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Spatial and Temporal Differences in Nutrient Concentrations at the Devil's Eye Spring and Devil's Cave System, Florida

Permanent Link: http://ufdc.ufl.edu/UFE0045121/00001

Material Information

Title: Spatial and Temporal Differences in Nutrient Concentrations at the Devil's Eye Spring and Devil's Cave System, Florida
Physical Description: 1 online resource (49 p.)
Language: english
Creator: Sandrey, Stacey
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2012

Subjects

Subjects / Keywords: cave -- nutrients -- springs
Forest Resources and Conservation -- Dissertations, Academic -- UF
Genre: Fisheries and Aquatic Sciences thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Springs and caves are a naturally occurring geologicalfeature in Florida and play vital roles economically, recreationally, andbiologically in the state. There is scientific research that suggests anincrease in macroalgae and invasive aquatic macrophyte (e.g., Hydrillaverticillata) growth, and degrading water quality in the springs and downstreamreceiving waters because of increased loads of nutrients (phosphorus, nitrogen,and nitrate) into the groundwater system. However, no studies have been conductedusing cave divers to determine if there are spatial and temporal differences innutrients in the cave systems of the springs. The primary goal of my researchwas to determine if nutrients (total phosphorus, total nitrogen, andnitrate-nitrogen) differed in the cave and how nutrient concentrations relateto emerging and surface waters. Water samples were collected by a team of twocertified cave divers on a monthly basis from February 2006 through June 2009and analyzed for total phosphorus, total nitrogen, and nitrate-nitrogen. Devil’s Eye Spring would be considered eutrophic with totalphosphorus concentrations averaging 34 µg/L at the surface and 36 µg/L at thevent and total nitrogen concentration averaging 1400 µg/L at the surface and1600 µg/L at the vent. There was a statistically significant difference in totalphosphorus concentrations among the four sampling locations. It was determinedthat a statistically significant difference in the mean River Intrusion Tunneltotal phosphorus concentration differed from the Insulation Room and the ventlocations. There was no statistically significant difference in the totalnitrogen or nitrate-nitrogen concentrations among the four sampling locations. The Santa Fe River stage level and rainfall data wereanalyzed and there were small, but positive correlations with the river stagelevel and rainfall. The surface total phosphorus, total nitrogen, andnitrate-nitrogen concentrations are all correlated to river level. Total phosphorus concentrations were highly variable andthere was no apparent overall increase or decrease over time. Total nitrogenconcentrations at the surface and vent showed a decline over time while theRiver Intrusion Tunnel and the Insulation Room both had concentrations thatstarted out high and then were fairly constant throughout the remainder of thestudy. Nitrate-nitrogen concentrations at all four sampling locations showed adecline until October 2008, at which time, all four locations increased. In comparing the nutrient concentrations from the Devil’sEye spring and cave system to other springs and caves I sampled, severallocations had similar concentration levels while others had different levels.Most of the springs and caves I sampled had nutrient concentrations that werethe same or similar in the cave compared to the surface and vent.
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 Stacey Sandrey.
Thesis: Thesis (M.S.)--University of Florida, 2012.
Local: Adviser: Canfield, Daniel E.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2012
System ID: UFE0045121:00001

Permanent Link: http://ufdc.ufl.edu/UFE0045121/00001

Material Information

Title: Spatial and Temporal Differences in Nutrient Concentrations at the Devil's Eye Spring and Devil's Cave System, Florida
Physical Description: 1 online resource (49 p.)
Language: english
Creator: Sandrey, Stacey
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2012

Subjects

Subjects / Keywords: cave -- nutrients -- springs
Forest Resources and Conservation -- Dissertations, Academic -- UF
Genre: Fisheries and Aquatic Sciences thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Springs and caves are a naturally occurring geologicalfeature in Florida and play vital roles economically, recreationally, andbiologically in the state. There is scientific research that suggests anincrease in macroalgae and invasive aquatic macrophyte (e.g., Hydrillaverticillata) growth, and degrading water quality in the springs and downstreamreceiving waters because of increased loads of nutrients (phosphorus, nitrogen,and nitrate) into the groundwater system. However, no studies have been conductedusing cave divers to determine if there are spatial and temporal differences innutrients in the cave systems of the springs. The primary goal of my researchwas to determine if nutrients (total phosphorus, total nitrogen, andnitrate-nitrogen) differed in the cave and how nutrient concentrations relateto emerging and surface waters. Water samples were collected by a team of twocertified cave divers on a monthly basis from February 2006 through June 2009and analyzed for total phosphorus, total nitrogen, and nitrate-nitrogen. Devil’s Eye Spring would be considered eutrophic with totalphosphorus concentrations averaging 34 µg/L at the surface and 36 µg/L at thevent and total nitrogen concentration averaging 1400 µg/L at the surface and1600 µg/L at the vent. There was a statistically significant difference in totalphosphorus concentrations among the four sampling locations. It was determinedthat a statistically significant difference in the mean River Intrusion Tunneltotal phosphorus concentration differed from the Insulation Room and the ventlocations. There was no statistically significant difference in the totalnitrogen or nitrate-nitrogen concentrations among the four sampling locations. The Santa Fe River stage level and rainfall data wereanalyzed and there were small, but positive correlations with the river stagelevel and rainfall. The surface total phosphorus, total nitrogen, andnitrate-nitrogen concentrations are all correlated to river level. Total phosphorus concentrations were highly variable andthere was no apparent overall increase or decrease over time. Total nitrogenconcentrations at the surface and vent showed a decline over time while theRiver Intrusion Tunnel and the Insulation Room both had concentrations thatstarted out high and then were fairly constant throughout the remainder of thestudy. Nitrate-nitrogen concentrations at all four sampling locations showed adecline until October 2008, at which time, all four locations increased. In comparing the nutrient concentrations from the Devil’sEye spring and cave system to other springs and caves I sampled, severallocations had similar concentration levels while others had different levels.Most of the springs and caves I sampled had nutrient concentrations that werethe same or similar in the cave compared to the surface and vent.
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 Stacey Sandrey.
Thesis: Thesis (M.S.)--University of Florida, 2012.
Local: Adviser: Canfield, Daniel E.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2012
System ID: UFE0045121:00001


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1 SPATIAL AND TEMPORAL DIFFERENCES IN NUTRIENT CONCENTRATIONS AT By STACEY A. SANDREY A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2012

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2 2012 Stacey A. Sandrey

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3 ACKNOWLEDGMENTS I thank Dr. Daniel E. Canfield, Jr., for giving me this opportunity and for serving as my advisor and committee chair. I also thank Dr. Charles Cichra and Dr. Thomas Frazer for serving on my graduate committee. I especially thank my cave diving buddies and friends Mr. Kenneth Dr. William Huth, and mentor, Mr. Monte Hancock. Thank you all for your patience and encouragement. Lastly, I thank Dr. Joanne Nesbitt for her constant encouragement and for never allowing me to give up and my parents for their support.

