aq uifer concentrations for TP and NO3-N were three times above background (or <0.10 mg P L-1) and 23 times above background (or <0.10 mg N L-1) concentrations, respectively, as define d by Maddox et al. (1992). Surfacewater NO3-N concentrations reflected the adjacent Floridan aquifer’s groundwater concentrations for NO3-N. Surfacewater basin concentrations of TP were driven by geological formations, point sources, and surface runoff. Thus, ground water from the uppe r Floridan aquifer plays a major role on the quality of surface water in regions where the Suwa nnee and Santa Fe rivers intersects the top of the upper Floridan aquifer. The regions of the MSRB and Lower Santa Fe River Basin (LSFRB) where the greatest increase in NO3-N concentrations occur are relatively sm all segments of river channel within each river system. The NO3-N was likely moving into the surfacewater system via ground water through springs and seeps in the riverbed. The soils adjacent to these segments were Entisols that have high leaching potential. Furthermore, the upper Floridan aquifer is unconfined in these regions. The coupling of the upper Floridan aqui fer being unconfined and overlain by soil with high leaching potential with landuses that are adding NO3-N via fertilizer crea tes the potential for contamination of the upper Floridan aqui fer. This resulted in increased NO3-N concentrations in reaches of the Suwannee and Santa Fe river whic h receive base flow from the upper Floridan aquifer. Two springs sampled in the segment of the MSRB where the highest increase in NO3-N loading occurred showed a linear relationship with K and NO3-N. Results from a USGS study showed that the NO3-N was from an inorganic source and th e age of the water was less than nine years (Katz et al., 1999). This is similar to the observed relationship of N fer tilizer sales data and riverine NO3-N concentration and the appare nt lag time of one to six years. Furthermore, for the Suwannee River this suggests that fertilizer is the major component of the observed increasing

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187 NO3-N trend in the Suwannee River at Branfor d. The Middle Suwannee and Lower Santa Fe rivers showed increased NO3-N concentrations from 2000-2001 to 2006 sampling events. This suggests that the NO3-N loading from the ground water to the surface water was increasing for the studied areas of the MSRB and LSFRB. Thus, understanding the aerial extent of the groundwater domains of the upper Floridan aquifer that supplies the water to the MSRB and the LSFRB and landuses that occur within the domains is needed to focus management activities. Groundwater domains were defined in the Suwannee River Water Management District (SRWMD) using potentiometric surface maps and water quality data of the upper Floridan aquifer. Nine distinct groundwat er domains were indentified in the upper Floridan aquifer within the SRWMD. The Santa Fe, Ichetucknee and Suwannee domains had the highest median NO3-N concentrations of the groundw ater domains within the SRWMD. These domains generally occurred in areas where the unc onfined Floridan aquifer underlie s Entisols with high leaching potential. Variation in the concentrations of NO3-N was due to anthropogenic factors, primarily the use of inorganic fertilizer. Relating landuse in a groundwater do main to observed upper Floridan NO3-N and TP concentrations yielded a correlation for leve l 2 Florida landuse codes (FLUC) for crop and pasture land and groundwa ter domain median NO3-N concentration. No other correlations with TP and NO3-N concentrations and other level 2 FLUC were identified. When the percentage of a groundwater domain area was greater than 12 percent crop and past ure land, the domain generally had elevated NO3-N concentrations. The major co mponent of the level 2 FLUC crop and pasture land class is improved pasture which also includes areas used for forage production. It is important that the regulating agencies continue to work with the point source discharges associated with phos phate mining in the upper Suwannee River Basin to maintain the

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188 declining trend in TP c oncentrations. Reducing NO3-N concentration in the Suwannee River will require continued implementation of best ma nagement practices (BMPs) by the agricultural producers. The Floridan aquifer is especia lly vulnerable in areas where the aquifer is unconfined and soils have high leaching potential. Development/implementation of BMPs on these areas should be given priority.

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189 APPENDIX A HISTORICAL TOTAL PHOSPHOR US AND NITRATE-NITROGEN 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.41971 1972 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006Water yearMedian Total P (mg/L) Figure A-1. Median TP concentration for the Suwannee River at Branford.

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190 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40195 4 19 5 6 1958 1960 1 96 2 1968 1970 197 2 19 7 4 1976 1978 1 98 0 1982 1984 198 6 1 98 8 1990 1992 199 4 1 99 6 1998 2000 200 2 20 0 4 2006Median NOx-N (mg/L) Figure A-2. Median NO3-N concentration for the Suwannee River at Branford.

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191 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.81954 1 956 1 9 58 1960 1 9 62 1 9 67 1 969 1 9 71 1973 1 97 5 1 9 77 1979 1 9 81 1983 1 98 5 1 9 87 1989 1 9 91 1993 1995 1 9 97 1999 2 0 01 2 0 03 2005Water YearMedian K (mg/L) Figure A-3. Median K concentration fo r the Suwannee River at Branford.

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192 APPENDIX B WATER QUALITY SUMMARY Table B-1. Summary of upper Floridan groundwater quality fo r the SRWMD (2001 to 2006). Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Minimum Maximum Temperature C 22.0 4.21 21.2 21.9 22.7 13.23 225 Specific Conductance mhos cm-1 369 171.6 282 352 437 2714 pH su 7.64 17.14 6.85 7.15 7.4 3.45 586 Dissolve Oxygen mg L-1 2.68 10.67 0.4 1.37 3.73 373 Turbidity (NTU) NTU 11.57 47.12 0.5 1.9 8.4 0.04 986 Total Dissolved Solids mg L-1 251.8 856 162 205 260 4 36800 Alkalinity mg L-1 171.44 64.36 133 170 207 0.3 660 Total Organic Carbon mg L-1 3.45 5.83 0.638 1.4 3.68 0.38 79.6 Dissolve Organic Carbon mg L-1 4.05 5.67 0.85 2.08 5 0.07 61.6 Potassium mg L-1 1.23 8.56 0.19 0.401 0.824 0.007 243 Sodium mg L-1 11.14 148.51 2.64 3.4 5.24 0.044 4800 Magnesium mg L-1 8.61 17.27 2.37 5.1 11.8 0.004 536 Calcium mg L-1 62.78 36.20 43.1 58.5 79.225 0.004 913 Chloride mg L-1 18 281.63 4.45 5.65 8.02 0.15 9870 Fluoride mg L-1 0.17 0.60 0.07 0.12 0.2 0.02 29.9 Sulfate mg L-1 12.75 46.24 2.16 5.17 10.8 0.11 1140 Iron mg L-1 0.94 3.30 0.031 0.159 0.909 0.003 131 Nitrate +Nitritenitrogen mg L-1 0.94 2.73 0.00 0.17 1.00 0.002 52.0 TKN mg L-1 0.33 0.43 0.11 0.2 0.4 0.04 8.5 Ammonia-nitrogen mg L-1 0.10 0.29 0.037 0.04 0.100 0.016 10.1 Total Phosphorus mg L-1 0.219 1.558 0.000 0.07 0.156 0.005 45.0

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193 Table B-2. Summary of water qualit y parameters for the Springs of Aucilla River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Aucilla Temperature C 20.4 2.85 20.1 20.5 21.4 13.3 26.6 Specific Conductance mhos cm-1 263 84.9 224.5 279.5 318 72 459 pH su 7.20 0.36 6.91 7.25 7.52 6.49 7.79 Dissolved Oxygen mg L-1 4.66 1.92 3.3 4.75 5.68 0.7 9.7 Total Organic Carbon mg L-1 11.96 11.52 0.4 6.5 24.4 0.3 31.7 Dissolved Organic Carbon mg L-1 1.1 1.82 0.38 0.45 0.63 0.3 5.6 Potassium mg L-1 0.54 0.44 0.3 0.4 0.7 0 2.3 Sodium mg L-1 4.05 3.14 2.9 3.2 4.1 2.1 19.1 Magnesium mg L-1 6.89 3.28 4.4 6.7 8.6 1.5 16.2 Calcium mg L-1 35.61 17.25 20.4 41.4 45.4 3.5 73.5 Chloride mg L-1 6.43 5.27 4.3 5.3 7 0.5 32 Fluoride mg L-1 0.09 0.05 0.06 0.08 0.12 0.04 0.26 Sulfate mg L-1 5.9 4.2 2 5 9 0.1 15 TKN mg L-1 0.39 0.29 0.14 0.36 0.63 0.04 0.93 Nitrate+Nitritenitrogen mg L-1 0.16 0.14 0.05 0.13 0.26 0 0.46 Ammonianitrogen mg L-1 0.024 0.015 0.02 0.02 0.027 0 0.07 Total Phosphorus mg L-1 0.053 0.052 0.036 0.043 0.056 0.009 0.319 Soluble reactive Phosphorus mg L-1 0.031 0.009 0.029 0.032 0.037 0.016 0.05

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194 Table B-3. Summary of water qualit y parameters for the Springs of Coastal Rivers Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Coastal Temperature C 21.3 2.67 20.3 21.3 22.3 10.5 25.5 Specific Conductance mhos cm-1 2927 5511.3 428 755 878 213 23700 pH su 6.99 0.24 6.84 6.96 7.12 6.4 7.65 Dissolved Oxygen mg L-1 2.89 2.58 0.5 2.8 4.7 0.1 8.7 Total Organic Carbon mg L-1 14.23 8.60 10.4 10.7 12.95 8.1 35.8 Dissolved Organic Carbon mg L-1 18.3 9.09 11.7 13.9 23.3 10.7 31.9 Potassium mg L-1 0.53 0.34 0.4 0.5 0.575 0 1.5 Sodium mg L-1 6.24 1.47 5.4 5.7 6.75 4.2 9.9 Magnesium mg L-1 16.09 3.513 15.73 16.15 17.75 5.9 20.3 Calcium mg L-1 115.07 22.93 113.5 120.5 127.5 42.9 132 Chloride mg L-1 10.04 4.90 5.5 11.2 14.15 1 16 Fluoride mg L-1 0.27 0.06 0.27 0.29 0.31 0.08 0.35 Sulfate mg L-1 56.59 18.51 50.5 62.8 68.23 3 74 TKN mg L-1 0.43 0.14 0.37 0.43 0.48 0.16 0.82 Nitrate+Nitritenitrogen mg L-1 0.05 0.06 0.02 0.025 0.05 0 0.38 Ammonianitrogen mg L-1 0.14 0.05 0.119 0.16 0.186 0.01 0.216 Total Phosphorus mg L-1 0.075 0.019 0.068 0.072 0.078 0.047 0.128 Soluble reactive Phosphorus mg L-1 0.057 0.018 0.054 0.063 0.066 0.002 0.087

