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Transformation and fate of dissolved organic matter originating in the Suwannee River watershed

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Title:
Transformation and fate of dissolved organic matter originating in the Suwannee River watershed a stable isotope approach
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Hall, Emily R., 1976-
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English
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xii, 158 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Carbon ( jstor )
Cell aggregates ( jstor )
Clams ( jstor )
Estuaries ( jstor )
Isotopes ( jstor )
Nitrogen ( jstor )
Oysters ( jstor )
Particulate materials ( jstor )
Rivers ( jstor )
Salinity ( jstor )
Dissertations, Academic -- Environmental Engineering Sciences -- UF ( lcsh )
Environmental Engineering Sciences thesis, Ph. D ( lcsh )
Suwannee River, FL ( local )
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bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 2004.
Bibliography:
Includes bibliographical references.
General Note:
Printout.
General Note:
Vita.
Statement of Responsibility:
by Emily R. Hall.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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TRANSFORMATION AND FATE OF DISSOLVED ORGANIC MATTER
ORIGINATING IN THE SUWANNEE RIVER WATERSHED: A STABLE ISOTOPE
APPROACH














By

EMILY R. HALL


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


2004














ACKNOWLEDGMENTS

Financial support for this work was provided in part, by the USDA (Grant # 2001-

35102-09857), NSF (Grant # OCE0240187), the University of Florida Women's Club,

and the University of Florida.

Everyone who I have had contact with in any way throughout my time at the

University of Florida has influenced my life in some way. I thank them all from the

bottom of my heart, even though I know simple thanks are not enough. I must

acknowledge them to the best of my ability on paper, but know that they all mean the

world to me.

First I must start with my family. My parents have been through thick and thin

with me, and I could not have done well without their support, both financially and

emotionally. My sister has been an ear for me to talk to, and she has taught me to live

free. My brother has been a source of energy, and he has taught me to enjoy life while

still working hard.

My mentors have been crucial in my academic journey. Dr. Brian Rood gave me

the first opportunity to pursue a career in environmental science. His enthusiasm and

love for the environment as well as his energy guided me towards this field of science.

Dr. Joseph Delfino, my committee chair for the past five and a half years, took over

where Dr. Rood left off. He guided me through tough times, scientifically and

administratively, and he has had continued faith in my abilities. Dr. Tom Frazer, my co-

chair, willingly provided me with a project without prior knowledge of my capabilities.








He allowed me to learn from my mistakes and he pushed me to become a better scientist.

I also acknowledge my committee members Dr. Jean-Claude Bonzongo and Dr. Mark

Brenner for their mentoring and involvement in my graduate education.

My peers have also had a large influence during my time at the University of

Florida. Unfortunately (but fortunately) this group is the largest, and I cannot mention

everyone individually. First I will start with my research groups in Black Hall and at the

Department of Fisheries and Aquatic Sciences. They provided me with friendships that I

will never forget as well as inspiration to work hard in science and in life. I also thank

the University of Florida Club Soccer program. It gave me an opportunity to continue to

play the sport I love, and to have some of the best friendships. Lastly, I thank Jason

Heggerick for being my strength and support during demanding times. He was a

shoulder to cry on and a friend to laugh with.

"The sea lies all about us. The commerce of all lands must cross it. The very

winds that move over the lands have been cradled on its broad expanse and seek ever to

return to it. The continents themselves dissolve and pass to the sea, in grain after grain of

eroded land. So the rains that rose from it return again in rivers. In its mysterious past it

encompasses all the dim origins of life and receives in the end, after, it may be, many

transmutations, the dead husks of that same life. For all at last returns to the sea-to

Oceanus, the ocean river, like the ever-flowing stream of time, the beginning and the

end" (Rachel Carson, The Sea Around Us). There are no limits for journeys of the mind.














TABLE OF CONTENTS

page

ACKNOW LEDGM ENTS ............................................................ .......................... ii

L IST O F TA B L E S ........................................................................ ............................. vi

LIST O F FIG U R E S ...................................................................... .............................. vii

A B STR A C T ....................................................................... ......................................... x

CHAPTER

S IN TR O D U C TIO N ................................................................. ..............................

B ackground................................... ...................................................................
Suwannee River and Estuary................................................... .........................
Nutrient Loading, Especially Nitrogen........................ ......................... 4
Clam and Oyster Ecology..................................................... ............................6
H um ic Substances.............................. ............................................................... 8
Flocculation .......................................................................................................... 11
Stable Carbon and Nitrogen Isotopes as Tracers of Material Transfer and Energy
Flow ......................... ..... ................................................................... 19
Proposed Research....................... ... .................... ............................. 29

2 STABLE CARBON AND NITROGEN ISOTOPE COMPOSITION OF ORGANIC
AGGREGATES PRODUCED BY SALINITY INDUCED FLOCCULATION OF
DISSOLVED ORGANIC MATTER FROM THE SUWANNEE RIVER................30

Introduction....................... ................................................................... 30
M methods and M materials ....................................................... ............................ 34
Site............................................................... ..............................34
Methods ...................................................................................... 35
DOC and Stable Isotope Analysis........................................ .........................36
Results............... ... ....................................................... 36
Discussion.................. ............................................................................. 46
Summary................ .......................................................................50
Conclusions................ .......................................................................50

3 SPATIAL GRADIENTS IN THE STABLE CARBON AND NITROGEN ISOTOPE
COMPOSITION OF SUSPENDED PARTICLES IN THE SUWANNEE RIVER
ESTUARY DURING DIFFERENT FLOW REGIMES............................................ 51








Introduction......................................................................... ..................................5 1
Methods, Materials, and Site Description..................... ........... ................53
Site D description ........................................ ..............................................53
M methods ......................................................................... ...............................54
R esults............................................................................... ....................................59
Physical Parameters......................... .......................... .........................59
Chemical Parameters..................... .......................................59
Biological Indicator.......................... ..................................65
Stable Isotope Analyses........................... ...... .........................65
Statistics....................................................................... ..................................77
D discussion .......................................................................... ...................................77
Sum m ary ............................................................................. .................................. 94
C onclusions......................................................................... ..................................95

4 STABLE ISOTOPES AS TRACERS IN FOOD WEB INVESTIGATIONS OF THE
SUWANNEE RIVER ESTUARY ................................... ........................96

Introduction.......................................................................... ................................. 96
M methods and M materials ........................................................ ........................... 99
Site D description ........................................................... ............................99
Sampling........................... ............................................100
Stable Isotope Analyses........................... ...... .........................101
R esults..................................................... ........................... ........................ 101
D discussion ......................................................................... ..................................103
Stable Carbon Isotopes..................... ....... .......................103
Stable Nitrogen Isotopes............................................. ............ 112
Multiple Stable Isotopes and Food Source....................................................112
Sum m ary ............................................................................. ................................118
C onclusions........................................................................ .................................118

5 SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS .........................120

Sum m ary ........................................................................... ..................................120
Conclusions............................. ....... ...................................................121
Recommendations for Further Research ........................................................ 122

APPENDIX

A SUPPLEMENTAL STABLE CARBON AND NITROGEN ISOTOPE DATA.....123

B SUPPLEMENTAL SIZE AND WEIGHT DATA OF CLAMS ............................133

C SUPPLEMENTAL SIZE AND WEIGHT DATA OF OYSTERS .......................... 140

LIST OF REFERENCES.................. ............................................................143

BIOGRAPHICAL SKETCH............................................................. ........................158














LIST OF TABLES


Table page

2-1. Analysis of Variance (ANOVA) Results for all of the Floc Studies......................38

3-1. Location and Site Names for Sampling Sites in the Suwannee River and its Estuary.57

3-2. Chemical and Biological Parameters in the Suwannee River and its Estuary for Each
Sam pling Event. .......................................... ...............................................60

3-3. Concentrations of Nitrogen Components (ig/L) in the Suwannee River and its
Estuary for Each Sampling Event. ................................ .........................63

3-4. Concentrations of Phosphorus Components (pg/L) in the Suwannee River and its
Estuary for each Sampling Event.................................... .................................64