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4 TABLE OF CONTEN TS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 3 LIST OF TABLES ................................ ................................ ................................ ............ 5 LIST OF FIGURES ................................ ................................ ................................ .......... 6 ABSTRACT ................................ ................................ ................................ ..................... 7 CHAPTER 1 INTRODUCTION ................................ ................................ ................................ ...... 9 2 METHODS ................................ ................................ ................................ .............. 16 3 RESULTS ................................ ................................ ................................ ............... 19 Spatial Variation in Nutrients ................................ ................................ ................... 19 Temporal Variation in Nutrients ................................ ................................ .............. 23 Percent Deviations for Nutrients ................................ ................................ ............. 27 4 DISCUSSION ................................ ................................ ................................ ......... 31 5 CONCLUSION ................................ ................................ ................................ ........ 39 APPENDIX WATER DATA ................................ ................................ ........................ 41 LIST OF REFERENCES ................................ ................................ ............................... 46 BIOGRAPHICAL SKETCH ................................ ................................ ............................ 49

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5 LIST OF TABLES Table page 3 1 Mean concentrations and range of total phosphorus, total nitrogen, and nitrate Gilchrist County, Florida, for 2006 2009. ................................ .......................... 19 3 2 Pearson Correlation Coefficients for total phosphorus, total nitrogen, and nitrate with rainfall and Santa Fe River levels for 2006 through 2009. .......................... 22 4 1 Arithmetic mean for total phosphorus, total nitrogen, and nitrate nitrogen from 1990 to 2003. Total nitrogen data are from 1997 to 2003. ................................ .. 31 4 2 Total phosphorus, total nitrogen, and nitrate nitrogen concentrations from were sampled on a one time basis. ................................ ................................ .... 34 4 3 General chemistry data for springs located by Florida county. ........................... 35 A 1 Water data collected between February 2006 through June 2009 from four spring/cave, Florida. ................................ ...... 41

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6 LIST OF FIGURES Figure page 1 1 ................................ ...................... 12 1 2 ample locations ................................ 12 1 3 Physiographic provinces of north Florida. ................................ .......................... 13 3 1 Total monthly rainfall and mean monthly Santa Fe River Florida, stage level. 21 3 2 Total phosphorus concentrations (g/L) from all four sampling locations between February 2006 a Cave System, Florida.. ................................ ................................ ....................... 24 3 3 Total nitrogen concentrations (g/L) from all four sampling locations between February 2006 and June 2009, at System, Florida. ................................ ................................ ................................ .. 25 3 4 Nitrate nitrogen concentrations (g/L) from all four sampling locations Cave System, Florida.. ................................ ................................ ....................... 26 3 5 Percent deviation from the overall median for TP concentration (g/L) at the River Intrusion Tunnel, Insulation Room, surface, and vent at the ................................ ......................... 28 3 6 Percent deviation from the overall median for TN concentration (g/L) at the River Intrusion Tunnel, Insulation Room, surface, and ................................ ......................... 29 3 7 Percent deviation from the overall median for NO 3 N concentration (g/L) at the River Intrusion Tunnel, Insulation Roo ................................ .................. 30

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7 Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requireme nts for the Degree of Master of Science SPATIAL AND TEMPORAL DIFFERENCES IN NUTRIENT CONCENTRATIONS AT By Stacey A. Sandrey December 2012 Chair: Daniel E. Canfield, Jr. Major: Fisheries & Aquatic Sciences Springs and caves are a naturally occurring geological feature in Florida and play vital roles economically, recreationally, and biologically in the state. There is scientific research that suggests an increase in macroalgae and invasive aquatic macrophyte (e.g., Hydrilla verticillata) growth, and degrading water quality in the springs and downstream receiving waters because of increased loads of nutrients (phosphorus, nitrogen, and nitrate) into the groundwater system. However, no studies have be en conducted using cave divers to determine if there are spatial and temporal differences in nutrients in the cave systems of the springs. The primary goal of my research was to determine if nutrients (total phosphorus, total nitrogen, and nitrate nitrogen ) differed in the cave and how nutrient concentrations relate to emerging and surface waters. Water samples were collected by a team of two certified cave divers on a monthly basis from February 2006 through June 2009 and analyzed for total phosphorus, tot al nitrogen, and nitrate nitrogen. concentrations averaging 34 g/L at the surface and 36 g/L at the vent and total nitrogen concentration averaging 1400 g/L at the surface and 1600 g/L at the vent.

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8 There was a statistically significant difference in total phosphorus concentrations among the four sampling locations It was determined that a statistically significant difference in the mean River Intrusion Tunnel total phosphorus concen tration differed from the Insulation Room and the vent locations. T here was no statistically significant difference in the total nitrogen or nitrate nitrogen concentrations among the four sampling locations. The Santa Fe River stage level and rainfall dat a were analyzed and there were small, but positive correlations with the river stage level and rainfall. The surface total phosphorus, total nitrogen, and nitrate nitrogen concentrations are all corre lated to river level. Total phosphorus concentrations we re highly variable and there was no apparent overall increase or decrease over time Total nitrogen concentrations at the surface and vent showed a decline over time while the River Intrusion Tunnel and the Insulation Room both had concentrations that star ted out high and then were fairly constant throughout the remainder of the study. Nitrate nitrogen concentrations at all four sampling locations showed a decline until October 2008, at which time, all four locations increased. In comparing the nutrient co system to other springs and caves I sampled, several locations had similar concentration levels while others had different levels. Most of the springs and caves I sampled had nutrient concentrations that we re the same or similar in the cave compared to the surface and vent.

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9 CHAPTER 1 INTRODUCTION Springs and caves are naturally occurring geological features in Florida, with more than 700 springs found in the state (F lorida G eological Society Bulletin 66, 20 04). The Florida Springs Task Force (2000) found that springs play a vital role economically, recreationally, and biologically in the state and support unique biota. Springs are not with the springs are caves, which provide habitat for specialized animals that live in the water filled caves such as blind albino cave crayfish, Pr ocambarus spp ., and the Georgia blind salamander, Haideotriton wallacei while the spring runs provide habitat for other species (Walsh, 2001). By the 1990s, there was scientific research that suggested an increase in macroalgae and invasive aquatic macrop hyte ( Hydrilla verticillata) growth in the springs and downstream receiving waters because of increased loads of nutrients (phosphorus and nitrogen) in the spring systems (Florida Springs Task Force, 2000; Notestein et al., 2003; Frazer et al., 2006). Un der the Clean Water Act (33 U.S.C. 1313(c)), states are required to adopt Water Quality Standards (WQS) for all water bodies of the United States. The Florida nutr ient concentrations of a body of water be altered so as to cause an imbalance in 302.530(47)(a) and (b), 62 302.700).

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10 In 1999, the Florida Department of Environmental Protection (FDEP) formed the protect and restore the springs. In 2001, former Governor Jeb Bush and the Florida Legislature created the Florida Springs Initiative, which was funded through the FDE P (F lorida Geological Society Bulletin 66, 2004). Since 2001, the Florida Springs Initiative has provided approximately $24.5 million per year to research, monitoring projects, and education (Florida Department of Environmental Protection, 2010). Current s ampling locations are established in springs at state parks and all first magnitude springs and monitored for water quality on a quarterly basis (Florida Springs Initiative Program Summary and Recommendations, 2007). When sampling the springs, samples are obtained at the spring vent. However, there was a time when samples were taken at the surface. In 2009, the United States Environmental Protection Agency ( U.S. EPA) determined that Florida needed to have numeric nutrient criteria established to meet the Cl ean Water Act requirements (U.S. Environmental Protection Agency Water Quality accumulating evidence and to protect the Florida springs and spring runs, the U. S. EPA finali pollution. They did not establish criteria for phosphorus pollution in springs. Under the new rule, the U. S. EPA has established nitrate nitrite criteria for Florida sp rings of 0.35 mg/L as an annual geometric mean, not to be exceeded more than once in a three year period (U.S. Environmental Protection Agency Water Quality Standards for the State of