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195 Table B-4. Summary of water quality parameters for the Springs of Lower Suwannee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Lower Suwannee Temperature C 21.6 0.82 21.4 21.7 22.1 10.2 25.9 Specific Conductance mhos cm-1 407 59.5 366 412 455 77 543 pH su 7.25 0.18 7.16 7.26 7.38 6.05 7.95 Dissolved Oxygen mg L-1 1.85 1.31 1 1.6 2.3 0.1 8 Total Organic Carbon mg L-1 3.77 4.84 0.7 1.8 5.4 0 54.8 Dissolved Organic Carbon mg L-1 4.01 4.90 0.9 2.2 5.92 0.2 47.6 Potassium mg L-1 1.30 1.24 0.5 0.8 1.6 0 8.6 Sodium mg L-1 3.66 1.41 2.7 3.5 4.4 0.1 28.7 Magnesium mg L-1 8.92 4.29 6 7.3 11.6 0 28.7 Calcium mg L-1 63.5 13.69 54.4 61.6 71.1 0 119 Chloride mg L-1 7.39 3.06 5.4 7 9 0 39 Fluoride mg L-1 0.11 0.051 0.08 0.11 0.15 0.02 0.39 Sulfate mg L-1 19.9 11.11 12 16.3 24.1 0.2 54.7 TKN mg L-1 0.16 0.64 0.04 0.1 0.16 0 17.8 Nitrate+Nitritenitrogen mg L-1 3.01 3.11 1.3 1.91 3.45 0 21.8 Ammonianitrogen mg L-1 0.035 0.030 0.02 0.02 0.04 0.001 0.205 Total Phosphorus mg L-1 0.051 0.030 0.032 0.047 0.064 0.004 0.43 Soluble reactive Phosphorus mg L-1 0.034 0.017 0.022 0.031 0.045 0.002 0.129

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196 Table B-5. Summary of water qualit y parameters for the Springs of Santa Fe River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Santa Fe Temperature C 22.2 0.93 21.7 22.2 22.4 17.1 28.1 Specific Conductance mhos cm-1 382 67.2 334 370.5 426.3 86 675 pH su 7.33 0.24 7.22 7.34 7.49 5.71 8.25 Dissolved Oxygen mg L-1 2.28 2.11 0.3 1.7 4 0.1 9.5 Total Organic Carbon mg L-1 4.36 7.20 0.52 1.6 5.3 0 52.9 Dissolved Organic Carbon mg L-1 4.30 6.64 0.8 1.9 5.6 0.1 53.9 Potassium mg L-1 0.67 0.48 0.3 0.5 1 0 5.4 Sodium mg L-1 5.76 3.08 2.9 5.2 8.4 1.8 19.8 Magnesium mg L-1 7.45 2.49 5.6 6.8 8.9 2.2 15.7 Calcium mg L-1 60.13 10.08 52.8 59.4 66.85 10.6 103 Chloride mg L-1 9.38 4.95 5.5 8 13.2 3 62 Fluoride mg L-1 0.15 0.067 0.1 0.15 0.19 0.02 0.66 Sulfate mg L-1 30.6 104.7 9.47 16.5 38.5 3.2 2550 TKN mg L-1 0.19 0.23 0.05 0.1 0.23 0 1.56 Nitrate+Nitritenitrogen mg L-1 0.90 1.60 0.39 0.58 1.01 0 26 Ammonianitrogen mg L-1 0.035 0.034 0.02 0.02 0.04 0.001 0.369 Total Phosphorus mg L-1 0.083 0.057 0.048 0.077 0.101 0.004 0.82 Soluble reactive Phosphorus mg L-1 0.064 0.038 0.033 0.06 0.088 0.004 0.309

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197 Table B-6. Summary of water quality parameters for the Springs of Upper Suwannee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Upper Suwannee Temperature C 21.0 1.29 20.5 20.8 21.3 17 27.6 Specific Conductance mhos cm-1 312 68.6 285.3 320 370 126 458 pH su 7.20 0.24 7.14 7.22 7.32 6.57 8.66 Dissolved Oxygen mg L-1 0.75 1.20 0.2 0.4 0.7 0 10.2 Total Organic Carbon mg L-1 8.04 6.59 2.9 6.3 10.8 0 24.8 Dissolved Organic Carbon mg L-1 8.38 6.10 3.6 6.7 10.8 0.8 26.4 Potassium mg L-1 0.73 0.51 0.4 0.6 1.25 0 3 Sodium mg L-1 4.17 3.82 2.8 3.4 4.1 0 37.7 Magnesium mg L-1 6.71 2.46 4.6 6.7 8.55 0 11.6 Calcium mg L-1 47.02 13.72 37.3 50 56.1 0.1 72 Chloride mg L-1 5.51 1.91 4.8 5.3 6.77 1 11.1 Fluoride mg L-1 0.14 0.04 0.11 0.13 0.16 0.02 0.32 Sulfate mg L-1 13.23 8.11 8.85 10.4 15.1 1 35.9 TKN mg L-1 0.36 0.33 0.105 0.28 0.48 0 1.8 Nitrate+Nitritenitrogen mg L-1 0.40 0.39 0.02 0.29 0.7 0 1.91 Ammonianitrogen mg L-1 0.064 0.10 0.02 0.04 0.099 0.001 1.1 Total Phosphorus mg L-1 0.102 0.045 0.060 0.110 0.136 0.004 0.22 Soluble reactive Phosphorus mg L-1 0.077 0.039 0.041 0.08 0.112 0.002 0.146

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198 Table B-7. Summary of water quality parameters for the Springs of Waccasassa River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Minimum Maximum Waccassasa Temperature C 22.4 0.30 22.1 22.3 22.7 22.1 22.7 Specific Conductance mhos cm-1 207 11.6 194 213 216 194 216 pH su 6.86 0.25 6.59 7.03 7.05 6.59 7.05 Dissolved Oxygen mg L-1 3.32 0.89 2.4 3.7 3.7 2.4 4.4 Total Organic Carbon mg L-1 Dissolved Organic Carbon mg L-1 Potassium mg L-1 Sodium mg L-1 Magnesium mg L-1 Calcium mg L-1 Chloride mg L-1 4.25 0.50 4 4 4.25 4 5 Fluoride mg L-1 Sulfate mg L-1 TKN mg L-1 Nitrate+Nitritenitrogen mg L-1 0.436 0.25 0.42 0.43 0.65 0.03 0.65 Ammonianitrogen mg L-1 0.02 0.00 0.02 0.02 0.02 0.02 0.02 Total Phosphorus mg L-1 0.045 0.01 0.043 0.045 0.048 0.039 0.053 Soluble reactive Phosphorus mg L-1 0.0317 0.00 0.0295 0.032 0.034 0.028 0.035

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199 Table B-8. Summary of water quality parameters for the Springs of Withlacoochee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Withlacoochee Temperature C 20.9 0.3 20.8 20.9 21 19.6 22.8 Specific Conductance mhos cm-1 287 17.2 278.3 286 289.2 237 383 pH su 7.50 0.21 7.42 7.55 7.63 6.78 7.92 Dissolved Oxygen mg L-1 1.85 1.03 1 1.7 2.3 0.2 5.3 Total Organic Carbon mg L-1 1.18 1.23 0.5 0.65 1.1 0.3 5.8 Dissolved Organic Carbon mg L-1 1.48 1.51 0.8 0.85 1.35 0.3 7.1 Potassium mg L-1 0.51 0.39 0.4 0.4 0.5 0.2 3 Sodium mg L-1 4.20 4.49 3.2 3.4 3.9 2.9 35.4 Magnesium mg L-1 8.33 0.64 7.95 8.4 8.9 6.3 9.8 Calcium mg L-1 40.9 2.80 39.5 41.1 42.7 33.1 48.9 Chloride mg L-1 5.74 0.88 5 5.7 6.2 4.3 7.7 Fluoride mg L-1 0.14 0.043 0.13 0.15 0.17 0.05 0.25 Sulfate mg L-1 12.8 1.4 11.75 12.7 13.65 10.6 16.4 TKN mg L-1 0.19 0.15 0.11 0.12 0.25 0.04 0.627 Nitrate+Nitritenitrogen mg L-1 1.34 0.34 1.17 1.39 1.58 0.27 1.94 Ammonianitrogen mg L-1 0.05 0.04 0.02 0.04 0.099 0.02 0.235 Total Phosphorus mg L-1 0.054 0.016 0.044 0.05 0.06 0.04 0.14 Soluble reactive Phosphorus mg L-1 0.035 0.01 0.0277 0.034 0.0435 0.019 0.056

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200 Table B-9. Summary of surfacewater quality parameters for the Al apaha River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Alapaha Temperature C 20.6 4.74 17.0 21.50 24.50 8.20 27.10 Specific Conductance mhos cm-1 84 36.7 56.5 77 104 210 pH su 6.14 0.70 5.60 6.25 6.7 3.98 7.51 Dissolved Oxygen mg L-1 7.78 1.53 6.7 7.5 8.7 3.8 11.9 Total Organic Carbon mg L-1 18.622 8.384 12.3 17.15 23.575 0.8 46.1 Potassium mg L-1 1.93 0.74 1.50 1.80 2.20 0.30 5.90 Sodium mg L-1 7.91 5.60 3.90 6.20 10.30 1.50 27.00 Magnesium mg L-1 2.04 0.74 1.50 1.90 2.50 0.40 7.10 Calcium mg L-1 4.64 5.61 3.00 3.90 4.90 1.40 62.50 Chloride mg L-1 9.65 2.76 8.00 9.80 11.30 0 18.20 Fluoride mg L-1 0.13 0.06 0.09 0.11 0.18 0.02 0.32 Sulfate mg L-1 7.7 6.5 3.0 6.0 10.4 0.8 45.3 TKN mg L-1 0.79 0.32 0.56 0.79 0.96 0 2.00 Nitrate+Nitritenitrogen mg L-1 0.48 0.44 0.14 0.31 0.72 0 2.00 Ammonianitrogen mg L-1 0.04 0.03 0.02 0.03 0.04 0 0.33 Total Phosphorus mg L-1 0.191 0.097 0.110 0.180 0.250 0.041 0.567 Soluble Reactive Phosphorus mg L-1 0.127 0.085 0.056 0.105 0.193 0.014 0.460

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201 Table B-10. Summary of surfacewater quality parameters for the Au cilla River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th PercentileMedian 75th PercentileMinimum Maximum Aucilla Temperature C 19.7 5.3 15.4 20.7 23.8 4.4 28.8 Specific Conductance mhos cm-1 194 109.4 69 257 293 28 330 pH su 7.03 0.98 6.35 7.31 7.86 4.67 8.32 Dissolved Oxygen mg L-1 7.37 1.80 6.1 7.4 8.9 2.5 10.9 Total Organic Carbon mg L-1 16.73 14.41 4.38 10.9 26.48 0.5 55.2 Potassium mg L-1 0.56 0.35 0.30 0.40 0.78 0 1.90 Sodium mg L-1 3.05 0.77 2.60 3.00 3.30 1.70 8.10 Magnesium mg L-1 5.15 2.77 2.13 6.40 7.60 0.80 10.60 Calcium mg L-1 28.65 17.55 8.60 37.85 44.55 0.40 51.70 Chloride mg L-1 5.62 1.36 5.00 5.50 6.18 0.5 11.10 Fluoride mg L-1 0.11 0.05 0.07 0.12 0.15 0.02 0.29 Sulfate mg L-1 3.4 2.5 0.8 4.0 5.4 0.1 12.3 TKN mg L-1 0.68 0.53 0.22 0.51 1.09 0.05 2.50 Nitrate+Nitritenitrogen mg L-1 0.05 0.05 0.01 0.03 0.07 0 0.44 Ammonianitrogen mg L-1 0.04 0.03 0.02 0.04 0.06 0 0.12 Total Phosphorus mg L-1 0.054 0.027 0.037 0.048 0.070 0.011 0.150 Soluble Reactive Phosphorus mg L-1 0.026 0.014 0.018 0.025 0.032 0.002 0.078