3-5. Stable Isotope Data of Suspended Particulate Organic Matter (SPOM) and
Dissolved Inorganic Nitrogen (DIN) for the 1996, 1997, and Two 2003 Sampling
Events. ............................................................. ........... ......................... 68

3-6. ANOVA Tables for the Effects of Salinity on the i'5N and 13C of Suspended
Particulate Organic Matter during Novermber 1996................................... ...80

3-7. ANOVA Tables for the Effects of Salinity on the 5'5N and 13C of Suspended
Particulate Organic Matter during March 1997......................................................81

3-8. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during December
2003 ....................................................... ............................. ............................82

3-9. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during May 2003.84

A-1. Stable Carbon and Nitrogen Isotopes of Clams, Oysters, and Suspended Particulate
Organic Matter (SPOM)..........................................................123

B-1. Size (mm) and Weight (g) Data of Clams. ....................... .........................133

C-l. Size (mm) and W eight (g) of Oysters..................................... .......................... 140














LIST OF FIGURES


Figure page

2-1. Salinity versus Dissolved Organic Carbon in the Upper and Lower Suwannee River
Floe Studies................................... .............................. .............. ...............39

2-2. Time versus Dissolved Organic Carbon for Floc Studies I and II...........................40

2-3. Salinity versus 615N for the Upper and Lower Suwannee River Flocculated Organic
A ggregates............................................ ........................................................ 41

2-4. Salinity versus 813C for the Upper and Lower Suwannee River Flocculated Organic
A ggregates................................................ ..........................................................42

2-5. Salinity versus Average 615N Signatures of the Upper and Lower Suwannee River
Floe Studies Including Standard Deviation Error Bars..........................................43

2-6. Salinity versus Average 6SC Signatures of the Upper and Lower Suwannee
River Floe Studies Including Standard Deviation Error Bars................................44

2-7. Salinity versus C:N Ratios of the Flocculated Organic Aggregates from the Upper
and Lower Suwannee River Floe Studies Including Standard Deviation Error
B ars............................................ ........ ................................. ............................... 45

3-1. Map of the Sampling Sites in the Suwannee River and its Estuary........................56

3-2. Monthly Streamflow Data for the Suwannee River near Wilcox, Florida (USGS,
2004).............................................................................. ....................................6 1

3-3. 615N Signatures of Surface Suspended Particulate Organic Matter (SPOM) for the
1996 and 1997 Sampling Events................................ ................................66

3-4. S&5N Signatures of Surface Suspended Particulate Organic Matter (SPOM) for the
Two 2003 Sampling Events. ........................ .......... ..........................67

3-5. 815N Signatures of Surface Dissolved Inorganic Nitrogen (DIN) for the March 1997
Sam pling E vent. ..................................................................... .................................70

3-6. S15N Signatures of Surface Dissolved Inorganic Nitrogen (DIN-Nitrate) for the 2003
Sam pling Events................................................................................................. 71








3-7. '15N Signatures of Zooplankton Collected during the May 2003 (High Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores). .....................................................................................................72

3-8. 6'5N Signatures of Zooplankton Collected during the December 2003 (Low Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores). ............................................................... ..................................73

3-9. Stable Carbon and Nitrogen Isotopes of Oysters Collected During the December
2003 Sam pling Event. .................................................. .............................74

3-10. 813C of the Suspended Particulate Organic Matter (SPOM) for the 1996 and 1997
Sam pling Events.................................................... ..................................... 75

3-11. S63C of the Suspended Particulate Organic Matter (SPOM) for the Two 2003
Sam pling Events........................................ ... .......................................... 76

3-12. 63C of Zooplankton Collected During the May 2003 Sampling Event (Cope =
Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores)........................78

3-13. 86"C of Zooplankton Collected During the December 2003 Sampling Event (Cope
= Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores). .....................79

3-14. Model of Spatial Gradients in the 1'5N Signatures of a Hypothetical Closed System
(redrawn from Montoya and McCarthy, 1995).......................................................89

3-15. Theoretical Curves Illustrating Spatial Variation in the f15N of Phytoplankton
along an Onshore/Offshore Gradient. Losses in the Bottom Panel Occur as a
Consequence of Grazing and Sedimentation Processes.........................................90

3-16. 615N vs. 613C of Oysters, Zooplankton, and SPOM for the December 2003
Sam pling Event.............................................................. .............................91

3-17. ~'N vs. 613C of Oysters, Zooplankton, and SPOM for the May 2003
Sampling Event..................... ...............................................................................92

4-1. Map of Sampling Sites for Clams, Oysters, and Suspended Particulate Organic
Matter (SPOM) in the Suwannee River Estuary ...............................................102

4-2. 61C of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River
Estuary Sites......................... ........................ .........................104

4-3. 615N of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River
Estuary Sites...................................... ...... .............. ..........................105

4-4. 6"C of Clams from Two Suwannee River Estuary Sites......................................106








4-5. 13C of Oysters from Two Suwannee River Estuary Sites....................................107

4-6. 615N of Clams from Two Suwannee River Estuary Sites......................................109

4-7. 615N of Oysters from Two Suwannee River Estuary Sites.................................... 10

4-8. 613C vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary
Sites.................................................................................. ................................. 113

4-9. 13C vs. Dry Body Weight (g) of Oysters from Two Suwannee River Estuary
Sites...................... ............... ......................... .............. ............. ............ .. 114

4-10. 815N vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary
Sites................................................................................. ................................. 115

4-11. s65N vs. Dry Body Weight (g) of Oysters from Two Suwannee River Estuary
Sites............................................ .............................. ................................... 16

4-12. The Suwannee River Estuary Food Web Structure Using 5"C and 65N............. 117













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
TRANSFORMATION AND FATE OF DISSOLVED ORGANIC MATTER
ORIGINATING IN THE SUWANNEE RIVER WATERSHED: A STABLE ISOTOPE
APPROACH

By

Emily R. Hall

December 2004

Chair: Joseph J. Delfino
Cochair: Thomas K. Frazer
Major Department: Environmental Engineering Sciences

Anthropogenic activities in a watershed can have significant impacts on the

ecology of downstream coastal environments. Surface runoffand groundwater inputs

from the Suwannee River watershed contribute high concentrations of nutrients (nitrates

>1 mg/L) to this blackwater river before it discharges into the Gulf of Mexico. High

concentrations of nutrients have the potential to affect the sustainability, productivity, and

growth of the oyster and clam aquaculture industries in the estuary. In determining

detrimental effects, it is important to establish a link between dissolved carbon and

nitrogen, suspended particulate organic matter (SPOM), and production of clam and

oyster biomass in the Suwannee River estuary.

Organic aggregates (a possible food source for the bivalves in the Suwannee River

estuary) were produced in the laboratory by adding salts to unfiltered fresh organic-

enriched Suwannee River surface water. They were analyzed for stable carbon and

nitrogen isotopes and the results indicate that the 615N signatures can be used as a tracer








of organic aggregate development. More importantly, however, the results suggest that

3"C signatures of organic aggregates can be used to quantify their role as a food source

for estuarine fauna.

Spatial gradients in nutrient concentrations, particularly nitrate, are characteristic of

estuarine systems. These gradients occur as a result of mixing processes and uptake and

assimilation by phytoplankton. Isotopic fractionation associated with this uptake and

assimilation can generate strong spatial gradients in the stable nitrogen isotope

composition of particulate nitrogen. In essence, stable nitrogen isotopes serve as in situ

tracers of the processing of nitrogen as it moves through an estuarine system.

Clams and oysters were seeded in the Suwannee River estuary near the river

mouth. Clams, oysters, and SPOM were sampled monthly for approximately one year

and subsequently analyzed for stable carbon and nitrogen isotopes. The results indicate

that the clams consumed the same source of organic material throughout the year (marine

SPOM), while the oysters' food source changed consistently with hydrologic patterns in

the river (e.g., more terrestrial origin during high flow and more marine origin during low

flow). Neither clams nor oysters consumed flocculated organic aggregates as a dominant

food source.