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11 While the focus has been on s ampling waters emerging from the springs, no studies have been conducted to determine if there are spatial and temporal differences in nutrients in the cave systems of the springs. The purpose of my research was to determine if nutrients (total phosphorus, total nitrogen, and nitrate nitrogen) differed within a well system were chosen for several reasons: 1) the River Intrusion Tunnel and the Insulation Room are located on different sides of the main conduit with the River Intrusion Tunnel being closer to the Santa Fe River; 2) during heavy rainfall and/or elevated river stage level, river intrusion seems to occur in the River Intrusion Tunnel based on cave diver observations; and 3) the Insulation Room has a biofilm on the floor that cave divers explain as looking like pink insulation and that could be due to increased nutrient concentrations. Study s ite : County in the western Santa Fe River basin of north central Florida along the Santa Fe River, a major tributary to the Suwanee River (Figure 1 1). The spring is located at F lorida G eological Society Bulletin 66 2004 ). The spring emerges from the ground, which then discharges into the Santa Fe River ( F lorida G eological Society Bulletin 66, 2004 ). The surface area of the spring is approximately 18.3 m by 9.1 m ( F lorida G eological Society Bulletin 66, 2004 ) and i t is 6 m deep. At the bottom of the spring is an entrance to an extensive cave system, which has been mapped by cave divers (Figure 1 2). The land immediately surrounding the spring is privately owned by Ginnie Springs Outdoors LLC, and is a

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12 private park. The park is well known for swimming, tubing, kayaking, canoeing, scuba diving, and cave diving (Ginnie Springs Outdoors LLC). Figure 1 1 Figure 1 splaying sample locations ( Adapted from Hancock J. 2008).

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13 The Santa Fe River originates from Little Santa Fe Lake in the Northern Highlands (Figure 1 3) physiographic province (Scott, 1991). As the river flows westward, it crosses the Cody Scarp, which i s the boundary between the Northern Highlands and the Gulf Coastal Lowlands and is also the transitioning area where the Floridan aquifer becomes unconfined (Scott, 1991). As the Santa Fe River reaches the Cody Scarp, it disappears into a sinkhole known as Depending on the discharge of the river, 4 to 73% of the water entering the sink re emerges approximately 5 km downstream at the River Rise (Hisert, 1994; Martin and Dean, 2001; Martin and Screaton, 2001). There are n umerous springs downstream from flows in and underground instead of remaining in the channel of the Santa Fe River as it flows through the High Springs Gap and makes it way to the Suwannee River and the Gulf Coastal Lowlands (Poucher and Copeland, 2006; White, 1970). Figure 1 3 Physiographic provinces of north Florida ( White, W.A. 1970 The Geomorphology of the Florida Peninsula Bulletin No 51, Florida Geological Survey, Tallahassee, FL. ).

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14 Florida has three major aquifer systems: the Floridan, the Intermediate, and the Superficial Aquifer systems (Scott, 1992). Most of the springs in Florida are discharged from the Floridan aquifer (Scott, 1992), the principal source of water supply for many cities and towns in Florida (Miller, 1997). The Floridan aquifer system is composed of carbonate rock (limestone and dolostone) of Tertiary age (Miller, 1997). Entisols, Histosols, Spodosols, and Ultisols (United States Department of Agriculture, 2010). Some of the more prevalent soil series found are Bigbee, fine sand that is deep, excessively drained, and rapidly permeable; Olena, clay over sand and clay loam that is poorly drained, slowly permeable soils; Penney, fine sand that is very deep, excessively drained, and rapidly permeable soils; Resota, fine sand that is very deep, moderately well drained, and very rapidly permea ble soils; Lakeland, fine sand that is very deep, excessively drained, and rapid to very rapidly permeable soils; and fluvaquents (United States Department of Agriculture, 2010). Spring water can indicate the quality of groundwater. The geology and soils of the area determine the amount of water and chemical components in groundwater discharging from springs ( F lorida G eological Society Bulletin 66, 2004 ). As acidic rainfall penetrates the sandy soils, the rainwater recharges the aquifer and dissolves the l imestone ( F lorida G eological Society Bulletin 66, 2004 ). Because of the sandy soils, the potential for nutrients leaching to the groundwater exists (Obreza and Means, 2006). High S prings Gap in the upper Floridan aquifer beneath the Santa Fe River and has been explored and mapped to over 914 meters (Figure 1 2) with exploration continuing

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15 today with over 7,000 meters surveyed (Kincaid, 1998). The cave system is characterized by a ne twork of conduits in the Ocala Limestone (Kincaid, 1998). The main conduit has numerous side tunnels that vary in size from 2 to 20 meters (Kincaid, 1998). The depth of the cave system is relatively constant at 30 meters, but recent exploration has found that areas can reach as deep as 45 meters. As the water flows out to the spring, the depth of the cave decreases in the last 90 meters from 30 meters deep to 6 meters deep before discharging to the Santa Fe River.

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16 CHAPTER 2 METHODS Underground water samp ling was focused on two sites, the River Intrusion Tunnel and the Insulation Room (Figure 1 2). Water samples were collected monthly by a team of two certified cave divers from February 2006 through June 2009 and analyzed for total phosphorus, total nitrog en, and nitrate nitrogen. The River Intrusion Tunnel is approximately 580 meters from the vent at a depth of 29 meters and was named by cave divers that noticed Santa Fe River water entering the cave system through this conduit during high water levels (St eve Forman, cave diving instructor and explorer, personal communication). The Insulation Room is approximately 670 meters from the vent at a depth of 26 meters and is named because of a biofilm found on the floor of the room that cave divers have described as looking like pink insulation (Steve Forman, cave diving instructor and explorer, personal communication). In addition to systems throughout Florida on a one time basis f ollowing the same procedures as above. Water samples were collected, using 125 mL and 250 mL acid washed, triple rinsed, opaque Nalgene bottles, from 0.5 m below the surface of the spring and at the vent approximately 5 meters deep. The first location sam pled within the cave was the Insulation Room and the second location was the River Intrusion Tunnel. This ordering of sampling was necessary to insure that the divers did not collect water samples with silt suspended from the bottom of the cave and also fo r safety reasons. To obtain water samples at depth, three 125 mL and three 250 mL bottles were rinsed at the surface of the spring and filled with surface water. At each underwater sampling location, one 125

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17 mL and one 250 mL bottle was inverted, flushed using 30 33% Nitrox from scuba cylinders, and refilled with cave water. This step was repeated twice at each sampling location. Water samples were taken to the surface and covered with ice, and then frozen until transported to the Florida LAKEWATCH water c hemistry laboratory at the University of Florida (Gainesville, Florida) for analyses. Total phosphorus concentrations (g/L) were determined using the procedures of Murphy and Riley (1962), with a persulfate digestion (Menzel and Corwin, 1965). Total nitro gen concentrations (g/L) were determined by oxidizing water samples with persulfate and determining resulting nitrate nitrogen concentration with second derivative spectroscopy Nitrate nitrogen concentrations (g/L as N) were determined using an automated cadmium reduction method (4500 NO3 F; APHA, 1992). Samples were not filtered. River stage level and rainfall data were obtained from the Suwannee River Water Management Distri ct (SRWMD). The SRWMD measured the Santa Fe River stage level at Highway 441 near High Springs, which is approximately 5 km upstream from the study site. Rainfall data were collected approximately 9 km northwest from the study site at Three Rivers Estates at Point Park. Total phosphorus concentrations for the Santa Fe River were also obtained from the SRWMD, which sampled on a monthly basis at the US 441 Bridge in Columbia County. Data were plotted by location for each nutrient concentration. The median per cent of deviation was calculated for each nutrient at each of the four sampling locations. Standard statistical analyses were performed using JMP 7.0 (SAS Institute

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18 1989) and Excel 2003 SP3 (Microsoft ). Data were not logarithmically transformed (base 10 ) as the data were normally distributed as verified using the Shapiro Wilk test. A one way ANOVA was used to determine if there were differences in nutrient concentrations among the four sampling locations. When a significant effect of location was found, location differences were analyzed using a Tukey HSD test. Statements of statistical significance imply alpha = < 0.05 unless otherwise stated.