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202 Table B-11. Summary of surfacewater quality parameters for the Coas tal Rivers Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th PercentileMedian 75th PercentileMinimumMaximum Coastal Temperature C 20.6 4.86 17 21.15 24.3 6.2 32.3 Specific Conductance mhos cm-1 2485 7331 170 364 586 33 4084 pH su 6.86 0.89 6.77 7.1 7.33 3.29 8.41 Dissolved Oxygen mg L-1 4.92 1.99 3.8 5.1 6.3 0.2 10.4 Total Organic Carbon mg L-1 42.41 33.07 18.9 36 53.6 2.5 213 Potassium mg L-1 13.58 52.18 0.20 0.50 1.00 0 570.00 Sodium mg L-1 377.40 1385.30 2.90 3.92 13.10 1.00 15050.00 Magnesium mg L-1 50.90 285.90 3.65 7.20 13.60 0.20 6890.00 Calcium mg L-1 56.76 51.01 26.00 47.20 70.93 1.00 352.00 Chloride mg L-1 704.00 4710.00 5.90 8.70 13.70 0 118000.00 Fluoride mg L-1 0.20 0.88 0.09 0.13 0.20 0.02 24.00 Sulfate mg L-1 119.6 349.2 2.1 8.0 29.1 0.1 4360.0 TKN mg L-1 1.46 1.94 0.57 1.00 1.53 0.09 26.00 Nitrate+Nitritenitrogen mg L-1 0.07 0.11 0.02 0.05 0.06 0 0.71 Ammonianitrogen mg L-1 0.39 1.22 0.02 0.04 0.10 0 17.00 Total Phosphorus mg L-1 0.285 0.707 0.054 0.091 0.139 0.010 9.600 Soluble Reactive Phosphorus mg L-1 0.169 0.389 0.027 0.050 0.082 0.000 4.000

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203 Table B-12. Summary of surfacewater quality parameters for the Lower Suwannee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th PercentileMinimumMaximum Lower Suwannee Temperature C 21.2 4.6 17.5 21.6 25.3 9 29.4 Specific Conductance mhos cm-1 247 105.8 163 263 337 29 918 pH su 7.15 0.62 6.82 7.24 7.6 3.79 9.83 Dissolved Oxygen mg L-1 6.43 1.41 5.5 6.4 7.37 1.2 26.3 Total Organic Carbon mg L-1 16.14 10.59 7.6 14 23.2 0.8 69 Potassium mg L-1 1.18 0.89 0.80 1.00 1.40 0.10 27.10 Sodium mg L-1 6.00 4.80 4.40 5.40 6.60 0.70 110.00 Magnesium mg L-1 5.86 2.78 3.50 6.00 7.90 0.60 28.40 Calcium mg L-1 32.94 15.91 20.00 34.40 46.20 2.30 85.20 Chloride mg L-1 8.07 8.25 6.50 7.50 8.50 0 170.00 Fluoride mg L-1 0.14 0.05 0.11 0.13 0.18 0.02 0.53 Sulfate mg L-1 16.4 8.0 9.8 17.0 22.6 0.8 47.3 TKN mg L-1 0.58 0.39 0.28 0.53 0.80 0 5.90 Nitrate+Nitritenitrogen mg L-1 0.57 0.33 0.31 0.56 0.81 0 2.44 Ammonianitrogen mg L-1 0.04 0.03 0.02 0.03 0.04 0 0.35 Total Phosphorus mg L-1 0.161 0.094 0.111 0.14 0.181 0.004 1.320 Soluble Reactive Phosphorus mg L-1 0.115 0.068 0.078 0.1 0.134 0.002 1.290

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204 Table B-13. Summary of surfacewater quality parameters for the Santa Fe River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Santa Fe Temperature C 20.5 4.3 18.1 21.3 23.6 5 31.3 Specific Conductance mhos cm-1 245 129.2 125 250 350 22 1948 pH su 6.81 0.92 6.41 7.09 7.45 3.21 8.36 Dissolved Oxygen mg L-1 5.70 1.71 4.6 5.5 6.7 0.5 14.4 Total Organic Carbon mg L-1 21.09 18.29 6.1 15.9 32.4 0 139.6 Potassium mg L-1 1.01 2.53 0.50 0.80 1.10 0 98.80 Sodium mg L-1 7.25 4.48 4.90 6.25 8.40 1.80 94.10 Magnesium mg L-1 5.80 3.01 3.30 6.00 7.40 0.10 15.70 Calcium mg L-1 31.45 21.89 11.00 25.70 52.20 0.90 111.00 Chloride mg L-1 14.06 8.53 9.00 12.20 16.70 0 88.30 Fluoride mg L-1 0.15 0.08 0.10 0.14 0.20 0.02 1.30 Sulfate mg L-1 17.6 16.2 5.2 13.0 25.0 0.8 105.0 TKN mg L-1 0.71 0.61 0.22 0.60 1.04 0 5.25 Nitrate+Nitritenitrogen mg L-1 0.34 0.32 0.07 0.26 0.56 0 4.80 Ammonianitrogen mg L-1 0.05 0.12 0.02 0.03 0.05 0 2.70 Total Phosphorus mg L-1 0.204 0.368 0.080 0.124 0.210 0.001 6.000 Soluble Reactive Phosphorus mg L-1 0.151 0.274 0.053 0.092 0.159 0.001 3.800

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205 Table B-14. Summary of surfacewater quality parameters for the Upper Suwannee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th Percentile Mi nimum Maximum Upper Suwannee Temperature C 20.8 5.6 16.5 21.5 25.3 5.6 32.5 Specific Conductance mhos cm-1 124 93.8 65.25 79 161.3 34 1570 pH su 5.47 1.45 4.01 5.38 6.93 2.34 8.05 Dissolved Oxygen mg L-1 6.14 1.92 5 6 7.3 0 22.4 Total Organic Carbon mg L-1 38.89 18.51 24.7 40.9 52 2.8 98 Potassium mg L-1 0.68 0.65 0.20 0.50 1.00 0 5.90 Sodium mg L-1 5.02 2.91 3.40 4.20 5.60 0 46.30 Magnesium mg L-1 2.81 2.51 1.00 1.80 4.10 0 15.00 Calcium mg L-1 11.48 12.93 1.80 4.90 18.28 0.10 55.00 Chloride mg L-1 7.53 2.64 6.00 7.60 8.70 0 65.00 Fluoride mg L-1 0.17 0.21 0.08 0.12 0.20 0.02 4.90 Sulfate mg L-1 9.9 11.3 1.1 5.5 15.0 0.2 120.0 TKN mg L-1 1.25 5.04 0.70 0.99 1.22 0.04 128.00 Nitrate+Nitritenitrogen mg L-1 0.15 0.31 0.03 0.05 0.20 0 8.04 Ammonianitrogen mg L-1 0.05 0.07 0.02 0.03 0.06 0 1.10 Total Phosphorus mg L-1 0.299 0.535 0.100 0.168 0.280 0.004 8.900 Soluble Reactive Phosphorus mg L-1 0.253 0.531 0.060 0.128 0.230 0.000 8.800

PAGE 206

206 Table B-15. Summary of surfacewater quality parameters for the Waccasassa River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th PercentileMinimumMaximum Waccasassa Temperature C 20.6 4.74 17 21.5 24.5 8.2 27.1 Specific Conductance mhos cm-1 409 369.2 273 358 434 52 3792 pH su 7.30 0.35 7.115 7.34 7.53 5.36 7.83 Dissolved Oxygen mg L-1 6.23 1.56 5.2 5.8 7.4 2.8 10.6 Total Organic Carbon mg L-1 16.64 10.97 7.2 14.8 24.5 1.6 45.9 Potassium mg L-1 1.16 3.75 0.20 0.40 0.80 0 37.70 Sodium mg L-1 26.32 101.85 4.54 6.40 10.35 1.80 1030.00 Magnesium mg L-1 10.25 12.69 6.10 8.70 10.40 1.40 133.00 Calcium mg L-1 50.93 18.54 38.20 49.30 60.05 8.40 140.00 Chloride mg L-1 30.48 73.87 8.55 12.00 17.00 2.7 554.00 Fluoride mg L-1 0.14 0.06 0.10 0.13 0.17 0.03 0.38 Sulfate mg L-1 17.4 8.8 10.1 15.7 45.5 3.0 318.0 TKN mg L-1 0.66 0.44 0.29 0.59 0.90 0.10 2.80 Nitrate+Nitritenitrogen mg L-1 0.10 0.09 0.02 0.09 0.16 0 0.49 Ammonianitrogen mg L-1 0.04 0.03 0.02 0.03 0.04 0 0.16 Total Phosphorus mg L-1 0.075 0.036 0.050 0.068 0.098 0.023 0.350 Soluble Reactive Phosphorus mg L-1 0.039 0.015 0.028 0.038 0.050 0.002 0.083

PAGE 207

207 Table B-16. Summary of surfacewater quality parameters for the Withlacoochee River Basin (1989 to 2006). Basin Parameter Units Mean Standard Deviation 25th Percentile Median 75th PercentileMinimumMaximum Withlacoochee Temperature C 19.9 5.03 16.15 21 24.1 5.7 29 Specific Conductance mhos cm-1 194 107.22 105.5 177 264 41 786 pH su 6.96 0.60 6.56 7 7.42 4.84 8.15 Dissolved Oxygen mg L-1 6.30 1.46 5.3 6 7.05 3 11.2 Total Organic Carbon mg L-1 11.39 6.44 6.2 10.8 16 0.1 45.5 Potassium mg L-1 2.17 1.15 1.50 2.10 0.10 Sodium mg L-1 10.42 10.23 4.50 6.60 11.75 2.10 74.00 Magnesium mg L-1 4.13 2.43 2.40 3.70 5.20 0.90 26.00 Calcium mg L-1 19.99 12.60 8.21 17.80 32.00 2.60 52.10 Chloride mg L-1 8.81 2.84 7.00 8.40 10.10 0 23.30 Fluoride mg L-1 0.14 0.06 0.10 0.13 0.18 0.02 0.74 Sulfate mg L-1 14.2 12.1 6.2 10.0 18.6 1.0 79.8 TKN mg L-1 0.57 0.33 0.30 0.56 0.77 0.04 2.10 Nitrate+Nitritenitrogen mg L-1 0.39 0.28 0.20 0.32 0.51 0 2.36 Ammonianitrogen mg L-1 0.04 0.06 0.02 0.03 0.05 0 0.86 Total Phosphorus mg L-1 0.137 0.098 0.093 0.115 0.147 0.010 1.100 Soluble Reactive Phosphorus mg L-1 0.082 0.058 0.048 0.067 0.095 0.015 0.461

PAGE 208

208 Table B-17A. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 1998. Contributing Basin Area (mi) Annual Loads kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee Reach 1 2,430 197,791.5 3.09 755,461.8 42.93 Alapaha River 1,801 264,561.0 4.13 195,610.3 11.11 Withlacoochee 2,382 841,213.913.14 263,494.5 14.97 Suwannee Reach 2 443 959,161.314.98 228,319.3 12.97 Suwannee Reach 3 824 2,910,823.945.47 188,536.7 10.71 Santa Fe Reach 1 820 59,007.1 0.92 108,270.9 6.15 Santa Fe Reach 2 564 1,017,344.315.89 107,829.0 6.13 Suwannee Reach 4,5, & 6 686 152,126.8 2.38 -87,569.7 -4.98 Total Load 9,950 6,402,029.7100.00 1,759,952.8 100.00 Table B-17B. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 1999. Contributing Basin Area (mi Annual Loads (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee Reach 1 2,430 75,192.5 1.76 206,590.9 33.12 Alapaha River 1,801 175,187.9 4.10 62,560.6 10.03 Withlacoochee 2,382 508,185.211.90 74,562.0 11.95 Suwannee Reach 2 443 383,006.3 8.97 64,285.4 10.31 Suwannee Reach 3 824 2,005,222.046.95 62,619.6 10.04 Santa Fe Reach 1 820 19,245.9 0.45 30,083.4 4.82 Santa Fe Reach 2 564 884,718.920.72 68,190.7 10.93 Suwannee Reach 4,5, & 6 686 220,026.0 5.15 54,856.9 8.79 Total 9,950 4,270,784.8100.00 623,749.4 100.00