CHAPTER 1
INTRODUCTION

Background

Anthropogenic activities in a watershed can have significant impacts on the

ecology of downstream coastal environments. The Suwannee River drains 28,000 km2 of

southern Georgia and north central Florida (Wolfe and Wolfe, 1985). Surface runoff and

groundwater inputs contribute high levels of nutrients to this blackwater river before it

discharges into the region of the Gulf of Mexico known as the Big Bend. This region of

Florida has a relatively low population density; however, there have been significant

increases in a variety of agricultural activities in the river basin. Nitrogen-enriched run-

off from these agricultural areas filters into the groundwater because of the porous nature

of the karst sediments characteristic of the region. Ultimately, these increases in

groundwater nitrogen are manifested as higher nitrate concentrations in the river, due to

numerous spring inflows. Nitrate levels within the Suwannee River are increasing and

concentrations near the mouth and in the upper reaches of the estuary now regularly

exceed 1 mg/L (Phlips and Bledsoe, 1997). This has brought on widespread concern

about the potential consequences of cultural eutrophication of the region on the

ecological health of the river and the coastal waters of the Big Bend.

Suwannee River and Estuary

The Suwannee River is a blackwater, tidally influenced river with its origin in the

Okefenokee Swamp in Georgia. The river is approximately 394 km in length, flows

southwest through Florida, and discharges into the Gulf of Mexico just north of Cedar








Key. Tributaries include the Alapaha, Withlacoochee, and Santa Fe Rivers. At the

mouth of the river there is a delta region which is characterized by a network of intertidal

and subtidal oyster reefs (Wolfe and Wolfe, 1985).

The geographical features of the Suwannee River and the Okefenokee Swamp

include flat terrace, the Trail Ridge sand barrier, and the Hawthorne Formation (Malcom

et al., 1989a). There are also shallow clay lenses near the headwaters of the river. Much

of the river and its watershed are underlain by karst limestone, allowing nutrients to leach

into the aquifer and ultimately enter the Suwannee River through the groundwater springs

along its banks (Crandall et al., 1999; Bledsoe and Phlips, 2000). Water is mixed

between the river and aquifer primarily through springs and diffuse groundwater seepage

(Pittman et al., 1997).

The water quality of the upper Suwannee River is indicated by low pH, low

concentration of dissolved inorganic solids, and high concentration of dissolved organic

substances, especially fulvic acids (Malcolm et al., 1989a). The lower Suwannee River

maintains a higher pH (6 to 9) (Wolfe and Wolfe, 1985). The source of the humic

substances in the water is predominantly fresh litter, leaf, and root exudates, and leaf

leachates. Very little of the colored dissolved organic matter (CDOM) is due to older and

more slowly decaying peat (Malcolm et al., 1989a). The concentration of these humic

substances has been shown to be an order of magnitude greater than that in most natural

stream waters. The dissolved organic carbon concentrations are in excess of 25 mg/L

(Malcolm et al., 1989b). High nutrient concentrations are also present in the river due to

the large amounts of fertilizer entering the system through groundwater and overland

flow (Suwannee River Water Management District, 2003).








The climate along the river is characterized by long, warm summers and short, mild

winters (Malcolm et al., 1989a; Crandall et al., 1999; Katz et al., 2001). Peak mean daily

discharge in the river usually occurs in March or April, and September due to continental

frontal systems (Crandall et al., 1999); however, discharge rates are generally fairly

uniform throughout much of the year (Malcolm et al., 1989b). A large source of water

for the Okefenokee Swamp, and hence the Suwannee River, is rainfall. Overland flow

and groundwater (via numerous springs) also contribute to the amount of water flowing

through this system (Wolfe and Wolfe, 1985; Crane, 1986). During the months of heavy

rains, the river flows more rapidly, and there is generally a higher organic content as a

result of drainage from the swamp and watershed to the river. When precipitation is low,

water is contributed to the river through springs and diffuse seepage fed by the Floridan

Aquifer (Crane, 1986).

There is much less land development and point source pollution in this river and its

plume than in most other coastal regions in Florida (Bass and Cox, 1988). Major land

uses in the watershed include forestry and agriculture (row crops, dairy, poultry, swine

farming operations, and pasture) (Katz et al., 2001). In 1995, wetlands comprised about

2% to 36% of the land use in Suwannee and Lafayette Counties (Katz et al., 2001).

Asbury and Oaksford (1997) characterized the watershed in the Suwannee basin as

50.4% forested, 15.9% wetland, 31.2% agriculture, and 0.8% residential. The land

immediately surrounding the river is predominantly used for pine forestry operations.

Fertilizer from pine forestry operations and waste material from dairy practices are

thought to be a significant source of non-point source nutrient loading to the river

(Asbury and Oaksford, 1997). The Suwannee River could potentially be highly








influenced by these large amounts of nitrogen coming into the system. The clam beds

and oyster reefs at the mouth of the river and in the estuary are harvested periodically

throughout the year. Increased nutrient loads may negatively affect these and other

species, although elevated nutrient concentrations can lead to high production of

phytoplankton. This production can lead to low dissolved oxygen concentrations, and, in

turn affect production and survivorship.

Nutrient Loading, Especially Nitrogen

River discharge provides a significant source of nutrients to estuaries; however this

can be considered contamination as well as a pathway for increased productivity. The

potential impact of a contaminant such as nitrogen in the environment depends not only

on the concentration and mobility of the species, but also on its bioavailability (Suffet

and MacCarthy, 1989). Increased nutrient loads can lead to the eutrophication of surface

waters, and high nitrate concentrations (>10 mg/L) especially pose a possible health risk

in drinking water (Asbury and Oaksford, 1997). Other possible effects include harmful

cause algal blooms and low dissolved oxygen concentrations, which can have detrimental

effects on the entire ecosystem.

Sources of nutrients in the Suwannee River include atmospheric deposition,

fertilizer, animal waste, and septic discharge, with nitrogen from fertilizer and animal

wastes predominating (Asbury and Oaksford, 1997). Asbury and Oaksford (1997)

estimated the nitrogen stream load per year in the Suwannee River as 9,700,000 kg/yr and

476 (kg/yr)/km2, and found that organic nitrogen was the most abundant nitrogen

compound. Nitrogen exists in the river largely in the form of NO3; however, nitrogen is

also a trace constituent in aquatic humic substances. According to Thurman and

Malcolm (1989), the nitrogen content of fulvic acids varies from 0.5 to 1.5 percent;








however aquatic humic acid has twice as much nitrogen as fulvic acid. In the Suwannee

River, the concentration of nitrogen in fulvic acid is 0.56 percent, and in humic acid it is

1.08 percent (Thurman and Malcolm, 1989). Frazer et al. (2002) found that nitrate

discharged from the lower Suwannee River was quickly diluted and/or assimilated as it

entered the Gulf of Mexico.

Agricultural activities and other land uses have impaired the quality of spring

waters by contributing large quantities of nutrients to groundwater recharge in many parts

of the world (Katz et al., 2001). During the past 50 years, nitrate-N concentrations in

groundwater discharging from several springs in the middle Suwannee River Basin have

increased from near background concentrations (less than 0.1 mg/L) in groundwater to

more than 5 mg/L (Katz et al., 2001). However, nitrate concentrations in the water from

four springs in Suwannee County generally have remained constant or have decreased

slightly in the last few decades following a decrease in the use of fertilizers (Katz et al.,

2001).

Many different factors in an ecosystem such as the Suwannee River impact the

nutrients once they enter the system, and nutrient concentrations can change with time.