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19 CHAPTER 3 RESULTS Spatial Variation in Nutrients Total phosphorus in the cave averaged 33 g/L. Total nitroge n averaged 1,450 g/L. Nitrate nitrogen was approximately 93% of total nitrogen (Table 3 1). Total phosphorus ranged between 12 and 46 g/L in the cave. Total nitrogen ranged between 100 and 2,000 g/L and nitrate nitrogen between 600 and 1,800 g/L (Table 3 1). Total phosphorus at the surface and vent averaged 35 g/L. Total nitrogen averaged 1,450 g/L. Nitrate nitrogen averaged approximately 93% of total nitrogen (Table 3 1). Total phosphorus ranged between 26 and 44 g/L at the surface and the vent. Tot al nitrogen ranged between 1,000 and 1,800 g/L and nitrate nitrogen between 400 and 1,800 g/L (Table 3 1). Table 3 1. Mean concentrations and range (inside parentheses) of total phosphorus, total nitrogen, and nitrate nitrogen for four sampling locations Cave system, Gilchrist County, Florida, for 2006 2009. Sampling Location Total Phosphorus g/L N Total Nitrogen g/L N Nitrate Nitrogen g/L N River Intrusion Tunnel 32 (24 40) 37 1,500 (900 1,700) 37 1,400 (800 1,800) 37 Insulat ion Room 34 (12 46) 36 1,400 (100 2,000) 36 1,300 (600 1,800) 36 Surface 34 (26 44) 36 1,400 (1,000 1,800) 36 1,400 (400 1,800) 36 Vent 36 (28 43) 37 1,500 (1,000 1,700) 37 1,300 (500 1,800) 36

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20 A single factor one way analysis of variances (ANOVA) was used to determine if the mean total phosphorus concentrations at the four sampling locations differed from the total phosphorus concentration means at these four sampling locations were not to conclude the mean concentrations of total nitrogen and nitrate nitrogen were equal among the four sampling locations (p = 0.279 and p = 0.753, respectively). Subsequent to the conclusion that the total phosphorus concentrations were not equal at the four sampling locations, a Tukey HSD test was used and determined that the River Intrusion Tunnel total phosphorus concentration mean signific antly differed from the Insulation The Santa Fe River stage level and rainfall data from the SRWMD (Figure 3 1) were analyzed to determine if either the river level or rain fall could be related to the total phosphorus concentration at the River Intrusion Tunnel location. Pearson Correlation Coefficients were computed for the nutrient concentrations and the environmental factors (river stage and rainfall). There were small, b ut positive correlations with both river stage and rainfall (Table 3 2). No significant correlation was observed between rainfall and the nutrient concentrations at any location (Table 3 2). The surface total phosphorus, total nitrogen, and nitrate nitroge n concentrations are all correlated to river level (Table 3 2).

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21 Figure 3 1 Total monthly rainfall and mean monthly Santa Fe River, Florida, stage level (Data from SRWMD).

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22 Table 3 2. Pearson Correlation Coefficients for total phosphorus, total nitrogen, and nitrate rainfall and Santa Fe River levels for 2006 through 2009. Rain fall P value River Levels P value Total Phosphorus River Intrusion Tunnel 0 .11 0.58 0.08 0.00 Insulation Room 0.02 0.94 0.29 0.00 Surface 0.03 0.90 0.48 0.00 Vent 0.23 0.27 0.30 0.18 Total Nitrogen River Intrusion Tunnel 0.19 0.35 0.01 0.08 Insulation Room 0.05 0.81 0.28 0.00 Surface 0.00 0.98 0.32 0.00 Vent 0. 20 0.33 0.03 0.10 Nitrate Nitrogen River Intrusion Tunnel 0.05 0.81 0.17 0.00 Insulation Room 0.13 0.54 0.26 0.00 Surface 0.02 0.91 0.27 0.00 Vent 0.03 0.90 0.30 0.00

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23 Temporal Variation in Nutrients Total phosphorus concentrations were temporally variable at the four sampling locations. However, there was no apparent overall incre ase or decrease with time (Figure 3 2 ). All four sampling locations had high TP values in August 2008, a time of high rainfall (Figures 3 2 ). Total nitrogen concentrations at the surface and vent exhibited similar patterns over time, showing a general decl ine (Figure 3 3 ). The Insulation Room had concentrations that started out high and were fairly constant throughout the remainder of the study (Figure 3 3 ). All four sampling locations had low total nitrogen values in August 2008 (Figure 3 3 ). All four sam pling locations exhibited a similar pattern in nitrate nitrogen values showing a decline until October 2008 at which time all four locations increased in nitrate nitrogen (Figure 3 4 ). Nitrate nitrogen concentrations at all locations exhibited a high degr ee of temporal variation throughout the study (Figure 3 4 ).

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24 A B C D Figure 3 2 Total phosphorus concentrations (g/L) from all four sam pling locations between February 2006 and Cave System, Florida. A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location three was the surface. D) Sampling location four was the vent.

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25 A B C D Figure 3 3 Total nitrogen concentrations (g/L) from all four sampling locatio ns betwe en February 2006 and Cave System, Florida. A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location three was the surface. D) Sampling location four was the vent.

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26 A B C D Figure 3 4 Nitrate nitrogen concentrations (g/L) from all four sampling locatio ns between February 2006 an d Cave System, Florida. A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location three was the surface. D) Sampling location four was the vent.

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27 Percent Deviations for Nutrients The percent of deviation s from the median was calculated for total phosphorus at the River Intrusion Tunnel, Insulation Room, surface, and vent. The range was 25% to 200% (Figure 3 5 ). Most locations did not exhibi t percent of deviation s in excess of 50% from the overall medians. A high (200%) percent of deviation did occur in August 2007 at the Insulation Room, a time of high rainfall. The percentage of deviation from the median was calculated for total nitrogen a t the River Intrusion Tunnel, Insulation Room, surface, and vent. The range was 30% to 1,300% (Figure 3 6 ). Most locations did not exhibit percent of deviation s in excess of value A high percent of deviation did occ ur in August 2007 in the Insulation Room, a time of high rainfall. Lastly, the percent of deviation from the median concentration was calculated for nitrate nitrogen at the River Intrusion Tunnel, Insulation Room, surface, and vent. The range was 22% to 900%. Most samples did not exhibit a percent of deviation in excess at the River Intrusion Tunnel in September and October 2008, when the river level was high (Figure 3 7 ). There was also a high percent of deviation (900%) at the Insulation Room in June 2007, a time of high rainfall, and in September and October 2008 (133%), at the surface in October 2008 (250%), and at the vent in August and September (100%), and Octo ber 2008 (180%).