PAGE 209

209 Table B-17C. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2000. Contributing Basin Area (mi) Annual Load (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 36,900.6 1.6% 82,096.2 25% Alapaha River 1,801 158,688.2 6.7% 71,765.6 22% Withlacoochee River 2,382 256,733.5 10.9% 39,748.6 12% Suwannee River Reach 2 443 281,498.4 11.9% 61,740.0 19% Suwannee River Reach 3 824 848,107.2 36.0% 0.0 0% Santa Fe River Reach 1 820 2,671.4 0.1% 5,748.8 2% Santa Fe River Reach 2 564 705,113.7 29.9% 52,714.2 16% Suwannee River Reaches 4, 5, & 6 686 69,110.1 2.9% 13,634.3 4% Total 9,950 2,358,000.0100.0% 327,600.0 100% Table B-17D. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2001. Contributing Basin Area (mi) Annual Load (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 30,716.1 1.1% 241,761.3 38% Alapaha River 1,801 344,868.412.8% 142,372.5 22% Withlacoochee River 2,382 543,940.120.2% 128,279.3 20% Suwannee River Reach 2 443 45,340.7 1.7% -112,024.0 -18% Suwannee River Reach 3 824 1,227,440.145.5% 103,347.9 16% Santa Fe River Reach 1 820 3,748.2 0.1% 10,820.0 2% Santa Fe River Reach 2 564 427,311.415.8% 26,890.0 4% Suwannee River Reaches 4, 5, & 6 686 75,818.6 2.8% 93,448.0 15% Total 9,950 2,699,183.5100.0% 634,895.1 100%

PAGE 210

210 Table B-17E. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2002. Contributing Basin Area (mi) Annual Load (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 17,576.2 0.7% 268,841.5 41.3% Alapaha River 1,801 96,958.3 3.6% 50,264.8 7.7% Withlacoochee River 2,382 236,861.6 8.9% 49,680.2 7.6% Withlacoochee GA 2,118 72,453.6 2.7% 53,895.0 8.3% Withlacoochee FL 264 164,408.0 6.1% -4,214.8 -0.6% Suwannee River Reach 2 443 174,178.7 6.5% -10,530.3 -1.6% Suwannee River Reach 3 824 783,503.0 29.3% 18,312.5 2.8% Santa Fe River Reach 1 820 2,698.4 0.1% 6,447.7 1.0% Santa Fe River Reach 2 564 522,922.8 19.6% 54,320.7 8.3% Suwannee River Reach 4 342 -161,535.1 -6.0% 6,461.7 1.0% Suwannee River Reaches 5 & 6 344 1,000,872.237.4% 207,890.2 31.9% Total 9,950 2,674,036.1100% 651,689.0 100.0% Table B-17F. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2003. Contributing Basin Area (mi) Annual Load Contribution (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 30,913.9 0.8% 792,541.7 54.1% Alapaha River 1,801 491,223.412.2% 271,328.3 18.5% Withlacoochee River 2,382 960,163.023.8% 346,609.1 23.7% Withlacoochee GA 2,118 801,011.619.8% 337,420.6 23.0% Withlacoochee FL 264 159,151.4 3.9% 9,188.5 0.6% Suwannee River Reach 2 443 -64,733.3 -1.6% -145,933.2 -10.0% Suwannee River Reach 3 824 1,386,940.134.4% 158,491.5 10.8% Santa Fe River Reach 1 820 26,674.5 0.7% 129,706.1 8.9% Santa Fe River Reach 2 564 626,407.015.5% 86,853.1 5.9% Suwannee River Reach 4 342 -184,172.2 -4.6% -121,628.5 -8.3% Suwannee River Reaches 5 & 6 344 763,194.1 18.9% -53,499.8 -3.7% Total 9,950 4,036,610.7100% 1,464,468.5 100.0%

PAGE 211

211 Table B-17G. TP and NO3-N loadings by watersheds/reach in the Suwannee River for water year 2004. Contributing Basin Area (mi) Annual Load Contribution (kg/year) Nitrate-N % of Load Tota l Phosphorus % of Load Suwannee River Reach 1 2,430 66,713.9 1.4% 867,015.6 100.2% Alapaha River 1,801 464,351.4 9.7% 174,172.1 20.1% Withlacoochee River 2,382 891,320.4 18.6% 172,898.5 20.0% Withlacoochee GA 2,118 309,349.1 6.5% 148,264.2 17.1% Withlacoochee FL 264 581,971.4 12.2% 24,634.3 2.8% Suwannee River Reach 2 443 -240,949.5 -5.0% -491,391.4 -56.8% Suwannee River Reach 3 824 1,660,115.3 34.7% 116,851.5 13.5% Santa Fe River Reach 1 820 13,469.1 0.3% 118,561.1 13.7% Santa Fe River Reach 2 564 1,014,996.9 21.2% 50,334.5 5.8% Suwannee River Reach 4 342 15,550.1 0.3% -121,249.5 -14.0% Suwannee River Reaches 5 & 6 344 903,821.5 18.9% -22,290.9 -2.6% Total 9,950 4,789,389.1 100% 864,901.4 100.0%

PAGE 212

212 MeanTotal Phoshorus Concentration (mg/L) October 2000 to September 2001TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Figure B-1A. Mean upper Floridan aquifer TP concentration contour map for water year 2001.

PAGE 213

213 MeanTotal Phoshorus Concentration (mg/L) October 2001 to September 2002TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Figure B-1B. Mean upper Floridan aquifer TP concentration contour map for water year 2002.

PAGE 214

214 Mean Total Phosphorus Concentration (mg/L) October 2002 to September 2003TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Figure B-1C. Mean upper Floridan aquifer TP concentration contour map for water year 2003.

PAGE 215

215 Mean Total Phosphorus Concentration (mg/L) October 2003 to September 2004TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Figure B-1D. Mean upper Floridan aquifer TP concentration contour map for water year 2004.

PAGE 216

216 Mean Total Phosphorus Concentration (mg/L) October 2004 to September 2005TP (mg/L) is a measure of the amount of total phosphorus in the ground water.>10 1 to 5 0.5 to 1 0.1 to 0.5 0.05 to 0.1 0.01 to 0.05 0 to 0.01 Note: This map represents a generalization of groundwater quality data. 5 to 10 Figure B-1E. Mean upper Floridan aquifer TP concentration contour map for water year 2005.

PAGE 217

217 Mean Nitrate Nitrogen Concentration (mg/L) October 2000 to September 2001 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.5 0 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Figure B-2A. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2001.

PAGE 218

218 Mean Nitrate Nitrogen Concentration (mg/L) October 2001 to September 2002 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.5 0 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Figure B-2B. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2002.

PAGE 219

219 Mean Nitrate-Nitrogen Concentration (mg/L) October 2002 to September 2003 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.5 0 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Figure B-2C. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2003.

PAGE 220

220 Mean Nitrate-Nitrogen Concentration (mg/L) October 2003 to September 2004 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.5 0 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Figure B-2D. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2004.

PAGE 221

221 Mean Nitrate-Nitrogen Concentration (mg/L) October 2004 to September 2005 Note: This map represents a generalization of groundwater quality data. >4.0 2.0 to 4.0 1.0 to 2.0 0.5 to 1.0 0.05 to 0.5 0 to 0.05Nitrate-nitrogen (mg/L) is a measure of the amount of nitrate dissolved in the ground water expressed in terms of the amount of nitrogen in the form of nitrate. Figure B-2E. Mean upper Floridan aquifer NO3-N concentration contour map for water year 2005.

PAGE 222

222 Mean Potassium Concentration (mg/L) October 2000 to September 2001K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.175 0.2 0.8125 1.425 2.65 5.1 10 40 50 Figure B-3A. Mean upper Floridan aquifer K concentration contour ma p for water year 2001.

PAGE 223

223 Mean Potassium Concentration (mg/L) October 2001 to September 2002K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.175 0.2 0.8125 1.425 2.65 5.1 10 40 50 Figure B-3B. Mean upper Floridan aquifer K concentration contour ma p for water year 2002.

PAGE 224

224 Mean Potassium Concentration (mg/L) October 2002 to September 2003K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.175 0.2 0.8125 1.425 2.65 5.1 10 40 50 Figure B-3C. Mean upper Floridan aquifer K concentration contour ma p for water year 2003.

PAGE 225

225 Mean Potassium Concentration (mg/L) October 2003 to September 2004K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.2 1.425 2.65 5.1 10 40 50 Figure B-3D. Mean upper Floridan aquifer K concentration contour ma p for water year 2004.

PAGE 226

226 Mean Potassium Concentration (mg/L) October 2004 to September 2005K (mg/L) is a measure of the amount of dissolved potassium in the ground water. Note: This map represents a generalization of groundwater quality data. 0 0.025 0.05 0.1 0.125 0.15 0.2 1.425 2.65 5.1 10 40 50 Figure B-3E. Mean upper Floridan aquifer K concentration contour ma p for water year 2005.

PAGE 227

227 Figure B-4A. Suwannee River Basin loadi ng by watershed/reach for water year 1998.

PAGE 228

228 Figure B-4B. Suwannee River Basin loadi ng by watershed/reach for water year 1999.

PAGE 229

229 Figure B-4C. Suwannee River Basin loadi ng by watershed/reach for water year 2000.

PAGE 230

230 Figure B-4D. Suwannee River Basin loadi ng by watershed/reach for water year 2001.

PAGE 231

231 Figure B-4E. Suwannee River Basin loadings by watershed/reach for water year 2002.

PAGE 232

232 Figure B-4F. Suwannee River Basin loadi ng by watershed/reach for water year 2003.

PAGE 233

233 Figure B-4G. Suwannee River Basin loadi ng by watershed/reach for water year 2004.

PAGE 234

234 APPENDIX C SELECTED MIDDLE SUWANNEE SPRINGS y = 0.2177x + 0.2391 R2 = 0.8543 0.0 1.0 2.0 3.0 4.0 5.0 6.0 0.02.04.06.08.010.012.014.016.018.020.0 NOx-N (mg/L)K (mg/L) Figure C-1. Plot of NO3-N versus K concentrations for spring SUW718971.

PAGE 235

235 y = 0.2499x 0.006 R2 = 0.7016 0.0 1.0 2.0 3.0 4.0 5.0 6.0 468101214161820 NOx-N (mg/L)K (mg/L) Figure C-2. Plot of NO3-N versus K concentrations for spring SUW725971.