Rates of change are a function of mixing and transport, emission rate, sinks, and

reactivity (Suffet and MacCarthy, 1989). Chemical influences on nutrients include

physiochemical reactions of the compounds (e.g., sorption, coagulation, acid-base

interactions, and complexation reactions), and chemical changes (e.g., oxidation,

reduction, hydrolysis, and photochemical reactions). Physical influences include

transport and dispersal. Biological influences include uptake and mineralization by

organisms and metabolic changes associated with receptor organisms and food web








interactions (Suffet and MacCarthy, 1989; Horrigan et al., 1990). Nutrients from

fertilizers will be taken up and used by organisms, such as algae, which will, in turn, be

consumed by higher trophic levels in river and estuarine systems. Nutrient flows through

these types of ecosystems have been studied in great detail (e.g., Kaul and Froelich, 1984;

Horrigan et al., 1990; Wada and Hattori, 1991; Schelske and Hodell, 1995).

Nitrate and ammonium are taken up by microbes, algae, and macrophytes, but

organic particles are generally consumed by organisms such as clams and oysters in

estuarine environments. As previously stated, there is a small amount of nitrogen present

in humic substances. Clams and oysters can readily consume phytoplankton (a known

source of good quality food), but organic nitrogen aggregates that are formed from

dissolved compounds have also been found to be an important source of nitrogen for

these consumers (Alber and Valiela, 1996).

Clam and Oyster Ecology

At the mouth of the Suwannee River and in the estuary oyster reefs are common.

In addition, there are a number of lease sites where hard clams are allowed to grow for

harvest. The predominant species are Crassostrea virginica and Mercenaria mercenaria.

The oysters, Crassostrea virginica, are well suited to estuarine conditions. They can

tolerate wide ranges of temperatures, salinity, turbidity, and dissolved oxygen. They can

also generate their own substrate by producing their own shells to which they attach (Day

et al., 1989; Ruppert and Barnes, 1994). These organisms are typically limited by space

(Day et al., 1989). Oysters are suspension feeders (pump and filter a large quantity of

water to obtain sufficient food of the proper quality), and it is important that the quality

(nutrient content) of the food be very high to achieve maximal growth. Adult oysters

actively pump (through ciliary action) several liters of water per hour across their gills








(Day et al., 1989; Ruppert and Barnes, 1994). Therefore, dense populations of

suspension feeders can become limited by food in areas with a lack of circulation (Day et

al., 1989). Ammonia and phosphorus are regenerated by these organisms as a

consequence of excretion and fecal production (as subsequent remineralization). Oyster

harvesting is an important industry for Florida's economy, and oysters also provide a

source of food for birds and several aquatic organisms (e.g., sea anemone, crabs,

flatworms, etc.) (Dunning and Adams, 1995; Colson and Stunner, 2000; Newell et al.,

2000).

The clam, Mercenaria mercenaria, is also an important food source for humans,

some birds, and aquatic organisms. It is one of the most important commercial bivalve

species on the eastern coast of the United States, and the Suwannee River estuary is the

most economical area to grow these clams in the natural environment (Pfeiffer et al.,

1999; Colson and Sturmer, 2000). They feed in a similar manner to the oysters

(suspension feeders), and as clams grow and population numbers increase, food

requirements grow exponentially (Ruppert and Barnes, 1994; Pfeiffer et al, 1999).

There are three trophic pathways by which clams and oysters might ingest and

subsequently assimilate detritus: (1) via direct uptake of dissolved organic matter (which

is released by both live and decaying producers), (2) ingestion of particulate detritus, and

(3) ingestion of organic aggregates (Alber and Valiela, 1994a). Alber and Valiela

(1994a) have also found that bivalves are capable of taking up bacteria. In a study by

Crosby et al. (1990), the oyster, Crassostrea virginica, was found to assimilate refractory

Spartina alterniflora-derived detritus with an efficiency of 2.7 percent, whereas material








that was colonized by bacteria was assimilated with an efficiency of 10.3 percent. These

findings suggest that bacteria can actually enhance the quality of food for the consumers.

Suspension feeders encounter food supplies of varying nutrient quality, quantity,

and size. Many bivalves are able to alter their capture rates and strategies to account for

lower quality food. Ward et al. (1997), for example, showed that oysters can select living

particles from non-living detritus on the gills. Ward et al. (1998), in a subsequent study,

determined that in the oyster, Crassostrea virginica, the ctenidia are responsible for

particle sorting while the labial palps have an accessory role in particle selection. There

have been several studies with bivalves demonstrating the ability to sort particles based

on size (e.g., Vahl, 1972; Stenton-Dozey and Brown, 1992; Defossez and Hawkins, 1997;

Raby et al., 1997; Brillant and MacDonald, 2000).

Humic Substances

Organics within a river system can be allochthonous (produced outside of the

system) or autochthonous (produced within the system). Allochthonous organic

materials include humic substances. The dissolved organic matter (DOM) in an average

river is typically composed of about 50% humic substances; however DOM is highly

variable depending on source of organic matter, temperature, ionic strength, pH, major

cation composition of the water, sorption processes, and microbial degradation processes

(Leenheer and Crou6, 2003; Schwarzenbach et al., 2003). In the case of the Suwannee

River, a blackwater river, there are high concentrations of dissolved humic substances in

the water, ranging up to 60 mg/L at its source. The water in the Suwannee River is dark

and acidic due to the high amounts of humic substances from decomposition of swamp

vegetation (Malcolm et al., 1989a). Much of this humic material originates in the








Okeefenokee Swamp. Along the river channel there are many pine forests which also

contribute to the high concentration of dissolved humic acids.

Humic substances are ubiquitous organic materials in the environment that result

from the decomposition of plant and animal residues (Suffet and MacCarthy, 1989;

MacCarthy, 2001). They can be expressed as dissolved organic carbon (aqueous

materials that pass through a 0.45-am filter); however, some of these materials may be in

colloidal form rather than in solution. Humic substances can assist with the transport of

metals through complexation and ion-exchange mechanisms, depending on the redox

state of the metal ions, leading to either solubilization or immobilization of the metals.

Humic substances also interact with nonionic compounds (pesticides and other river

contaminants) via sorption, causing the immobilization of such compounds in

sedimentary organic matter (Schwarzenbach et al., 2003). Humic substances in solution

consist of amino acids, sugars, various aliphatic and aromatic acids, and a variety of more

complex organic compounds. They can be somewhat polar in that they contain numerous

oxygen-containing functional groups including carboxy-, phenoxy-, hydroxy-, and

carbonyl- substituents (Stumm and Morgan, 1996; MacCarthy, 2001; Schwarzenbach et

al., 2003). This allows them to interact with water-soluble compounds. However, they

also consist of nonpolar constituents which allow them to interact with water-insoluble

compounds (Calace et al., 1999). In soils, sediments, and suspensions, humic substances

are often bound with inorganic materials (i.e., clays and metals) (Suffet and MacCarthy,

1989; Meier et al., 1999; Schwarzenbach et al., 2003).

Humic substances are typically fractionated into the following groups: humic acid -

the fraction of humic substances that is not soluble in water under acidic conditions








(pH<2) but is soluble at higher pH values; fulvic acid the fraction of humic substances

that is soluble in water under all pH conditions; and humin the fraction of humic

substances that is not soluble in water at any pH value. There are different concentrations

of each of these groups in different river systems. Studies show that typically 90% of

dissolved humic substances is fulvic acid and 10% is humic acid (Suffet and MacCarthy,

1989; Hautala et al., 1998). In the Suwannee River, fulvic acids are most dominant

(Malcolm et al., 1989a).

Humic substances can be a food source for organisms in river and estuarine

environments. Detritus humicc substances) is generally a year-round source of food and

may be more abundant than phytoplankton at times (Alber and Valiela, 1996). However,

it is also found to be very recalcitrant to biological and chemical degradation (Wang et

al., 2000). Therefore, humic substances are often poor quality food (Alber and Valiela,

1994a). Before many humic substances can be eaten, some detritivores depend on

microbes to decompose and alter the quality of the detritus by increasing both its

available nitrogen content (see below) and availability to consumers (Alber and Valiela,

1994a). The dissolved organic matter is, therefore, a growth substrate for bacteria (Sun et

al., 1997). It has been shown that bacteria use dissolved organic matter at specific size

ranges (small>medium>large); however higher molecular weight dissolved organic

matter (as humic substances) is generally most available (Engelhaupt et al., 2002). Sun et

al. (1997) found that bacterial growth was positively correlated with H:C and N:C ratios,

and negatively correlated with O:C ratios. Colonization by bacteria can enhance the

quality of the food for consumers through metabolism of larger nitrogen containing

molecules to smaller, more available forms.