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28 A B C D Figure 3 5 Percent deviation from the overall median for TP concentration (g/L) at the River Intrusion Tunnel, A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location three was the surface. D) Sampling loca tion four was the vent.

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29 A B C D Figure 3 6 Percent deviation from the overall median for TN concentration (g/L) at the Riv A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location three was the surfa ce. D) Sampling location four was the vent.

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30 A B C D Figure 3 7 Percent deviation from the overall median for NO 3 N concentration ( g/L) at A) Sampling location one was River Intrusion Tunnel. B) Sampling location two was Insulation Room. C) Sampling location thr ee was the surface. D) Sampling location four was the vent.

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31 CHAPTER 4 DISCUSSION The water chemistry of springs is dependent upon origin, residence time, and the composition of the rocks the water comes in contact with (St. Johns River Water Management District, 2007). Determining the water chemistry that a spring discharges is a way of determining the water chemistry in the aquifer as well as possible anthropogenic impacts on the springshed (Scott et al., 2006). My research showed no differen ce in total nitrogen or nitrate nitrogen concentrations within the cave but there was a difference with the total phosphorus concentration. Strong (2004) found that for 94 springs in the State of Florida, the mean total phosphorus concentration was 54 g /L (Table 4 1 ). Based on 52 springs, total nitrogen concentration had a mean of 1,600 g/L, while for 90 springs, the mean nitrate nitrogen concentration was 1,130 g/L (Table 4 1 ). Table 4 1 Arithmetic mean for total phosphorus, total nitrogen, and nitra te nitrogen from 1990 to 2003. Total nitrogen data are from 1997 to 2003 (Strong, 2004). Analyte Mean Minimum Maximum Std. Dev. Total Phosphorus (g/L) ((g/L) (g/L) (g/L) (g/L) (g/L) 54 (0 0 1,110 43 Total Nitrogen (g/L) 1,600 30 8,800 1, 920 Nitrate nitrogen (g/L) 1,130 0 10,300 1,350 surface and vent, and total nitrogen concentrati ons averaged 1,500 g/L at the surface and vent (Table 3 1), suggesting that it is biologically a productive spring system (Odum, 1957; Duarte and Canfield, 1990). When comparing the results of my nitrate m (Table 3

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32 results of 90 springs (Table 4 1 ), I had a mean of 1,300 g/L while Strong had 1,130 g/L (Table 4 1 ). Jackson Blue Spring had total phosphorus concentrations averaging 15.5 g/L at the surface and the vent and 15 g/L wit hin the cave, while total nitrogen concentrations averaged 2,600 g/L at the surface and vent and 900 g/L within the cave (Table 4 2 ). Nitrate nitrogen concentrations measured 1,700 g/L at the vent and averaged 9 00 g/L within the cave (Table 4 2 ). Cow Spring had total phosphorus averaging 32 g/L at the surface and vent and 30.5 g/L within the cave (Table 4 2 ). Total nitrogen concentrations averaged 2,550 g/L at the surface and the vent and 2,500 g/L within the cave (Table 4 2 ). Nitrate nitrogen conc entrations measured 2,250 g/L at the surface and the vent and 2,300 g/L within the cave (Table 4 2 ). Little River Spring had total phosphorus concentrations that averaged 19.5 g/L at the surface, vent, and within the cave, with total nitrogen concentrat ions averaging 1,250 g/L at the surface and vent, and 1,150 g/L within the cave and nitrate nitrogen concentrations averaging 1,100 g/L at the surface, vent, and within the cave (Table 4 2 ). Peacock Spring had total phosphorus concentrations averaging 41 g/L at the surface and the vent and 36 g/L within the cave, with total nitrogen concentrations averaging 2,100 g/L at the surface and vent, and 2,000 g/L within the cave (Table 4 2 ). The nitrate nitrogen concentrations averaged 2,100 g/L at the sur face and the vent and measured 2,000 g/L within the caves (Table 4 2 ). Madison Blue Spring had total phosphorus concentrations averaging 33 g/L at the surface and vent and 36.5 g/L within the cave (Table 4 2 ). Total nitrogen and nitrate nitrogen concent rations averaged 1,450 g/L at the surface and the vent (Table 4 2 ). Total nitrogen concentrations averaged 1,400 g/L

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33 in the cave while nitrate nitrogen concentrations averaged 1,450 g/L (Table 4 2 ). Lastly, total phosphorus concentrations at Manatee Spr ing averaged 26 g/L at the surface and the vent, 21.5 g/L within the cave, and total nitrogen and nitrate nitrogen concentrations averaged 1,900 g/L at the surface and the vent (Table 4 2 ). Total nitrogen averaged 2,200 g/L and nitrate nitrogen measure d 2,300 g/L within the cave (Table 4 2 ). In comparing total phosphorus, total nitrogen, and nitrate nitrogen sampled, several of the locations had similar concentration le vels while other locations differed. It was also interesting to note that most of the springs and caves I sampled had the same or similar total phosphorus, total nitrogen, and nitrate nitrogen concentrations in the cave compared to the surface and vent I had not expected (keep your past tense) the samples to have the same or similar concentration levels because of the potential differences in the watershed area, differences in flow rates within the cave, and also differences in the origin of the water.

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34 Tab le 4 2 Total phosphorus, total nitrogen, and nitrate nitrogen concentrations from select sprin were sampled on a one time basis. Date County Spring Sample Location Total Phosphorus (g/L ) Total Nitrogen (g/L) Nitrate Nitrogen (g/L) 2/11/06 Gilchrist Surface 34 1,400 1,400 6/20/09 Vent 36 1,500 1,300 River Intrusion Tunnel 32 1,500 1,400 Insulation Room 34 1,400 1,300 9/30/06 Jackson Jackson Blue Surface 15 3, 200 Vent 16 1,900 1,700 Conduit 1 13 900 900 Conduit 2 17 8 00 900 9/8/08 Suwannee Cow Surface 32 2,600 2,200 Vent 32 2,500 2,300 Conduit 1 31 2,600 2,100 Conduit 2 30 2,400 2,500 6/03/06 Suwannee Little River Surface 19 1,300 1, 200 Vent 20 1,200 1,000 Conduit 1 19 1,300 1,300 Conduit 2 20 1,000 900 4/30/06 Suwannee Peacock Surface 39 1,900 1900 Vent 42 2,300 2,300 Conduit 1 34 1,900 Conduit 2 38 2,100 2,000 5/29/06 Madison Madison Blue Surface 29 1,40 0 1,400 Vent 37 1,500 1,500 Conduit 1 37 1,400 1,400 Conduit 2 36 1,400 1,500 10/22/06 Levy Manatee Surface 26 1,900 1,900 Vent 26 1,900 1,900 Conduit 1 22 2,100 Conduit 2 21 2,300 2,300 ate that springs in Florida have a wide range of total phosphorus concentrations (8 to 124 g/L), total nitrogen concentrations