PAGE 236

236 APPENDIX D WATER QUALITY SUMMARY BY GROUNDWATER DOMAINS Table D-1. Groundwater quality statis tical summary by gr oundwater domain. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Temperature C Alapaha 21.42 1.08 20.90 21.20 21.70 17.70 24.00 Aucilla 20.72 2.31 20.40 21.00 21.40 0.00 23.60 Coastal 21.56 1.40 20.60 21.80 22.40 16.90 27.50 Dixie 22.22 1.67 20.93 21.90 23.70 18.80 24.30 Ichetucknee 21.17 4.02 21.60 22.00 22.56 0.00 24.14 Santa Fe 19.60 7.77 21.77 22.64 23.17 0.00 24.56 Steinhatchee 20.18 5.25 20.90 21.20 21.80 0.00 25.83 Suwannee 20.80 7.93 21.20 21.99 22.70 0.00 225.00 Waccasassa 21.26 6.89 22.89 23.08 23.57 0.00 30.02 Specific Conductance mho cm-1 Alapaha 375.1 141.9 240.0 363.0 498.0 6.0 695.0 Aucilla 273.1 129.4 217.0 258.5 344.5 0.0 695.0 Coastal 499.9 373.0 340.0 396.0 497.0 174.0 2301.0 Dixie 474.7 62.4 410.5 475.5 534.0 385.0 590.0 Ichetucknee 361.8 140.0 284.0 334.0 420.0 0.0 1170.0 Santa Fe 294.2 103.7 258.8 301.5 355.0 0.0 617.0 Steinhatchee 461.8 273.0 341.0 469.0 541.0 0.0 2714.0 Suwannee 360.9 171.6 284.0 358.5 440.0 0.0 1815.0 Waccasassa 370.2 183.5 329.5 353. 0 537.0 0.0 588.0 pH su Alapaha 7.33 0.29 7.14 7.24 7.50 6.58 8.05 Aucilla 9.60 39.05 6.52 6.90 7.31 0.00 542.00 Coastal 6.88 0.43 6.70 6.85 7.14 5.50 8.02 Dixie 6.77 0.44 6.53 6.80 6.99 5.72 7.76 Ichetucknee 7.03 1.30 7.01 7.33 7.53 0.00 8.67 Santa Fe 7.04 1.59 7.18 7.37 7.53 0.00 8.42 Steinhatchee 6.63 0.91 6.47 6.77 6.98 0.00 7.64 Suwannee 7.58 19.33 6.81 7.10 7.33 0.00 586.00 Waccasassa 6.86 0.69 6.75 7.01 7.24 4.22 7.68

PAGE 237

237 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Turbidity NTU Alapaha 2.34 3.30 0.15 0.85 3.60 0.00 18.20 Aucilla 12.28 45.98 0.55 4.63 10.33 0.00 508.00 Coastal 14.86 19.86 1.00 11.00 16.50 0.00 110.00 Dixie 1.14 1.19 0.28 0.85 1.68 0.00 4.90 Ichetucknee 3.94 11.22 0.24 0.75 3.00 0.00 175.00 Santa Fe 2.33 7.53 0.24 0.64 1.65 0.00 77.50 Steinhatchee 29.50 103.38 3.80 9.00 18.10 0.00 986.00 Suwannee 13.30 51.95 0.35 1.55 7.80 0.00 750.00 Waccasassa 8.62 9.46 1.72 4.03 15.45 0.00 44.50 Total Dissolved Solids mg L-1 Alapaha 230.20 86.85 149.50 217.00 293.00 102.00 480.00 Aucilla 168.47 80.83 123.00 145.00 204.50 22.00 440.00 Coastal 1002.00 4395.00 201.00 234.00 291.00 120.00 36800.00 Dixie 239.40 91.90 232.80 265.00 295.00 0.00 325.00 Ichetucknee 222.09 100.08 169.00 204.00 250.00 0.00 972.00 Santa Fe 170.29 45.55 144.00 173.00 201.00 40.00 312.00 Steinhatchee 326.80 359.50 211.00 319.00 345.00 0.00 4040.00 Suwannee 231.40 299.10 168.30 208.00 260.00 0.00 10200.00 Waccasassa 228.70 79.30 176. 50 200.50 302.00 26.00 341.00 Alkalinity mg L-1 Alapaha 190.99 75.20 125.00 174.00 243.00 52.50 369.00 Aucilla 135.80 77.38 89.03 124.50 178.75 0.30 359.00 Coastal 197.62 57.95 141.50 190.00 265.00 88.00 310.00 Dixie 208.40 76.00 201.80 237.50 255.80 0.00 270.00 Ichetucknee 161.38 48.62 132.00 164.00 188.00 0.00 294.00 Santa Fe 141.23 41.10 127.75 142.00 163.00 15.00 343.00 Steinhatchee 234.48 89.45 184.00 275.00 293.00 0.00 660.00 Suwannee 171.03 62.57 139.00 176.00 211.00 0.00 486.00 Waccasassa 211.20 76.20 173.50 184.50 283.00 5.60 293.00

PAGE 238

238 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Total Organic carbon mg L-1 Alapaha 2.54 2.78 0.68 1.70 3.71 0.00 15.90 Aucilla 3.33 5.36 0.64 1.13 3.48 0.00 33.20 Coastal 4.40 4.75 0.75 2.48 7.94 0.00 21.20 Dixie 1.31 1.03 0.60 1.18 2.07 0.00 3.99 Ichetucknee 1.76 3.13 0.38 0.71 1.79 0.00 35.20 Santa Fe 1.47 2.18 0.38 0.64 1.63 0.00 20.64 Steinhatchee 11.44 12.29 3.07 8.30 16.60 0.00 79.60 Suwannee 2.93 5.45 0.59 1.10 3.00 0.00 57.20 Waccasassa 3.24 2.67 1. 06 2.68 5.61 0.00 10.80 Dissolved Organic carbon mg L-1 Alapaha 3.11 2.75 1.00 2.37 4.29 0.38 16.00 Aucilla 4.14 5.76 0.91 2.08 4.92 0.38 48.40 Coastal 5.44 4.45 1.53 4.44 8.08 0.80 19.50 Dixie 3.39 4.22 0.85 1.69 4.51 0.85 19.10 Ichetucknee 2.52 3.47 0.85 1.14 2.92 0.00 34.70 Santa Fe 2.82 2.66 0.85 1.82 4.20 0.38 21.07 Steinhatchee 11.74 9.87 4.04 8.30 17.54 0.00 56.76 Suwannee 3.98 5.93 0.85 1.96 4.71 0.00 61.60 Waccasassa 4.74 3.67 1. 51 5.04 6.45 0.85 18.70 Potassium mg L-1 Alapaha 1.13 0.59 0.49 1.31 1.62 0.14 2.80 Aucilla 0.37 0.35 0.21 0. 33 0.44 0.01 4.22 Coastal 7.57 38.75 0.17 0.26 0.40 0.05 243.00 Dixie 0.08 0.05 0.04 0.05 0.15 0.02 0.16 Ichetucknee 0.76 2.29 0.28 0.51 0.90 0.05 49.30 Santa Fe 0.67 1.62 0.16 0.30 0.68 0.01 16.70 Steinhatchee 1.08 6.00 0. 11 0.18 0.51 0.00 68.10 Suwannee 1.26 6.07 0.20 0.41 0.81 0.00 200.00 Waccasassa 0.63 0.60 0.13 0.17 1.27 0.05 1.55

PAGE 239

239 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Sodium mg L-1 Alapaha 7.25 6.01 3.14 4.30 10.45 0.94 21.50 Aucilla 5.82 15.67 2.36 2.80 3.39 0.71 107.00 Coastal 156.10 785.20 3.13 3.54 4.67 2.77 4800.00 Dixie 8.08 2.50 6.90 7.92 9.52 1.79 13.60 Ichetucknee 5.79 4.43 2.97 4.30 6.52 0.38 23.00 Santa Fe 4.00 2.10 2.47 2.98 6.04 0.42 13.50 Steinhatchee 14.65 67.51 3.94 4.45 5.00 0.00 722.00 Suwannee 5.44 16.04 2.52 3.11 4.56 0.04 329.00 Waccasassa 3.95 1.11 2.99 3.18 5.16 2.20 5.64 Magnesium mg L-1 Alapaha 14.12 11.77 3.63 10.50 25.50 1.17 41.10 Aucilla 7.94 8.60 2.41 4.50 7.32 0.00 41.70 Coastal 32.35 74.05 16.05 18.40 20.25 10.50 536.00 Dixie 1.34 0.22 1.20 1.37 1.46 0.87 1.86 Ichetucknee 8.81 7.56 2.81 5.45 14.80 0.03 32.80 Santa Fe 5.21 4.68 1.48 3.53 7.72 0.35 17.80 Steinhatchee 7.77 4.76 3.86 7.86 10.40 0.00 28.80 Suwannee 7.02 11.27 1.98 4.27 9.05 0.03 290.00 Waccasassa 8.83 2.32 9.01 9.30 9.75 0.49 10.40 Calcium mg L-1 Alapaha 54.16 17.62 40.20 59.90 66.75 7.14 86.30 Aucilla 43.18 23.11 32.10 39.10 62.60 0.09 112.00 Coastal 64.60 26.80 47.65 56.50 80.15 22.70 221.00 Dixie 94.98 9.89 89.90 96.15 101.75 67.80 108.00 Ichetucknee 59.27 27.59 40.40 52.30 74.30 3.52 215.00 Santa Fe 51.54 16.41 39.83 52.90 63.98 6.70 118.00 Steinhatchee 80.67 35.03 67.60 95.10 107.00 0.00 138.00 Suwannee 67.48 43.37 48.30 62.70 83.80 0.02 913.00 Waccasassa 69.46 27.61 54.30 58.50 96.23 0.66 105.00

PAGE 240

240 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Chloride mg L-1 Alapaha 6.36 3.58 3.65 6.07 8.46 1.56 30.10 Aucilla 4.94 1.88 3.97 4.51 5.43 1.62 18.20 Coastal 292.00 1496.00 5.32 5.99 6.96 3.22 9870.00 Dixie 11.66 5.63 10.13 11.70 15.13 0.00 21.90 Ichetucknee 9.41 11.29 4.66 5.93 8.46 0.00 76.10 Santa Fe 6.93 3.64 4.80 5.48 7.37 0.15 24.30 Steinhatchee 17.93 56.51 6.97 8.15 9.43 0.00 457.00 Suwannee 7.66 11.64 4.19 5.44 7.87 0.00 222.00 Waccasassa 6.06 1.44 4.98 5.54 7.44 3.00 9.02 Fluoride mg L-1 Alapaha 0.29 0.18 0.11 0.32 0.45 0.02 0.78 Aucilla 0.21 0.14 0.11 0.16 0.27 0.02 0.76 Coastal 0.61 3.15 0.14 0.20 0.25 0.03 29.90 Dixie 0.05 0.04 0.02 0.04 0.06 0.00 0.17 Ichetucknee 0.20 0.15 0.07 0.15 0.31 0.00 0.84 Santa Fe 0.14 0.09 0.07 0.10 0.22 0.02 0.51 Steinhatchee 0.12 0.09 0.06 0.11 0.15 0.00 0.53 Suwannee 0.11 0.09 0.05 0.10 0.15 0.00 1.14 Waccasassa 0.15 0.05 0.11 0.14 0.18 0.05 0.25 Sulfate mg L-1 Alapaha 9.28 14.22 2.05 5.27 11.50 0.00 99.10 Aucilla 2.25 2.56 0.40 1.72 3.09 0.00 18.30 Coastal 53.40 191.00 1.01 6.38 40.20 0.00 1140.00 Dixie 7.93 4.39 6.99 7.82 9.89 0.00 18.70 Ichetucknee 15.80 40.20 1.92 4.86 10.60 0.00 271.00 Santa Fe 3.92 2.55 1.88 4.18 5.51 0.00 13.20 Steinhatchee 2.34 3.71 0.18 0.96 3.53 0.00 22.40 Suwannee 11.85 3.56 2.48 6.37 13.30 0.00 52.00 Waccasassa 1.18 2.93 0.18 0.53 1.30 0.00 19.60