The dissolved organic carbon concentration in colored surface waters is extremely

variable and typically ranges from about five to more than 50 mg of carbon/L (Suffet and

MacCarthy, 1989). The fraction of the total dissolved organic carbon that is in the form

of humic substances varies considerably and can be up to 80% (Suffet and MacCarthy,

1989). According to Wang et al. (2000), the nitrogen contained in humic substances can

be released as low molecular weight species through photochemical processes or

reactions, and therefore becomes more readily available for biological use. They found

that solar irradiation of dissolved organic matter results in conversion of recalcitrant

dissolved organic nitrogen to ammonium, which is more readily assimilated by microbes.

These photochemical reactions may play a significant role in the cycling of the nitrogen

through the ecosystem.

Flocculation

The terms flocculant and aggregate, often used interchangeably refer to "fragile,

amorphous, macroscopic or microscopic particles consisting of organic and inorganic

material" (Zimmerman-Timm, 2002; p. 197). Aggregates are ubiquitous in moving

surface water (rivers, tidally-influenced rivers, and estuaries); however, they have been

found to be more concentrated in an estuarine environment where fresh water meets salt

water, and where there is wave influence and turbulence. The main characteristics that

affect organic aggregates in moving water have been presented by Zimmerman-Timm

(2002) as hydrological regime, waves, shipping, channel deepening, precipitation,

stagnation, transport, aggregate composition, organic content, size, sedimentation,

saltwater interaction, and resuspension.

The hydrological regime affecting aggregates includes current velocity, horizontal

transport, wave action, and discharge rate. According to Berger et al. (1996) and








Zimmerman (1997), increasing current velocity and freshwater discharge rate result in a

large amount of aggregates in the water column. With a higher density of aggregates in

the water column, however, the probability of particle contact is more likely, and an

increase in the number of aggregates is unlikely. Horizontal transport and water

residence times are other hydrological factors that can affect aggregates in most running

surface water systems. The water residence times in estuaries are influenced by

interactions between tides and water flow, and circulation patterns (Day et al., 1989;

Zimmerman-Timm, 2002). Wave action also influences the generation of aggregates, as

waves can stir up the bottom sediment, causing particles to interact with each other and

aggregate. In areas of stagnation, however, low amounts of aggregates are generally

present (Zimmerman-Timm, 2002). In these locations, particles settle to the bottom as

there are few physical disturbances to bring them back into the water column.

The composition of aggregates can be made up of organic and inorganic,

allochthonous and autochthonous materials. According to Zimmerman-Timm (2002), the

composition of aggregates may include non-living geologic components (clays, mica,

quartz, etc.), anthropogenic components (organic and inorganic contaminants), non-living

biogenic material (silica, calcite, etc.), attached organisms (algae, bacteria, fungi, etc.),

macrophytes, detritus (dead and dying organic material), and fecal pellets. Conners and

Naiman (1984) have shown that 85-97 percent of the particulate organic carbon in large

rivers is autochthonous in nature. Suffet and MacCarthy (1989) found that, in most

cases, higher humic substance concentrations correspond to higher concentration of

aggregates. The aggregates in the Suwannee River consist predominantly of humic

substances brought into the system from the Okefenokee Swamp. However, clays and








bacteria, as well as salinity, might have a strong influence on the formation of the

aggregates (Meier et al., 1999). Algae and bacteria hold the aggregates together with

sticky mucous substances. Kepkay and Johnson (1988) found that after 15 minutes of

bubbling coastal seawater, DOC was reduced by 43% and the production of organic

particles increased after surface coagulation initiated a rapid bacterial response. Alber

and Valiela (1994b) showed that aggregates from dissolved organic matter released by

macrophytes are biotic in nature and contain large numbers of bacteria. Alber and

Valiela (1994b), in studying the carbohydrate, protein, lipid, carbon, and nitrogen

composition of aggregates, macrophytes, and bacteria, showed also that the biochemical

composition of the aggregates is closer to that of bacteria than the macrophytes.

Flocculated organic aggregates have different forms and sizes, all of which are

greater than or equal to 0.45 Im. Size is important when determining transport properties

(settling and movement through a system) (Jackson and Burd, 1998). Three size classes

of these flocculants have been determined by Alldredge and Silver (1988) and Perret et

al. (1994) and include macroscopic aggregates (>150 pm), microaggregates (<150 pm),

and submicron particles (<1 ljm). Typical sizes of aggregates are 5,000 aim and smaller

(Zimmerman-Timm, 2002). Size of the aggregates influences how quickly they will

settle out. Aggregates in the 2,400 to greater than 5,000 Am size range settle at an

average of 25 times more rapidly than single algal cells (Alldredge and Gotschalk, 1988).

Larger size aggregates can be easily broken down by mechanical disruption (waves,

wind, mixing, etc.), consumer interaction, and microbial decomposition. Physical motion

breaks down aggregates near the surface in rivers (Argaman and Kaufman, 1970; Parker

et al., 1972). In the Elbe, the River Rhine, and the Zaire River Estuary, a decrease in








aggregate size has been found to occur with an increase in salinity due to decreased

colonization by microbes and bacteria (Zimmerman-Timm, 2002). Larger size

aggregates are also more accessible to larger consumers that are less efficient at

consuming small particles (Alber and Valiela, 1994).

The mechanisms underlying the formation of aggregates are often debated.

Although flocculation of dissolved organic matter has been shown to occur in many

estuarine ecosystems, it has not been proven if the cause of this flocculation is solely salt

induced, bacteria induced, physically induced, or a mixture of these. Many argue that it

is a complex process controlled by several variables (O'Melia, 1987; Eisma, 1993;

Stumm and Morgan, 1996) including particle concentration, stickiness of the particle

surface, velocities, and probability of attachment. The higher the concentration of

particles, the more aggregates will be formed. If the concentration is too low,

flocculation will be less likely to occur because the collision frequency will be too low

(Zimmerman-Timm, 2002).

Physical and chemical processes that have been found to produce aggregates

include Brownian motion, shear forces, differential settling, filtration, bubbling surface

coagulation, precipitation, adsorption, attractive and repulsive properties, bridging with

divalent cations, and spontaneous coagulation of dissolved organic matter. Brownian

motion is the movement and collision of particles smaller than 8 im under the influence

of heat energy induced motion of water molecules (Eisma, 1986; Zimmerman-Timm,

2002; Schwarzenbach, 2003). Shear forces refers to the strength of laminar and turbulent

shear which determines the frequency and the push of particles (Jackson and Burd, 1998;

Zimmerman-Timm, 2002). Differential settling is a mechanism that is dependent on








aggregate composition, size, and abundance. Larger particles are formed as the larger

and more rapidly sinking particles interact with the smaller particles during vertical

transport (Zimmerman-Timm, 2002). Gas bubbles can be released from sediments or

formed by waves breaking at the surface. They will rise through the water column until

they burst or collapse. Particles can concentrate along the border of the bubble, and can

then be transported as aggregates (Johnson, 1976; Kepkay and Johnson, 1988).

Attractive and repulsive surface properties refer to the charge on particles and depend on

the size, composition, and chemical coating on the particle. Most particles are negatively

charged at their surface because the organic material has many carboxyl or hydroxyl

groups associated with it (especially humic substances) (Suffet and MacCarthy, 1989;

Zimmerman-Timm, 2002). Positive cations (such as those found in saline waters) can act

as chemical bridging agents, enhancing the attraction properties of electronegatively

charged particles. This is why salt-induced flocculation is one explanation for the

aggregates found in rivers where fresh water enters salt water.