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35 (200 to 3400 g/L), and nitrate nitrogen concentrations (900 to 2500 g/L. The springs and caves that I sampled had similar mean s to each other for total phosphorus, total nitrogen, and nitrate nitrogen concentrations with the exception of Jackson Blue Spring (Table 4 2 ). Strong (2004) sampled several local springs (Table 4 3 ) and showed that there is a wide range in total phosphor us concentrations (15 to 400 g/L), total nitrogen concentrations (300 to 3,200 g/L), and nitrate nitrogen concentrations (500 to 2,300 g/L) depending on spring location. Even springs located within the same county can have a wide range of nutrient conce ntrations. In Gilchrist County, for example, mean total phosphorus concentrations ranged from 34 to 80 g/L, mean total nitrogen concentrations ranged from 900 to 1,800 g/L, and mean nitrate nitrogen concentrations from 1,000 to 1,700 g/L (Tables 4 2 and 4 3 ). Table 4 3 General chemistry data for springs located by Florida county (Strong, 2004). County Spring Total Phosphorus (g/L) Total Nitrogen (g/L) Nitrate Nitrogen (g/L) Alachua Glen Spring 400 700 1300 Alachua Hornsby Spring 100 500 600 Ala chua Poe Spring 100 300 500 Columbia Ichetucknee Spring 30 800 Gilchrist Ginnie Springs 40 1800 1300 Gilchrist Blue Spring 40 1100 1700 Gilchrist Hart Spring 80 1600 1100 Gilchrist Otter 50 1000 1300 Gilchrist Rock Bluff Spring 70 900 1000 Stro ng (2004) found no statistically significant changes in the mean total phosphorus concentrations when he compared data from 1907 1979, 1980 1989, and 1990 2003. Strong (2004) did find, however, statistically significant increases in the mean nitrate nitrog en concentrations from the time period 1907 1979 compared to

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36 1980 1989 (82%) and 1907 1979 compared to 1990 2003 (126%). Strong (2004) also found that, out of 73 springs, 17 showed significant increases in their mean nitrate nitrogen concentration. My rese arch demonstrated that total phosphorus concentrations were relatively consistent over the study period at each of the sampling locations Total nitrogen was also relatively consistent at th ree of the sampling locations, but there appeared to be a decrease at the Insulation Room Nitrate nitrogen concentrations showed a general decrease at all four sampling locations during th e study period When the Santa Fe River reache s high stages during heavy rainfall events and seasonal flooding, I observed a reducti on in the usual crystal clear groundwater within the cave system, which has been attributed by other cave divers to river water intrusion. When the Santa Fe River is high and the tannin colored river water starts to mix with the spring water at the Eye, a tarp is placed between the river and the spring by employees of Ginnie Springs Outdoors. The tarp was placed between the river and the spring after Tropical Storm Fay crossed Gainesville on August 22, 2008. Despite the tarp, I observed diminished visibilit y in the cave system, and the tannin color typical of the river could be seen throughout the cave system including the main conduit and the River Intrusion Tunnel, indicating river water was intruding and mixing with the spring water. In addition to the vi sibility being reduced in the cave, I also noticed the perceived flow was also reduced; however, it did not reverse flow. I took water samples nine days after the tropical storm moved through Gainesville. Total phosphorous concentrations in the River Intru sion Tunnel and the Insulation Room increased to 40 g/L and 46 g/L, respectively, which was the highest concentration measured in the In sulation Room during the study Both total nitrogen and nitrate nitrogen concentrations decreased in

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37 the River Intrusi on Tunnel (1200 g/L and 800 g/L, respectively) and Insulation Room (1300 g/L and 800 g/L, respectively) occurs rapidly (Kincaid, 1998). Kincaid used Radon 222 to quantify th e exchanges and collected water samples throughout the cave system including the River Intrusion Tunnel and near the Insulation Room (Kincaid, 1998). He found that in as little as one or two days after heavy rainfall in the Northern Highlands, river water intrusion can occur and that approximately 50 70% of the water in the River Intrusion Tunnel is river water while 20 50% of the water in the Insulation Room is river water (Kincaid, 1998). When the rainfall is in the lowland regions, the water in the cave will be clear (Kincaid, 1998). The River Intrusion Tunnel is located on the south side of the main conduit and is closer to the Santa Fe River while the Insulation Room is on the north side of the main conduit and further away from the Santa Fe River, whic h indicates that river water is entering the cave system from the conduits closest to the river (Kincaid, 1998). Although I found the River Intrusion Tunnel total phosphorus concentration to be slightly correlated with the river stage level, it does not me an the total phosphorus concentration at the River Intrusion Tunnel was not affected by the river stage level or rainfall but that it may not be immediately affected. In reviewing the analysis for the total phosphorus concentrations in the Santa Fe River and the River Intrusion Tunnel, when there is an increase or decrease in the total phosphorus concentration in the Santa Fe River, there appears to be a corresponding increase or decrease in the total phosphorus concentration at the River Intrusion Tunnel 57% of the time, 41% of the time for both the Insulation Room and the surface, and 63%

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38 of the time for the vent Although the total phosphorus concentrations in the Santa Fe River may contribute to the total phosphorus concentrations in the cave, the vent, and the surface, there are other factors involved such as flow and source of the water. Although total nitrogen and nitrate nitrogen concentrations do not show a statistically significant difference among the four sampling locations, the total phosphorus connection between the River Intrusion Tunnel and the Santa Fe River does exist and that the river is contributing phosphorus to the River Intrusion Tunnel.

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39 CHAPTER 5 CONCLUSION W be a concern. The U. S. EPA has mandated numerical nitrate springs and monitoring the springs will be needed to assess if this criterion is bein g met. Based on my research, water samples can be taken either just below the surface of the spring or spring vent for most springs without concern for sampling bias. Nutrient concentrations differed statistically within the cave for total phosphorus but not for total nitrogen or nitrate nitrogen. This could be related to flow rate or locations, but few caves have been studied. The occurrence of stochastic events like Tropical Storm Fay and hurricanes on cave systems and water chemistry deserve further st udy. cave system, there is a biofilm. I sampled the biofilm, found in the Insulation Room, and examined it under the microscope but could not identify it. Other specialists at the University of Florida also could not identify the organisms. When the biofilm was viewed under the microscope, long, cylindrical shapes were observed. There are several types of microbial communities that could constitute the biofilm, but specific microbes have not been identified (Dr. William Huth, University of West Florida, personal communication). I also found one other location in the cave that has the biofilm. This location is approximately 820 meters from the vent and is also on the north sid e of the main conduit. certain areas of the cave are still unresolved questions. Hence more research on environmental factors influencing life in caves, including biofilm, is needed Finally,

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40 purposes as well as for concerned citizens. In 2011, the Florida Legislature eliminated funding for springs due to budget constraints. If funding for monitoring sp rings is to be reduced in the future, the FDEP could work with Florida LAKEWATCH, as volunteer cave divers are willing and able to sample the springs and spring runs.