PAGE 241

241 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Iron mg L-1 Alapaha 0.25 0.43 0.02 0.08 0.36 0.00 2.84 Aucilla 1.26 4.55 0.03 0.49 1.48 0.00 54.10 Coastal 1.32 1.63 0.04 0.72 2.45 0.01 9.01 Dixie 0.21 0.88 0.01 0.01 0.02 0.00 3.94 Ichetucknee 0.31 0.91 0.02 0.06 0.23 0.00 12.50 Santa Fe 0.31 1.46 0.03 0.10 0.25 0.00 16.70 Steinhatchee 2.70 2.47 1.28 1.68 3.57 0.00 15.50 Suwannee 1.02 4.07 0.03 0.13 0.97 0.00 131.00 Waccasassa 1.62 1.14 0.50 1.72 2.63 0.42 4.46 Lead mg L-1 Alapaha 0.003 0.002 0.002 0.003 0.003 0.000 0.025 Aucilla 0.004 0.006 0.002 0.003 0.003 0.000 0.043 Coastal 0.003 0.001 0.002 0.003 0.003 0.000 0.009 Dixie 0.002 0.001 0.002 0.003 0.003 0.000 0.003 Ichetucknee 0.003 0.003 0.002 0.003 0.003 0.000 0.064 Santa Fe 0.002 0.002 0.002 0.003 0.003 0.000 0.010 Steinhatchee 0.003 0.007 0.002 0.003 0.003 0.000 0.064 Suwannee 0.005 0.058 0.002 0.003 0.003 0.000 2.100 Waccasassa 0.002 0.001 0.002 0.003 0.003 0.000 0.006 Nitrate+Nitrite-Nitrogen mg L-1 Alapaha 0.18 0.56 0.00 0.01 0.09 0.00 3.94 Aucilla 0.62 1.12 0.01 0. 03 0.62 0.00 4.16 Coastal 0.09 0.17 0.00 0.02 0.11 0.00 1.05 Dixie 0.02 0.02 0.00 0.02 0.03 0.00 0.07 Ichetucknee 0.62 1.74 0.01 0.25 0.73 0.00 27.20 Santa Fe 1.41 1.73 0.02 1.21 1.62 0.00 10.60 Steinhatchee 0.03 0.09 0.00 0.01 0.03 0.00 0.73 Suwannee 1.69 13.79 0.02 0.31 1.31 0.00 488.00 Waccasassa 0.01 0.02 0.00 0.01 0.01 0.00 0.09

PAGE 242

242 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum TKN mg L-1 Alapaha 0.36 0.37 0.14 0.26 0.50 0.04 2.43 Aucilla 0.33 0.37 0.11 0.24 0.37 0.04 3.00 Coastal 0.52 0.87 0.16 0.30 0.56 0.05 6.00 Dixie 0.20 0.13 0.11 0.17 0.25 0.05 0.60 Ichetucknee 0.24 0.23 0.11 0.18 0.31 0.04 2.00 Santa Fe 0.24 0.33 0.11 0.15 0.27 0.04 3.70 Steinhatchee 0.69 0.70 0.30 0.53 0.91 0.00 5.22 Suwannee 0.32 0.44 0.11 0.20 0.38 0.00 8.50 Waccasassa 0.40 0.23 0.20 0.37 0.60 0.05 0.94 Ammonia-nitrogen mg L-1 Alapaha 0.13 0.30 0.04 0.04 0.10 0.00 2.40 Aucilla 0.06 0.08 0.02 0.04 0.05 0.00 0.50 Coastal 0.18 0.58 0.02 0.04 0.20 0.00 5.25 Dixie 0.03 0.03 0.02 0.04 0.04 0.00 0.10 Ichetucknee 0.06 0.10 0.02 0.04 0.06 0.00 1.01 Santa Fe 0.06 0.22 0.02 0.04 0.04 0.00 3.54 Steinhatchee 0.16 0.15 0.04 0.12 0.22 0.00 0.59 Suwannee 0.09 0.33 0.02 0.04 0.09 0.00 10.10 Waccasassa 0.19 0.16 0.04 0.18 0.31 0.00 0.61 Total Phosphorus mg L-1 Alapaha 0.087 0.087 0.040 0.070 0.109 0.000 0.598 Aucilla 0.325 0.545 0.050 0.133 0.480 0.000 4.870 Coastal 0.258 0.228 0.081 0.151 0.522 0.000 0.814 Dixie 0.028 0.019 0.010 0.030 0.042 0.000 0.056 Ichetucknee 0.144 0.359 0.035 0.053 0.100 0.000 3.640 Santa Fe 0.102 0.204 0.040 0.055 0.105 0.000 2.240 Steinhatchee 2.610 9.960 0.040 0.068 0.461 0.000 25.000 Suwannee 0.321 1.758 0.044 0.070 0.145 0.000 45.100 Waccasassa 0.195 0.037 0.189 0.196 0.209 0.078 0.303

PAGE 243

243 Table D-1. continued. Variable Units Basin Mean Standard Deviation 25 th Percentile Median 75 th Percentile Minimum Maximum Cadmium mg L-1 Alapaha 0.002 0.001 0.000 0.002 0.003 0.000 0.004 Aucilla 0.002 0.002 0.000 0.002 0. 003 0.000 0.007 Coastal 0.002 0.001 0.000 0.001 0.003 0.000 0.004 Dixie 0.002 0.001 0.000 0.002 0.003 0.000 0.004 Ichetucknee 0.002 0.001 0.000 0.002 0.003 0.000 0.004 Santa Fe 0.002 0.002 0.000 0.002 0.003 0.000 0.005 Steinhatchee 0.002 0.002 0.000 0.002 0.003 0.000 0.010 Suwannee 0.002 0.007 0.000 0.002 0.003 0.000 0.257 Waccasassa 0.002 0.002 0.000 0.002 0.003 0.000 0.004 Arsenic mg L-1 Alapaha 0.009 0.006 0.005 0.010 0.010 0.000 0.023 Aucilla 0.011 0.007 0.009 0.010 0. 010 0.000 0.050 Coastal 0.010 0.006 0.007 0.010 0.010 0.000 0.023 Dixie 0.009 0.006 0.005 0.010 0.010 0.000 0.023 Ichetucknee 0.010 0.007 0.005 0.010 0.010 0.000 0.037 Santa Fe 0.009 0.008 0.005 0.010 0.010 0.000 0.050 Steinhatchee 0.011 0.014 0.005 0.010 0.010 0.000 0.100 Suwannee 0.011 0.013 0.005 0.010 0.010 0.000 0.286 Waccasassa 0.010 0.006 0.009 0.010 0.010 0.000 0.023

PAGE 244

244 Table D-2A. The Kruskal-Wallis Test for the gr oundwater domains differences using nine domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 794.4 -8.45 Aucilla 188 0.033 1180.2 -2.90 Coastal 93 0.018 822.6 -6.55 Dixie 20 0.017 657.5 -3.95 Ichetucknee 479 0.253 1318.3 -0.60 Santa Fe 262 1.205 1681.9 7.60 Steinhatchee 131 0.010 684.7 -9.92 Suwannee 1320 0.306 1495.0 10.41 Waccasassa 44 0.005 476.6 -7.46 Overall 2674 1337.5 H = 388.20 DF = 8 P = 0.000 H = 388.93 DF= 8 P = 0.000 (adjusted for ties) Table D-2B. The Kruskal-Wallis Test for the gr oundwater domains differences using eight domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 738.8 -8.09 Aucilla 188 0.033 1097.5 -2.23 Coastal 93 0.018 767.4 -6.20 Dixie 20 0.017 609.2 -3.85 Ichetucknee 479 0.253 1232.2 0.90 Steinhatchee 131 0.010 635.7 -9.65 Suwannee 1320 0.306 1383.4 13.71 Waccasassa 44 0.005 442.4 -7.35 Overall 2414 1206.5 H = 344.82 DF = 7 P = 0.000 H = 345.52 DF = 7 P = 0.000 (adjusted for ties)

PAGE 245

245 Table D-2C. The Kruskal-Wallis Test for the groundwater domains differences using seven domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 604.4 -7.89 Aucilla 188 0.033 884.2 -2.14 Coastal 93 0.018 631.9 -5.93 Dixie 20 0.017 504.9 -3.72 Steinhatchee 131 0.010 525.5 -9.38 Suwannee 1320 0.306 1110.9 16.64 Waccasassa 44 0.005 365.1 -7.24 Overall 1933 967.0 H = 330.08 DF = 6 P = 0.000 H = 330.77 DF = 6 P = 0.000 (adjusted for ties) Table D-2D. The Kruskal-Wallis Test for the gr oundwater domains differences using six domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 287.4 -1.47 Aucilla 188 0.033 376.1 6.42 Coastal 93 0.018 307.1 0.00 Dixie 20 0.017 264.6 -1.09 Steinhatchee 131 0.010 271.4 -2.60 Waccasassa 44 0.005 198.1 -4.23 Overall 613 307.0 H = 53.36 DF = DF= 5 P = 0.000 H = 53.99 DF = DF= 5 P = 0.000 (adjusted for ties)

PAGE 246

246 Table D-2E. The Kruskal-Wallis Test for the gr oundwater domains differences using five domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 221.0 0.92 Coastal 93 0.018 236.9 2.12 Dixie 20 0.017 203.7 -0.35 Steinhatchee 131 0.010 209.0 -0.45 Waccasassa 44 0.005 154.0 -3.37 Overall 425 213.0 H = 14.50 DF = 4 P= 0.006 H = 14.73 DF = 4 P= 0.005 (adjusted for ties) Table D-2F. The Kruskal-Wallis Test for the groundw ater domains differences using four domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0.005 176.8 1.63 Dixie 20 0.017 166.2 -0.01 Steinhatchee 131 0.010 169.9 0.52 Waccasassa 44 0.005 124.6 -3.11 Overall 332 166.5 H = 10.11 DF = 3 P= 0.018 H = 10.29 DF = 3 P= 0.016 (adjusted for ties)

PAGE 247

247 Table D-2G. The Kruskal-Wallis Test for the groundwater domains differences using three domains. Groundwater Domain N Median Ave Rank Z Alapaha 1 37 0 0.005 165.9 1.64 Steinhatchee 1 31 0 0.010 159.8 0.55 Waccasassa 44 0 0.005 117.3 -3.11 Overall 3 12 156.5 H = 9.98 DF = 2 P= 0.007 H = 10.16 DF = 2 P= 0.006 (adjusted for ties) Table D-2H. The Kruskal-Wallis Test for the gr oundwater domains differences using two domains. Groundwater Domain N Median Ave Rank Z Alapaha 137 0 5000.000 97.2 2.81 Waccasassa 44 0 5000.000 -71.7 2.81 Overall 181 91.0 H = 7.88 DF = 1 P= 0.005 H = 8.10 DF = 1 P= 0.004 ( (adjusted for ties)