Schwarzenbach et al. (2003) presented a discussion on how the presence of the

predominant inorganic ionic species found in natural waters generally decrease the

aqueous solubility, or increase the aqueous activity coefficient, of nonpolar or weakly

polar organic compounds. The magnitude of this effect is termed "salting-out". An

empirical formula established by Setschenow (1889) (as cited by Schwarzenbach et al.,

2003) is presented to support this idea. This formula relates organic compound

solubilities in saline aqueous solutions to those in pure water by relating the effectiveness

of a particular salt or combination of salts to the change in solubility of a given








compound (in terms of a salting constant). It shows that the "salting-out" effect increases

exponentially with increasing salt concentration (see below).

Csaiw,sa = Csaiw 10-Ki[salt]to (1-1)

In the above equation, Csaiw,sat is the organic compound solubility in saline aqueous

solutions, C"ai is the organic compound solubility in pure water, [salt]otal is the total

molar salt concentration, and Ksi is the Setschenow, or salting constant (Schwarzenbach

et al., 2003). This can also be presented in terms of activity coefficients:

_w, at = w* 1+Ksi[salt]tot (1-2)

This equation shows that -, ,,lt increases exponentially with increasing salt

concentration. Essentially, predominant ionic species, such as salts from sea water,

generally decreases the solubility of nonpolar or weakly polar, such as natural dissolved

organic matter.

Some experiments have been performed to produce aggregates in a laboratory

setting. Sholkovitz (1976), in a classic study, produced aggregates at varying salinities

from 0%o (parts per thousand) to 30%o by mixing filtered river water and sea water. He

found that no more changes were noticeable in color or concentration of flocculants after

about 159%o to 20%o, naming this the salinity of maximum removal of dissolved organic

carbon. Other elements were present in his river water sample that could have had an

effect on the flocculants, including aluminum and calcium. Fox (1983) attempted to

repeat (with minor differences) the study by Sholkovitz. In two of three estuaries studied,

he found that salt-induced removal of dissolved humic acid was insignificant. Eisma

(1986) also determined that salt induced flocculation plays only a minor role, and that

flocs are formed more by a combination of forces including viscous flow, gravity, and








Brownian motion. Alber and Valiela (1994) produced aggregates in the laboratory using

dissolved organic matter from different macrophyte species. They bubbled the samples

and the formed aggregates ranged in size from a few micrometers to 500 jim across.

Esteves et al. (1999) concluded that mixing freshwater and seawater in a laboratory

setting removes 5% to 10% of dissolved organic matter as particulate matter. Thill et al.

(2001), in studying water from Rhone River, France, found that particle aggregation and

adsorption are not an instantaneous process. The Rhone river particulate matter had a

poor average reactivity regarding salt induced flocculation. Reaction kinetics depend on

the electrostatic repulsion between particles, which is dependent on the salinity.

However, when shear collision dominates a system, the kinetics are proportional to the

particle volume fraction. They also stated that higher particle concentrations favor the

faster formation of aggregates (Thill et al., 2001).

Field studies have also shown the production of aggregates. A study by Del

Castillo et al. (2000) found that flocculation of dissolved organic matter in the Peace

River, Florida occurred at the mixing interface of salt and fresh water. Del Castillo and

colleagues hypothesized that the importance of the salt induced flocculation might be

overshadowed by large concentrations of CDOM in the mouth of the river. To test this

hypothesis, the possible effects of flocculation were modeled, and it was found that 11%

of the dissolved organic matter was lost and 20% of the color was removed during

flocculation as reported by Sholkovitz et al. (1976). Milligan et al. (2001) found that in

the ACE Basin, South Carolina, suspended material was dominated by high

concentrations of flocculated sediment. They stated that this was probably due to a

suppression of turbulence and salinity gradients. In the Rhone River, France, salt induced








flocculation was found to be a minor factor unless mixing conditions were adequate for

the formation of floes (Thill et al., 2001).

The use of organic aggregates as a food resource by consumers has been

hypothesized by several investigators (e.g., Alber and Valiela, 1994; Zimmerman-Timm,

2002). However, this hypothesis has not been adequately addressed. Alber and Valiela

(1996) found that in the aggregate detritus pathway, dissolved organic matter released by

primary producers is transformed into organic aggregates, which are then ingested by

consumers (in this case, bivalves). They also found that the aggregates could meet a

substantial portion of the nutritional requirements of bay scallops (Argopecten irradians)

in the field. Other experiments have also shown that benthic organisms are able to ingest

aggregates as a food source. The food quality of the aggregates can be characterized by

their composition. Alber and Valiela (1994) found that aggregates have lower C:N

values and are higher in protein than the macrophyte-derived detritus in their study,

explaining why aggregates are more readily consumed. The ingestion of aggregates as a

food source forms a link between the microbial food web and the higher trophic levels.

As bivalves consume the aggregates, they are also consuming the bacteria associated with

the aggregates, thus repackaging the smaller microbial particles.

Collection of aggregates can be troublesome. Filtration and centrifugation have

been shown to destroy the typical structure of the fragile aggregates, producing an

amorphous mass of organic and inorganic material (Thill et al., 2001; Zimmerman-Timm,

2002). It can be difficult to analyze aggregates as well. Laboratory produced aggregates

are often different from field aggregates because the conditions of their formation are

somewhat different. In the natural environment, there are higher numbers of organisms








and larger size classes than those produced in the lab, and the physical parameters are not

completely representative. However, it is worthwhile to construct laboratory experiments

to mimic field conditions to get an understanding of different mechanisms that may cause

the formation of aggregates.

Stable Carbon and Nitrogen Isotopes as Tracers of Material Transfer and Energy
Flow

Anthropogenic perturbations can alter the pathways of material transfer and energy

flow through an ecosystem. For example, excess fertilization in a watershed can alter the

abundance and flow of elements such as nitrogen in a stream within that watershed.

Stable carbon and nitrogen isotope ratios (5sN) can be used to follow the changes caused

by excessive fertilization and show which processes or components are altered (i.e.

foodweb, trophic changes, etc.), as well as determine the source of carbon and nitrogen

fueling production of consumers (Mariotti et al., 1984; Owens, 1985; Peterson and Fry,

1987; Fry, 1988; D'Avanzo et al., 1991; Wada et al., 1991; Holmes et al., 1996; Riera,

1998; Fry, 1999; Hamilton et al., 2001; Lehmann et al., 2001; McKinney et al., 2002).

Owens (1987) collected data available on the distribution of '5N for various

environments. In estuarine systems, the average s15N value of all collected materials was

4.6 2.0 for 199 observations. The average stable nitrogen isotope signature for all

materials in freshwater was 4.3 2.7 for 64 observations, and the terrestrial average was

3.9 + 3.1. Differences in ecosystems provide a possible reason for using "SN as a tracer.

The use of stable isotopes to address issues related to energy flow is increasing because

stable isotope data can contribute both source-sink data (tracer) and process information

(Peterson and Fry, 1987; Fry, 1988; Montoya et al., 1990; D'Avanzo et al., 1991; Holmes








et al., 1996; Riera, 1998; Hamilton et al., 2001; Lehmann et al., 2001; McKinney et al.,

2002).

The stable isotopic signature of inorganic and organic nitrogen provides an

integrative tool for studying the sources of nitrogen supporting production in an

ecosystem (Valiela et al., 1997). The stable carbon isotope signature provides a tool for

determining the source of organic matter in these ecosystems. Most systems have several

inputs of organic carbon as a food source, e.g. C3 terrestrial plant material (8'3C = -23 to

-30%o), seagrasses (-3 to -15%o), macroalgae (-8 to -27%o), C3 marsh plants (-23 to -

26%o), C4 marsh plants (-12 to -14%o), benthic algae (-10 to -20%o), and marine

phytoplankton (-18 to -24%o) (Fry and Sherr, 1984; Michener and Schell, 1994). The

major source of terrestrial-derived DOM is vascular plants, which are confined

essentially to land and characteristically contain high concentrations of recalcitrant,

nitrogen-free biomacromolecules such as lignin and tannin (Hedges et al., 1997). These

plants have distinct stable carbon isotope compositions and can be used as a biomarker of

terrestrial origin (Fry and Sherr, 1984; Hedges et al., 1997). There can be, however,

some overlap of stable isotope signatures (e.g., C3 terrestrial plants, C3 marsh plants, and

marine phytoplankton). Detailed investigations of individual ecosystems should be

studied to differentiate sources of organic carbon.