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41 APPEND IX WATER DATA Table A 1. Water data collected between February 2006 through Jun e 2009 from four Month Day Year Station TP g/L TN g/L NO3 N g/L 2 11 2006 Surface 40 1700 1600 2 11 2006 Vent 36 1700 1600 2 11 2006 Insulation Room 39 1700 1600 2 11 2006 River Intrusion Tunne l 32 1700 1600 3 19 2006 Surface 39 1800 1500 3 19 2006 Vent 41 1600 1700 3 19 2006 Insulation Room 38 1800 1700 3 19 2006 River Intrusion Tunnel 35 1700 1600 4 26 2006 Surface 39 1700 1700 4 26 2006 Vent 37 1700 1700 4 26 2006 Insulation Room 36 17 00 1400 4 26 2006 River Intrusion Tunnel 32 1700 1700 5 24 2006 Surface 34 1700 1600 5 24 2006 Vent 31 1200 1700 5 24 2006 Insulation Room 38 1800 1800 5 24 2006 River Intrusion Tunnel 30 1700 1800 6 18 2006 Surface 33 1600 1200 6 18 2006 Vent 36 13 00 1200 6 18 2006 Insulation Room 36 1300 1500 6 18 2006 River Intrusion Tunnel 25 1200 1000 7 29 2006 Surface 29 1300 1800 7 29 2006 Vent 33 1400 1700 7 29 2006 Insulation Room 37 1700 1800 7 29 2006 River Intrusion Tunnel 30 1500 1500 8 17 2006 Su rface 29 1700 1600 8 17 2006 Vent 32 1600 1800 8 17 2006 Insulation Room 31 1700 1600 8 17 2006 River Intrusion Tunnel 24 1000 1700 9 27 2006 Surface 30 1100 1200 9 27 2006 Vent 31 1700 1200

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42 Table A 1 (C ontinued) Month Day Year Station TP g/L TN g/L NO3 N g/L 9 27 2006 Insulation Room 42 2000 1600 9 27 2006 River Intrusion Tunnel 28 1500 1600 10 27 2006 Surface 29 1400 1400 10 27 2006 Vent 29 1600 1700 10 27 2006 Insulation Room 33 1600 1700 10 27 2006 River Intrusion Tunnel 32 1700 12 29 2006 Surface 33 1200 1200 12 29 2006 Vent 37 1500 1200 12 29 2006 Insulation Room 35 1000 12 29 2006 River Intrusion Tunnel 30 1300 1400 1 6 2007 Surface 29 1100 1 6 2007 Surface 32 1300 1 6 2007 Vent 35 1300 1 6 2007 Vent 34 1400 1 6 2007 Insulation Room 35 1400 1700 1 6 2007 River Intrusion Tunnel 33 1600 1700 2 3 2007 Surface 35 1500 1700 2 3 2007 Vent 35 1600 1600 2 3 2007 Insulation Room 36 1300 2 3 2007 Insulation Room 21 700 2 3 2007 River Intrusion Tunnel 34 900 2 3 2007 River Intrusion Tunnel 29 1600 3 25 2007 Surface 35 1400 1600 3 25 2007 Vent 38 1600 1500 3 25 2007 Insulation Room 34 1500 1500 3 25 2007 River Intrusion Tunnel 31 1600 1700 4 22 2007 Surface 33 1500 1600 4 22 2007 Vent 40 1600 4 22 2007 Insulation Room 39 1600 1600 4 22 2007 River Intrusion Tunnel 38 1400 1700 5 29 2007 Surface 31 1600 5 29 2007 Vent 37 1600 1600

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43 Table A 1 (C ontinued) Month Day Year Station TP g/L TN g/L NO3 N g/L 5 29 2007 Insulation Room 35 1500 1600 5 2 9 2007 River Intrusion Tunnel 35 1600 1600 6 3 2007 Surface 35 1500 6 3 2007 Vent 35 1600 1600 6 3 2007 Insulation Room 40 1600 6 3 2007 River Intrusion Tunnel 31 1500 7 29 2007 Surface 35 1600 1600 7 29 2007 Vent 41 1700 1600 7 29 2007 Insula tion Room 40 1600 1400 7 29 2007 River Intrusion Tunnel 34 1700 1700 8 19 2007 Surface 36 1600 1600 8 19 2007 Vent 38 1600 1300 8 19 2007 Insulation Room 12 100 1600 8 19 2007 River Intrusion Tunnel 31 1600 1500 9 3 2007 Surface 34 1600 1500 9 3 200 7 Vent 38 1600 1500 9 3 2007 Insulation Room 34 1600 1500 9 3 2007 River Intrusion Tunnel 30 1600 1500 10 21 2007 Surface 36 1600 1600 10 21 2007 Vent 37 1600 1500 10 21 2007 Insulation Room 33 1600 1200 10 21 2007 River Intrusion Tunnel 40 1500 1300 1 21 2008 Surface 36 1500 1400 1 21 2008 Vent 36 1600 1400 1 21 2008 Insulation Room 38 1500 1400 1 21 2008 River Intrusion Tunnel 36 1600 1500 2 9 2008 Surface 29 1500 1400 2 9 2008 Vent 30 1500 1400 2 9 2008 Insulation Room 33 1400 1400 2 9 2008 River Intrusion Tunnel 24 1600 1500 3 1 2008 Surface 26 1400 1400 3 1 2008 Vent 32 1200 1300

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44 Table A 1 (C ontinued) Month Day Year Station TP g/L TN g/L NO3 N g/L 3 1 2008 Insulation Room 31 1400 1300 3 1 2008 River Intrusion Tunnel 33 1600 150 0 4 29 2008 Surface 34 1000 1300 4 29 2008 Vent 38 1200 1100 4 29 2008 Insulation Room 36 1300 1200 4 29 2008 River Intrusion Tunnel 34 1500 1300 5 18 2008 Surface 34 1300 1300 5 18 2008 Vent 39 1100 1000 5 18 2008 Insulation Room 29 1400 900 5 18 2008 River Intrusion Tunnel 31 1600 900 6 21 2008 Surface 36 1300 1400 6 21 2008 Vent 28 1300 1100 6 21 2008 Insulation Room 37 1300 1200 6 21 2008 River Intrusion Tunnel 35 1400 1400 7 13 2008 Surface 31 1300 1200 7 13 2008 Vent 38 1400 1200 7 13 2 008 Insulation Room 38 1300 1100 7 13 2008 River Intrusion Tunnel 35 1500 1100 8 31 2008 Surface 44 1000 8 31 2008 Vent 43 1000 8 31 2008 Insulation Room 48 800 8 31 2008 Insulation Room 44 800 8 31 2008 River Intrusion Tunnel 38 1100 8 31 2008 River Intrusion Tunnel 41 1200 9 14 2008 Surface 40 1400 800 9 14 2008 Vent 42 1300 700 9 14 2008 Insulation Room 44 1200 600 9 14 2008 River Intrusion Tunnel 40 1400 800 10 11 2008 Surface 33 1400 400 10 11 2008 Vent 33 1400 500 10 11 2008 Insulation Room 33 1200 600 10 11 2008 River Intrusion Tunnel 35 1500 800

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45 Table A 1 (C ontinued) Month Day Year Station TP g/L TN g/L NO3 N g/L 12 21 2008 Surface 33 1400 1000 12 21 2008 Vent 30 1400 900 12 21 2008 Insulation Room 40 1400 1000 1 2 21 2008 River Intrusion Tunnel 35 1700 1000 1 31 2009 Surface 32 1400 1000 1 31 2009 Vent 32 1400 1000 1 31 2009 Insulation Room 29 1400 1000 1 31 2009 River Intrusion Tunnel 25 1500 1000 2 21 2009 Surface 33 1400 1000 2 21 2009 Vent 34 1400 1000 2 21 2009 Insulation Room 32 1400 1000 2 21 2009 River Intrusion Tunnel 24 1500 1000 3 29 2009 Surface 30 1500 1000 3 29 2009 Vent 31 1400 1000 3 29 2009 Insulation Room 35 1300 1000 3 29 2009 River Intrusion Tunnel 32 1500 1000 4 18 2009 Surface 34 1500 1500 4 18 2009 Vent 1500 4 18 2009 Insulation Room 32 1400 1400 4 18 2009 River Intrusion Tunnel 33 1400 1400 5 30 2009 Surface 37 1400 1600 5 30 2009 Vent 39 1200 1400 5 30 2009 Insulation Room 37 1400 1200 5 30 2009 River Intrusion Tunnel 33 1400 1300 6 20 2009 Surface 30 1400 1400 6 20 2009 Vent 38 1400 1400 6 20 2009 Insulation Room 35 1500 1400 6 20 2009 River Intrusion Tunnel 34 1600 1300