PAGE 248

248 30 20 40 50 60 70 80 10 50 40 30 20 10 50 20 30 40 50 60 70 80 30 40 50 040Miles N Figure D-1. 1985 potentiometric surface map for the Suwannee Rive r Water Management District (Rosenau and Meadows, 1986). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

PAGE 249

249 3 04 02 01 06 07 09 05 08 05 07 05 06 08 0 040Miles N Figure D-2. 1990 potentiometric surface map for the Suwann ee River Water Management District (Meadows, 1991). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

PAGE 250

250 2 01 05 03 08 06 04 07 01 07 06 08 06 05 04 05 04 08 03 04 06 06 05 05 04 07 0 040Miles N Figure D-3. 1995 potentiometric surface map for the Suwannee River Water Management Di strict (Mahon et al., 1996). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

PAGE 251

251 1 04 008 05 07 06 03 02 04 04 03 05 02 05 07 07 05 04 003 05 05 06 07 07 06 08 06 02 0 040Miles N Figure D-4. 2002 potentiometric surface map for the Suwa nnee River Water Management District (SRWMD, 2002). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

PAGE 252

252 4 03 01 05 02 06 07 08 09 0007 08 02 08 005 06 06 08 06 01 05 06 07 09 08 04 002 03 02 002 04 06 06 08 02 05 07 08 08 006 08 02 01 05 06 07 09 08 04 002 03 02 002 04 06 06 08 02 05 07 08 08 006 08 02 0 040Miles N Figure D-5. 2005 potentiometric surface map for the Suwa nnee River Water Management District (SRWMD, 2005). 20 Potentiometric Contour – Groundwater level in feet above msl. Contour intervals 10 fee t

PAGE 253

253 LIST OF REFERENCES Andrews, W.J. 1994. Nitrate in ground water and spring water near four dairy farms in north Florida. Water Resour. Investigations Rep. 94-4162. U.S. Geol. Survey, Reston, VA. Arthur, J.D. 1991. The geomor phology. geology and hydrogeology of Lafayette County, Florida. Open File Report 46. Florida Geol. Survey, Tallahasee, FL. Asbury, C.E. and E.T. Oaksford. 1997. A comparison of drainage basin nu trient inputs with instream nutrient loads for seven rivers in Georgia and Florida, 1986-90. Water Resour. Investigation Report 97-4006. U.S. Geol. Survey, Reston, VA. Back, W. 1961. Techniques for mapping of hydr ochemical facies. Professional Paper 424-D. U.S. Geol. Survey, Reston, VA. Back, W and B.B. Hanshaw. 1965. Chemical geohydrology. Adv. Hydro Science, v.1, p. 49-109. Bass, D.G. and D.T. Cox. 1985. River habitat and fishery resources of Florida. p. 121-187 In : W. Seaman, Jr. (ed.), Florida Aquatic Habitat and Fishery Resources. Florida Chapter, American Fisheries Society, Kissimmee, FL. Berndt, M.P. 1996. Ground-water quality assessment of the Georgia-Flor ida Coastal Plain Study unit – analysis of available information on nut rients, 1972-92. Water Re sour. Investigations Report 95-4039. U.S. Geol. Survey, Reston, VA. Berndt, M.P., H.H. Hatzell, C.A. Crandall, M. Turtora, J.R. Pittman, and E.T. Oaksford. 1998. Water quality in the Georgia-Florida Coasta l Plain, Georgia and Fl orida, 1992-96. Circular 1151. U.S. Geol. Survey, Reston, VA. Buchanan, T.J. and W.P. Somers, 1969. Discharge measurements at gaging stations. Techniques of Water Resour. Investigations of the U.S. Geol. Survey, Book 3, Chap. A8. U.S. Geol. Survey. Burg, A. and T.H.E. Heaton. 1998. The relations hip between the nitrat e concentration and hydrology of a Small Chalk Spring, Isr ael. J. of Hydrology 204:68-82. Buzek, F., R. Kadlecova and K. Zak. 1998. Nitrat e pollution of a karstic groundwater system. Isotope Techniques in the Study of Environm ental Change, International Atomic Energy Agency Report 1024, Vienna, Austria. Brady, N.C. and R.R. Weil, 2000. Elements of the Nature and Properties of Soils. Prentice-Hall. Upper Saddle River, NJ. Carlisle, V.W., M.E. Collins, F. Sodek, III, a nd L. C. Hammond. 1985. Char acterization data For selected Florida soils. Soil and Water Science Department, Institute of Food and Agricultural Sciences, Soil Science Research Report Number 85-1. University of Florida, Gainesville, FL.

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254 Ceryak, R., M.S. Knapp and T.Q. Burnson. 1983. The geology and water resources of the upper Suwannee River Basin, Florida. Rep. of Investig ation No. 87. Florida Department of Natural Resources, Bureau of Geology, Tallahassee, FL. Collins, M.E., 2003. Key to soil orders in Florida. Fact Sheet SL-43. Soil and Water Science Department, Florida Cooperative Extension Se rvice, Institute of Food and Agricultural Sciences, University of Fl orida, Gainesville, FL. Copeland, R., J. Davis and P. Hansard. 1999. Ni trate source impacts on private drinking well waters in northwest Lafayette County, Florid a. Florida Department of Environmental Protection Ambient Newsletter, Tallahassee, FL. Davis, J.C. 1973. Statistics and Data Analysis in geology. John Wiley and Sons, Inc., New York. Davis, H. 1996. Hydrogeologic investigation and simulation of ground-water flow in the Upper Floridan aquifer of north-central Florida and southwestern Georgia and delineation of contributing areas for selected City of Ta llahassee, Florida, water-supply wells. Water Resour. Investigations Rep. 95-4296. U. S. Geological Survey, Reston, VA. Dietrich, P.G. and D. Hebert. 1997. Regional discharge of a Triass ic astestian karst aquifer: mixing and age of spring waters in the T huringian Basin, Germany, Estimated by Isotope Methods. In Gunay, G. and A.I. Johnson (Eds.), Kars t waters and environmental impacts. A.A. Balkema, Rotterdam. Dingman, S.L. 2002. Physical Hydrology (2nd ed.). Prentice-Hall, Upper Saddle River, NJ: Fernald, E.A. and E. D. Purdum (eds.). 1998. Wate r Resources Atlas of Fl orida. Institute of Science and Public Affairs, Florida State Univ.. Tallahassee, FL. Fetter, C.W. 1988. Applied Hydrogeology. Pr entice Hall: Upper Saddle River, NJ. Flipse, W.J. Jr., and F.T. Bonner 1985. Nitrogen-isotope ratios of nitrate in grou nd water under fertilized fields, Long Island, New York. Ground Water 23:59-67. Florida Department of Environmental Prot ection (FDEP). 1979. Agri culture nonpoint source element: state water quality management plan. Tallahassee, FL. Florida Department of Environmental Pr otection (FDEP). 1998. Florida water quality assessment-305(b) report. Tallahassee, FL. Florida Department of Environmental Protecti on (FDEP). 2000. Florida’s sp rings: strategies for protection and restorat ion. Tallahassee, FL. Florida Department of Environmental Protec tion (FDEP). 2001. Basin status report: Suwannee. Tallahassee, FL.

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256 Hirten, J.J., 1996. Geochemical and hydraulic dyn amics of the Suwannee River and the upper Floridan aquifer system near Branford, Florid a. Masters Thesis, University of Florida, Gainesville, FL. Hochmuth, G.J. and E.A. Hanlon. 2000. IFAS sta ndardized fertilization recommendations for vegetable crops. Circular 1152. Florida Cooperative Extension Service, Institute of Food and Agricultural Sciences, University of Florida, Gainesville, FL Hornsby, D. and R. Ceryak. 1998, Springs of th e Suwannee River Basin in Florida, Water Resour. Rep. WR99-02. Suwannee River Water Management District, Live Oak, FL. Hornsby, D. and R. Ceryak. 1999. Groundwater quality report 1998. Water Resour. Rep. WR9903. Suwannee River Water Manageme nt District, Live Oak, FL. Hornsby, D. and R. Mattson. 1998. Surfacewater qua lity and biological monitoring annual report 1997. Water Resour. Rep. WR98-03 Suwannee River Water Mana gement District, Live Oak, FL. Hornsby, D. and M. Raulston. 2000. Suwannee Ri ver Basin 1998 surface water quality report: Florida and Georgia. Water Resour. Rep. WR00-06. Suwannee River Water Management District, Live Oak, FL. Hornsby, D., R. Mattson, and T. Mirti. 2000. Surfacewater quality and biology: 1999 annual report. Water Resour. Rep. WR00-04. Suwannee River Water Management District, Live Oak, FL. Hornsby, D., R. Mattson, and T. Mirti. 2004. Surfacewater quality and biology: 2003 annual report. Water Resour. Rep. WR03/04-03. Suwann ee River Water Management District, Live Oak, FL. Hornsby, D., R. Mattson and T. Mirti. 2005A. Surfacewater quality and biological monitoring annual report 2004. Water Resour. Rep. WR04/ 05-02. Suwannee River Water Management District, Live Oak, FL Hornsby, D., R. Ceryak and W. Zwanka. 2005B. Groundwater quality report 2004. Water Resour. Rep. WR04/05-03Suwannee River Wate r Management District, Live Oak, FL. Hornsby, D., P. Batchelder, T. Mirti, R. Ceryak and W. Zwanka. 2005C. WARN water monitoring atlas Fiscal Year 2005. Water Re sour. Rep. WR04/05-01. Suwannee River Water Management District, Live Oak, FL. Houston, T.B., M.W. Hazen, Jr., T.C. Mathews and G.A. Brown. 1965. Soil survey of Suwannee County, Florida. United States Department of Agriculture Soil Conservation Service Series 1961, Number 21.

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257 Hull, R.W., J.E. Dysart and W. B. Mann. 1981. Qu ality of surface water in the Suwannee River Basin, Florida, 1968 through December 1977: Wa ter Resour. Investigations Rep. 80-110. U.S. Geol. Survey, Reston, VA. Jones, G.W. and S.B. Upchurch, 1993. Origin of nutrients in ground water discharging from Lithia and Buckhorn Springs. Southwest Florid a Water Management District, Brooksville, FL. Jones, G.W., S.B. Upchurch and K. M. Ch ampion, 1996. Origin of nitrate in ground water discharging from Rainbow Springs, Marion Co unty, Florida. Southwest Florida Water Management District, Brooksville, FL. Katz, B.G. and R.S. DeHan. 1996. The Suwannee Ri ver Basin pilot study: issues for watershed management in Florida. Fact Sheet FS -080-96. U.S. Geol. Survey, Reston, VA. Katz, B.G., H.D. Hornsby, J.F. Bohlke and M.F. Mokray. 1999. Sour ces and chronology of nitrate contamination in spring waters, Suwa nnee River Basin, Florida. Water Resour. Investigations Rep. 99-4252. U.S. Geol. Survey, Reston, VA. Katz, B.G., J.F. Bohlke, and H.D. Hornsby, 2001. Timescales for nitrate contamination of spring waters, Northen Florida, USA. Chemical Geology, 179:167-186. Kreitler, C.W. 1975. Determining the source of nitrate in ground water by nitrogen isotope studies. Report of investigation Number 83. Bureau of Economic Geology, The Univ. of Texas at Austin. Kreitler, C.W. and L.A. Browning. 1983. Nitrogen -isotope analysis of groundwater nitrate in carbonate aquifers: Natural Sources Versus Human Pollution. J. Hydrology 61:285-301. Kwansirikul, K., F.S. Sinharajwarapan, I. K ita and I. Takashima. 2005. Hydrochemical and isotopic characteristics of groundwater in the Lampang Basin. Northern Thailand. ScienceAsia 31:77-86. Lawrence, F.W. and S.B. Upchurch, 1978. Identifi cation of geochemical patterns in groundwater by numerical analysis. Informa tion Circular Number 6. Suwa nnee River Water Management District, Live Oak, FL. Lawrence, F.W. and S.B. Upchurch, 1982. Identifi cation of recharge areas using geochemical factor Analysis. Ground Water 20:680-687. Maddox, G.L., J.M. Lloyd, T.M. Scott, S.B. Upchurch, and R. Copeland (editors). 1992. Florida’s ground water quality monitoring pr ogram background hydrogeochemistry. Special Pub. Num. 34. Florida Geol .Survey, Tallahassee, FL.