The implications for the use of stable nitrogen and carbon isotopes in food web

investigations are also significant (DeNiro and Epstein, 1981; Fry, 1988; Wada et al.,

1991; Canuel et al., 1995; Cabana and Rasmussen, 1996; Vander Zanden and Rasmussen,

1999; Jepsen and Winemiller, 2002). DeNiro and Epstein (1981) found that the 6'5N of

organisms reflects the 1'5N signature of the diet; however, the animal is generally








enriched in 5N, and isN values are approximately 3 to 5%o greater than the diet. This is

mainly due to excretion of isotopically light nitrogen in urine (Minagawa and Wada,

1984; Owens, 1987; Peterson and Fry, 1987; Fry, 1988; Wada et al., 1991; Lajtha and

Michener, 1994; Cabana and Rasmussen, 1996; Gue et al., 1996). Stable carbon isotopes

of animals reflect those of the diet within approximately 1%o (DeNiro and Epstein, 1978;

Peterson and Fry, 1987; Michener and Schell, 1994; O'Donnell et al., 2003). Animals

may be isotopically enriched relative to their diet as a consequence of the preferential loss

of 12CO2 during respiration, the preferential uptake of 13C compounds during digestion, or

metabolic fractionation during synthesis of different tissue types (DeNiro and Epstein,

1978; Rau et al, 1983; Tieszen et al., 1983; Fry et al., 1984). A determination of an

organisms trophic status can be facilitated by the simultaneous measure of 6'N and "3C

signatures (Peterson et al., 1985). Stable carbon and nitrogen isotopes are a useful

method for following the flow of energy in a system such as the Suwannee River and its

estuary.

Many chemical and physical processes are accompanied by significant isotopic

fractionation which results in an enrichment or depletion of the heavy isotope (Peterson

and Fry, 1987; Wada et al., 1991; Lajtha and Michener, 1994). Fractionation can occur

during kinetic and equilibrium processes. Equilibrium isotope effects are common where

chemical exchange occurs between two molecules, whereas kinetic isotope effects are

involved with more complex reactions (Peterson and Fry, 1987). In biochemical

processes involving nutrient uptake, the substrate is enriched and the product is depleted

in heavy isotopes when the substrate pool is infinite (Montoya et al., 1990). This is due

to the fact that autotrophs, e.g. phytoplankton, preferentially assimilate lighter nitrogen.








In the process of nitrogen fixation, however, the 1'SN values are near 0%o. In the

processes of nitrification and denitrification, residual ammonium-N and nitrate-N,

respectively, are enriched with heavy nitrogen. According to Owens (1987), there is a

large fractionation effect associated with denitrification. The residual nitrate substrate

exhibits isotopic enrichment in situ, however, a large pool of dissolved N2 can preclude

any significant depletion of the accumulated product (Owens, 1987). With regard to

animals, preferential excretion of 5N-depleted nitrogen has been found, generally in the

form of urea and ammonia, resulting in and isotopic enrichment of the animal tissue

(Minagawa and Wada, 1984).

Most nitrogen is present as N2 gas in the atmosphere with an isotopic composition

essentially constant at 0%o (Peterson and Fry, 1987). Nitrogen in the rest of the biosphere

has a typical isotopic composition around 0%o as well (ranging from -10 to 10%o). The

nitrogen cycle, however, involves processes with notable fractionation effects that affect

i'5N signatures of nitrogen pools. For example, there is a cumulative faster loss of '4N

than 15N during particulate nitrogen decomposition in soil and water, resulting in 85N

increases of 5 to 10%o with increasing depth (Peterson and Fry, 1987). Nitrification and

denitrification in the oceans involve substantial isotope effects. As animals are on

average 3 to 5%0 heavier than dietary nitrogen (Minagawa and Wada, 1984; Owens,

1987; Peterson and Fry, 1987; Fry, 1988; Wada et al., 1991; Lajtha and Michener, 1994;

Cabana and Rasmussen, 1996; Gu et al., 1996), nitrogen isotopic values may increase by

10 to 15%o in many food webs, due to the presence of three to five successive trophic

transfers (Peterson and Fry, 1987). Volatization of nitrogen also causes fractionation

effects because the lighter isotope (14N) is more volatile than the heavier isotope (15N).








For example, Flipse and Bonner (1985) found that the average 615N values of fertilizers

was 0.2%0 (potato farm) and -5.9%0 (golf course), and the average 3 5N values of the

groundwater nitrate in these systems were 6.2%o and 6.5%0, respectively. It was

determined that higher 5"N values of groundwater nitrate were caused by isotopic

fractionation during the volatile loss of ammonia from nitrogen applied in reduced forms.

The elements carbon, nitrogen, sulfur, hydrogen, and oxygen all have more than

one stable isotope and their relative abundances can be measured with a mass

spectrometer (Peterson and Fry, 1987). The isotopic compositions of different materials

will change in predictable ways as elements cycle through the biosphere and also as a

consequence of isotopic fractionation (Owens, 1987; Peterson and Fry, 1987; Lajtha and

Michener, 1994). According to Owens (1987), however, these changes aren't always

apparent due to a degree of overlap between different types of samples. Therefore, a

combination of elements (e.g. carbon, nitrogen, and sulfur) and their isotopes are often

used. For example, Peters et al. (1978) found a high correlation between tSN and 63C

values in sedimentary organic matter. Peterson et al. (1985) found that the use of a

combination of the stable isotopes of sulfur, carbon, and nitrogen helped to delineate food

sources and characterize the trophic structure in an estuary where there was more than

one source of food for the ribbed mussel (Geukensia demissa). Gu et al. (1996) used

stable carbon and nitrogen isotopes to identify food sources and describe trophic transfer

pathways within a lake ecosystem. Vander Zanden and Rasmussen (1999) also used

stable carbon and nitrogen isotopes as indicators of trophic structure within a freshwater

lake system, and determined that 5N values of higher consumers could not be used

alone because of the high variability of 65N values of primary consumers. Carbon and








nitrogen element ratios might also assist in understanding 5N values. For example, Guo

and Santschi (1997) studied the elements carbon, nitrogen, and sulfur, as well as isotopic

composition of colloidal organic matter to investigate sources and turnover rates of

dissolved organic matter in Chesapeake Bay and Galveston Bay, USA.

A number of studies have been done on nitrogen isotopes in freshwater, estuarine,

and marine ecosystems. Wada et al. (1981) studied highly enriched algal felt in saline

and non-saline lakes in the Antarctic. The epibenthic algae in this system were depleted

in '5N as a result of isotopic fractionation associated with slow growth rates in low light

and a high nitrate environment. The source of nitrogen for the algae was avian excreted

ammonium, which had a large fractionation effect during volatization of ammonium.

Therefore the nitrogen available to the algae was likely to be highly enriched (Wada et

al., 1981). Owens (1987) presented data from numerous studies and found that the 65'N

signature ofphytoplankton ranges from 3%o to 12%o. It was predicted that phytoplankton

in the field would tend to exhibit a lower 15N content because of fractionation effects

(Owens, 1987). In the turbidity maximum (area where material is periodically

resuspended from the surface sediments) of the Tamar River estuary, Britain, Owens

(1985) showed a distinction between at least two different populations of particles using

'"N analyses. In the marine end of the estuary (salinity 33.8%0), the 6'iN values were

4.96 1.03%o, in the freshwater end, the 8'5N values were 2.29 2.23%o, and

intermediate 6i5N values ranged from 1.79 1.63%o to 14.73 0.7%0. The highest values

were found in the turbidity maximum, due to the longer residence time (and thus,

increased microbial decomposition) of the particles at this site (Owens, 1985). The low

815N values (close to 0%o) were similar to values typical of terrestrial material, which








reflects the dominance of atmospheric nitrogen (Owens, 1985). Wada et al. (1991) also

found this to be the case for particulate organic matter in Otsuchi River and its receiving

waters. Low 8'SN values (0.2 to 0.7%o) were found in the particulate matter of the upper

reaches of the river, while high 615N values (6.4 1.8%o) were found in the bay (Wada et

al., 1991). Sigleo and Macko (1985) also reported similar findings for suspended

particulate material in the Patuxent Estuary, Maryland.