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46 LIST OF REFERENCES A merican Public Health Association (1992). Standard Methods for the Exam ination of Water and Wastewater, 18 th edn. American Public Health Association, Washington, D.C. Canfield, Jr., D.E., Brown, C.D., Bachmann, R. W., and Hoyer, M.V. (2002). Volunteer Lake Monitoring: Testing the Reliability of Data Collected by the Florida L AKEWATCH Program. Lake and Reservoir Management, 18(1): 1 9. Champion, K.M. and Starks, R. (2001, Revised 2011). Hydrology and Water Quality of Select Springs in the Southwest Florida Water Management District. Water Quality Monitoring Program, Southwest F lorida Water Management District, Brooksville, FL. inaqueous samples using persulfate digestion. Limnology and Oceanography, 22: 760 764. Duarte, C.M. and D.E. Canfield, J r. (1990). Macrophyte Standing Crop and Primary Production in some Florida Spring Runs. Water Resources Bulletin, 26(6): 927 934. Florida Department of Environmental Protection. (2010). Available URL: http://www.floridasprings.org/protecting/initiative/ Florida Department of Environmental Protection. (2010). Florida Springs Initiative Monitoring Network Report and Recognized Sources of Nitrate. Tallahassee, FL. Florida Department of Stat e, Florida Administrative Code. Chapter 62 302, Surface Water Quality Standards. Tallahassee, FL. Available URL: https://www.flrules.org/gateway/chapterhome.asp?chapter=62 302 Restoration. Prepared by The Florida Springs Task Force. Tallahassee, FL. Frazer, T.K., Notestein, S.K. and Pine Jr., W.E. (2006). Changes in the Physical, Chemical and Vege tative Characteristics of the Homosassa, Chassahowitzka and Weeki Wachee Rivers. Final Report. Southwest Florida Water Management District, Brooksville, FL. Ginnie Springs Outdoors LLC. (2012). Available URL: www.ginniespringsoutdoors.com/

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47 Hisert, R.A. (1994). A multiple tracer approach to determine the ground and surface water relationships in the western Santa Fe River, Columbia County, Florida: Ph.D. Disse rtation, University of Florida, 212 pp. Kincaid, T. R. (1998). River water intrusion to the unconfined Floridan Aquifer. Environmental & Engineering Geoscience, Vol. IV, No. 3: 361 374. Kincaid, T. R. (2004). A hydrogeologic overview of the springs and un derwater caves of north Society/National Speleological Society Cave Diving Section Field Trip. Martin, J.B. and Dean, R.W. (2001). Exchange of water between conduits and matrix in the Flor idan aquifer. Chemical Geology, 179: 145 165. Martin, J.B. and Screaton, E.J. (2001). Exchange of matrix and conduit water with examples from the Floridan aquifer. Water Resources Investigations Report 01 0411: 38 44. Menzel, D. W. & Corwin N. (1965). The measurement of total phosphorus in seawater based on the liberation of organically bound fractions by persulfate oxidation. Limnology and Oceanography 10: 280 282. Miller, J. A. (1997). Hydrogeology of Florida. In A. Randazzo and D. Jones (Eds.). The Geol ogy of Florida (pp. 69 88). Gainesville: University Press of Florida, Gainesville, FL. Murphy J. and Riley J.P. (1962). A modified single solution method for thedetermination of phosphate in natural waters. Analytica Chimica Acta 27: 31 36. Notestein, S.K ., Frazer, T.K., Hoyer, M.V, and Canfield, Jr. D.E. (2003). Nutrient Limitation of Periphyton in a Spring Fed, Coastal Stream in Florida, USA. Journal of Aquatic Plant Management 41: 57 60. Obreza, T. and Means, G. (2006). Characterizing agriculture in F Suwannee River Basin Area, Soil and Water Science Department, Florida Cooperative Extension Services, Institute of Food and Agricultural Sciences. University of Florida, Fact Sheet SL 241. Odum, H.T. (1957). Trophic Structure and Productivit y of Silver Springs, Florida. Ecol. Monogr 27:55 112. Poucher, S. and Copeland, R. (2006). Speleological and Karst Glossary of Florida and the Caribbean. Gainesville, FL. Scott, T. M. (1991). The geology of the Santa Fe River basin, central northern Penin sular Florida. Hydrogeology of the Western Santa Fe River Basin, Field Trip Guidebook No. 32: Southeastern Geological Society, Tallahassee, FL.

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48 Scott, T.M. (1992). A geological overview of Florida, Florida Geological Survey Open File Report 50, 78 pp. Sim al J., Lage M.A., and Iglesias I. (1985). Second derivative ultraviolent spectroscopy and sulfamic acid method for determination of nitrates in water. Journal of Analytical Chemistry 68: 962 964. Smith, V.H., S.B. Joye, and R.W.Howarth (2006). Euthrophic ation of freshwater and marine ecosystems. Limnology and Oceanography 51: 351 355 The Springs of Florida. (2004). Bulletin No. 66, Florida Geological Survey, Tallahassee, FL. United States Department of Agriculture, Natural Resources Conservation Service Major Land Resource Areas in Florida. Available URL: http://www.mo15.nrcs.usda.gov/technical/mlra_fl.html [Accessed April 22, 2010]. United States Department of Agriculture, Natural Re sources Conservation Service, Official Soil Series Descriptions (OSD) with series extent mapping capabilities. Available URL: http://soils.usda.gov/technical/classification/osd/i ndex.html [Accessed April 20, 2010]. United States Department of Agriculture, Natural Resources Conservation Service, Soil Classification. Available URL: http://soils.usda.gov/technical/class ification/ [Accessed April 22, 2010]. United States Department of Environmental Protection Agency, Water: Drinking Water Contaminants, National Primary Drinking Water Regulations. Available URL: http:// water.epa.gov/drink/contaminants/index.cfm#Inorganic [Accessed October 15, 2011]. United States Department of Environmental Protection Agency. Water Quality http://water.epa.gov/lawsregs/rulesregs/florida_index.cfm [Accessed November 16, 2010]. Walsh, S.J. (2001). In Eve L. Kuniansky, editor, U.S. Geological Survey Karst Interest Group Proceedings, U.S. Geological Survey Karst Interest Group Proceedings, St. Petersburg, Florida, February 13 16, 2001: USGS Water Resources Investigations Report 01 4011 White, W.A. ( 1970 ). The G eomorphology of the Florida Peninsula Bulletin No. 51, Florida Geological Survey, Tallahassee, FL. Wollin K. M. (1987). Nitrate determination in surface waters as an example of the application of UV derivative spectrometry to environmental analysis. ActaHydrochemica et Hydrobiologica 15: 459 469.

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49 BIOGRAPHIC AL SKETCH Stacey Ann Sandrey was born in Levittown, Pennsylvania. She graduated from Neshaminy High School in 1985. She received a Bachelor of Science degree Magna cum Laude in Business Administration with an emph asis in Finance from Rider University. In 2004, she decided to move to Gainesville, Florida, to pursue her love of cave diving and is employed at the University of Florida. She has always been interested in wildlife and water I n 2006, she decided to pursue a graduate degree at the research in 2012.