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258 Madison, R.J., and Brunett, J.O., 1985. Overview of the occurrence of nitrate in ground water of the United States, in National Water Summar y 1984; Hydrologic events, selected waterquality trends, and ground-wa ter resources. Water-Supply Paper 2275. U.S. Geol. Survey, Reston, VA.. Mahon, G.L., A.F. Choquette and A.A. Sepulve da. 1997. Potentiometric surface of the upper Floridan aquifer in the Suwannee River Water Management District, Fl orida, May and June 1995. Open File Rep. 96-617. U.S. Geol. Survey, Reston, VA. Manassaram, D.M., L.C. Baker and D.M. Moll. 2006. A review of nitrates in drinking water: maternal exposure and adverse reproductive and developmental outcomes. Environmental Health Perspec tives 114:320-327. Marella, R.L. 2004. Water Withdrawals, Use, Discha rge, and trends in Fl orida, 2000. Scientific Investigations Rep. 2004-5151. U.S. Geol. Survey, Reston, VA. Meadows, P.E. 1991. Potentiometric surface of th e upper Floridan aquifer in the Suwannee River Water Management District, Florida, May 1990. Open File Rep. 90-582. U.S. Geol. Survey, Reston, VA. Miller, J.A. 1982. Geology and configuration of the top of the tertiary limestone aquifer system, southeastern United States. Open-File Re port 81-1178. U.S. Geol. Survey, Reston, VA. Miller, J.A., 1997. Hydrogeology of Florida. p. 69-88 In A.F. Randazzo and D.S. Jones (eds.), The Geology of Florida. Univ. of Florida Press, Gainesville, FL. Minnesota Pollution Control Agency and Minnesota Department of Agriculture (MPCAMDA). 1991. Nitrogen in Minnesota Ground Water. Prepared for the Legislative Water Commission. Morgan, C.O. and M.D. Winner Jr. 1962. Hydrochemical faci es in the 400 foot and 600 foot sands of Baton Rouge Area Louisian a. Professional Paper 450-B. U.S. Geol. Survey. Mueller, D.K., P.A. Hamilton, D.R. Helsel, K. J. Hitt, and B.C. Ruddy. 1995, Nutrient in ground water and surface water of the United States – an analysis of data through 1992. Water Resour. Investigation Report 95-403 1. U.S. Geol. Survey, Reston, VA. Mylavarapu, R., D. Wright, G. Kidder and C.G. Chamblis. 2007. UF/IFAS standardized fertilization recommendations for agronomic crops. Fact Sheet SL-129. Soil and Water Science Department, Florida Cooperative Ex tension Service, Institute of Food and Agricultural Sciences, University of Florida, Gainesville, FL. Mytyk, N.R. and J.J. Delfino, 2004. Evaluation of nitrate data in the Ocklawaha River Basin, Florida (19532002). Journal of the American Water Reso urces Assocaiton. Volume 40:913924.

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259 Nair, V.D., K.M. Portier, D.A. Graetz, and M. L. Walker. 2004. An envi ronmental threshold for degree of phosphorus saturation in sandy soils. Journal of Environmental Quality, Volume 33:107-113. Obreza, T. and G. Means. 2006. Characterizing agriculture in Florida’s lower Suwannee River Basin Area. Soil and Water Science Department Florida Cooperative Extension Service, Institute of Food and Agricultural Sciences, Un iversity of Florida, Fact Sheet SL 241. Ott, R.L. and M. Longnecker. 2001. An Introducti on to Statistical Methods and Data Analysis. Thomson Learning. 5th ed. Duxbury: Pittman, J.R., H.H. Hatzell and E.T. Oaksford. 1997. Spring contributions to water quantity and nitrate loads in the Suwannee River during base flow in July 1995. Water Resour. Investigations Rep. 97-4152. U.S. Geol. Survey, Reston, VA. Planert, M. 2007. Simulation of regional ground -water flow in the Suwannee River Basin, Northern Florida and Southern Georgia. Scie ntific Investigations Rep. 2007-5031. U.S. Geol. Survey, Reston, VA. Puri, H.S. and R.O. Vernon, 1964. Summary of the geology of Florida and guidebook to the classic exposures. Special Pub. No. 5. Florida Geol. Survey, Tallahassee, FL. Quinlan, E.B., 2003. Consequences of nutrient loading in the Suwannee River and Estuary, Florida, USA. Dissertation Univ. of Florida, Gainesville, FL. United States Department of Agriculture (US DA), 1991. Nitrate occurrence in U.S. Water: a reference summary of published sources from an agricultural perspectiv e. Washington, D.C. United States Department of Agriculture Soil Conservation Services (USDA), 1993. South East Middle Suwannee River AreaWatershed Protec tion Plan and Environmental Assessment. Gainesville, Florida. United States Environmental Protection Agency (EPA), 1983. Methods for chemical analysis of water and wastes. Environ. Monitori ng and Support Lab., Cincinnati, OH. United States Environmental Protection Agency (EPA). 1991. Nitrogen work group. Nitrogen action plan (draft). NTIS #40 0/3-90/003. U.S. Environ. Protection Agen cy. Washington, D.C. United States Environmental Protection Agency (EPA). 1994. National water quality inventory 1992 Report to Congress. Fact Sheet EPA841F-94-002. U.S. Environ. Protection Agency. Washington, D.C. United States Geological Survey (USGS), 1997. Modeling ground-water flow with MODFLOW and related programs. Fact Sheet 121-97. Reston, VA.

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260 University of Florida, Warrington College of Business Administration, Bureau of Economic and Business Research (BEBR), 2001. Historical census counts for Florida and its Counties 1830 through 2000. Gainesville, Florida. University of Florida, Warrington College of Business Administration, Bureau of Economic and Business Research (BEBR), 2004. Estimates of population by County and Municipality in Florida: April 1, 2004. Gain esville, Florida. Upchurch, S.B. and B.W. Goodwin. 2000. Ground water monitoring Plan for the Suwannee River Water Management District. Environm ental Resources Management, Tampa, FL. Upchurch, S.B., D. Hornsby, R. Ceryak and W. Zwanka, 2001. A strategy for characterization of first magnitude Springs. Water Resour. Re p. WR02-01. Suwannee River Water Management District, Live Oak, FL. Upchurch, S.B., K. Champion, J. Schneider, D. Hornsby, R. Ceryak, and W. Zwanka, 2006. Identifying water-quality domains near Iche tucknee Springs, Columbia County, Florida. National Ground Water Association 4th Conference on Hydrogeology, Ecology, Monitoring, and Management of Gr ound Water in Karst Terrains. Rosenau, J.C. and P.E. Meadows. 1986. Potentiometr ic surface of the Floridan aquifer system in the Suwannee River Water Management Di strict, Florida, May 1985. Water Resour. Investigation 86-4184. U.S. Geol. Survey, Reston, VA. Seaber, P.R. 1962. Cation hydrochemical facies of groundwater in the Englishtown Formation, New Jersey. Professional Paper 627-C. U.S. Geological Survey, Reston, VA. Sabesan, A. 2004. Geo-spatial assessment of the im pact of land cover dynamics and distributions of land resources on soil and water quality in the Santa Fe River Wate rshed. Master’s Thesis, University of Florida, Gainesville, FL. Scott, T.M., G.H. Means, R.C. Means and R. P. Meegan. 2002. First Magnitude Springs of Florida. Open File Rep. No. 85. Flor ida Geol. Survey, Tallahassee, FL. Scott, T.M., G.H. Means, S.B. Upchurch, R.E. Copeland, J. Jones, T. Roberts and A. Willet. 2004. Springs of Florida. Bulletin No. 66. Florida Geol. Survey, Tallahassee, FL. Shoemaker, W.B., A.M. O’Reilly, N. Seplveda S.A. Williams, L.H. Motz, and Q. Sun, 2004. Comparison of estimated areas contributing rech arge to selected springs in North-Central Florida by using multiple ground-water flow models. Open-File Report 03-448. U.S. Geol. Survey, Reston, VA. Soil Survey Staff. 1997. Major Land Resource Areas in Florida [Online WWW]. Available URL: http://www.mo15.nrcs.usda.gov/technical/mlra_ fl.html [Accessed 14 September 2007]. Natural Resources Conservation Serv ice, U.S. Dept. of Agriculture.

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261 Soil Survey Staff. 2007. Soil Classifica tion [Online WWW]. Available URL: http://soils.usda.gov/technical/classifica tion/" [Accessed 14 September 2007]. Natural Resour. Conservation Service, U.S. Dept. of Agriculture. Spalding, R.F. and Exner, M.E., 1993, Occurrence of nitrate in groundwater – A Review. J of Environ. Qual. 22:392-402. Suwannee River Water Management District (S RWMD). 1997. Map of land use/ cover in the Suwannee River Water Management District, 1995. Live Oak, FL. Suwannee River Water Management District (S RWMD). 2002. Map of potentiometric surface of the Floridan aquifer in the Suwannee River Wa ter Management District, 2002. Live Oak, FL. Suwannee River Water Management District (S RWMD). 2005. District Potentiometric Map. Live Oak, FL. Water Resource Associates (WRA) and SDII Gl obal Corporation (SDII). 2005. Strategies and recommendations for protecting Silver a nd Rainbow Springs. Marion County, Florida Springs Protection Program, Ocala, FL. White, W.A., 1970. The geomorphology of the Florid a peninsula. Geological Bulletin No. 71. Florida Bureau of Geol., Tallahassee, FL. Winter, T.C., J.W. Harvey, O.L. Franke and W.M. Alley. 1998. Ground water and surface water: a single resource. Circular 1139. U. S. Geol. Survey, Reston, VA. Zagier, A.S. 2003. Deep trouble: soiling the Gu lf. Naples Daily News September 28, 2003.

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262 BIOGRAPHICAL SKETCH H. David Hornsby was born on October 4, 1966, in Baton Rouge, Louisiana. David received a bachelor’s in chemistry from the University of Flor ida in 1991. He earned a Master of Science in soil and water science with a minor in environmental engineer ing sciences from the University of Florida in 1994. He worked for the Suwannee River Water Management District from 1994 to 2005 as a water qualit y analyst and a water resources scientist, for the Florida Department of Environmental Protection from 2005 to 2007 as an environmental administrator and the St. Johns River Water Management Di strict starting 2007as a water supply planning project manager.