Mariotti et al. (1984) found substantial spatial differences in the 15N content of

ammonium and nitrate in particulate material in the Scheldt Estuary, France. The

upstream zone was depleted in dissolved oxygen and was a site of denitrification (low

concentration of nitrate and high concentration of ammonium). In this zone, the 615N of

ammonium was 10%o and the 'SN of nitrate was 18%o. However, in the lower estuary,

where dissolved oxygen was high and nitrification was active, the 68"N values were

reversed (nitrate 2 to 5%o and ammonium 29%o) (Mariotti et al., 1984). This indicates

that the nitrogen cycle is very important when interpreting '5N data. Katz et al. (2001)

studied nitrate-N flowing out of springs into the Suwannee River using 8'SN as well as

other tracers. Water discharging from springs in Suwannee County had lower S15N

values (2.7-6.2 %o) than Lafayette County (4.5-9.1%o). The average concentration of

nitrate in Suwannee County springs was higher (1.5-37 mg/L) than the average

concentration of nitrate in Lafayette County springs (1.7-5.5 mg/L). These differences

were attributed to local differences in land use and nitrate source. The springs with the

highest concentration of nitrate (and lowest 15N values) were near cropland farming

areas that were intensively fertilized and irrigated, and the springs with the lowest

concentration of nitrate (and highest i 5N values) were near recharge areas with








concentrated animal feeding operations (animal waste sources of nitrate) (Katz et al.,

2001).

A number of studies have been done with 15N being used as a food web tracer as

well. DeNiro and Epstein (1980) found through studying animals raised in the laboratory

on diets of known and constant 85N values, that the isotopic composition of nitrogen in

an animal reflects the nitrogen isotopic composition of its diet. In general, the 85N value

of an organism is greater than the 515N of its diet (DeNiro and Epstein, 1980; Owens,

1987, Wada et al., 1991). According to Peterson and Fry (1987), stable nitrogen isotopes

in animals average 3-5 %o heavier than dietary nitrogen. Alber and Valiela (1994) found

that two different species of mussels incorporated 15N-labelled nitrogen when fed

aggregates derived from dissolved organic matter released by labeled macrophytes,

demonstrating that nitrogen can be transferred from decomposing macrophytes to

suspension-feeding consumers through the aggregate detrital pathway. They also showed

that both species of mussels incorporated significantly more nitrogen when they were fed

aggregates than when they were fed either dissolved organic matter or particulate detritus

(Alber and Valiela, 1994; Alber and Valiela, 1996). However, the nitrogen incorporation

rate of scallops that were fed phytoplankton was significantly greater than that of scallops

fed aggregates (Alber and Valiela, 1996). Fry (1999) studied the clam, Potamocorbula

amurensis, in San Francisco Bay and found that nitrogen isotopic compositions of clams

were representative of watershed nutrient loading. Higher b 5N values were found in the

South Bay, where there was a stronger input of anthropogenic nitrogen than in the North

Bay. In the freshwater end of the North Bay, however, a discrepancy was noted between

the 515N values of the filter-feeders and seston (seston 5%o and large zooplankton 9 to








14%o), and three possible explanations were presented: (1) there was an intermediate

trophic linkage in the microbial component of the food web leading to higher 61"N values

in filter-feeders, (2) detrital river material colonized by bacteria immobilize enriched 15N

from the water column, and filter-feeders consuming these bacteria have higher 15N

values, and (3) a large quantity of riverine seston (which is largely terrestrial and

refractory to food web use) masked a relatively minor "1N-enriched river/estuarine

phytoplankton component that was selectively used by filter-feeders (Fry, 1999).

s15N values have also been used to provide insight into the source of nitrogen

supporting autotrophic production in a system. For example, Frazer et al. (2002) found

that the 61sN values of submerged aquatic vegetation were low in the Chassahowitzka

River. This was consistent with the idea that fertilizers have contributed significantly to

nitrate pollution of the system. Fry et al. (2001) determined that nitrogen isotope assays

were useful for detecting watershed nitrogen loading in four National Estuarine Research

Reserve (NERR) sites on the west coast of the United States. Isotope values of

ammonium and nitrate (ranging from -0.3 to 19.6%o) showed a trend towards higher

values in those estuaries associated with higher watershed nitrogen loading (Fry et al.,

2001). Some studies have even broken the S15N values of each organism down to

individual tissues and excretory products because isotopic variation can exist among

different tissues and metabolites of different animals (DeNiro and Epstein, 1981;

Peterson and Fry, 1987). For example, Alber and Valiela (1994) found that whatever '5N

was present in the guts of two species of mussels was released after 48 hours. Excretory

products are consistently depleted in 5N relative to the diets, which also explains why

'5SN values are higher in the organism compared to its diet (DeNiro and Epstein, 1981;








Owens, 1987; Peterson and Fry, 1987; Alber and Valiela, 1994). Another problem to

consider is that there could be variations in the 815N values of food sources over time.

For example, a study by Zieman et al. (1984) showed that while the 15N content of sea

grasses did not change as they degraded over time, the 1SN content of mangrove leaves

varied by up to 10%o.

Studies have also been done using 15N values as indicators of trophic level.

Nitrogen isotopes are assumed to increase progressively with each trophic transfer (Wada

et al., 1981). Minagawa and Wada (1984) found, in a study on marine and freshwater

animals from the East China Sea, the Bering Sea, Lake Ahinoko, and the Usujiri

intertidal zone, that all consumers, zooplankton, fish, and birds exhibited stepwise

enrichment of 15N with increasing trophic level. Fry (1988) found a general trend of

increasing s35N and 813C with increasing trophic levels; however, he also found that 8'3C

and 8'5N were not correlated. "N increases were more consistent indicating that LSN is a

more reliable trophic indicator than a13C (Fry, 1988). Gu et al. (1996) found that

enriched 81N values in medium and large fish in Lake Apopka, Florida resulted from

diets consisting of other fishes occupying high trophic levels. Riera (1998) found

through analysis of 81SN of Crassostrea gigas in Marennes-Oleron Bay, France, that the

oysters exhibited direct utilization of benthic diatoms as a food source near intertidal

mudflats. However, in the upper estuarine reaches, they were also found to utilize

terrestrial detritus as a food source. It was suggested that 6'5N can be a useful tool in

characterizing trophic levels in an estuarine food web as long as different feeding habitats

are considered (Riera, 1998).






29

Proposed Research

The overall goal of this research is to study the transformation and fate of dissolved

organic matter (DOM) originating in the Suwannee River using stable carbon and

nitrogen isotopes. This includes three main objectives: (1) determining if flocculated

organic aggregates could be produced in the laboratory and if they maintained a

terrestrial isotopic signature, (2) characterizing the spatial pattern of stable isotope

signatures in particulate organic matter in the Suwannee River and its estuary during two

different flow regimes, and (3) using stable isotope ratios to investigate aspects of the

food web in the Suwannee River estuary.













CHAPTER 2
STABLE CARBON AND NITROGEN ISOTOPE COMPOSITION OF ORGANIC
AGGREGATES PRODUCED BY SALINITY INDUCED FLOCCULATION OF
DISSOLVED ORGANIC MATTER FROM THE SUWANNEE RIVER

Introduction

Terrestrial dissolved organic matter (DOM) discharged by rivers into estuarine and

marine systems represents a significant source of carbon and other elements (e.g.,

McCarthy et al., 1996; Opsahl and Benner, 1997; Dagg et al., 2004) and is a potentially

important source of energy for consumers in coastal ecosystems. Much of the DOM

originating in terrestrial systems is degraded by a broad suite of physical, chemical, and

biological processes as it is transported to and mixed with ocean waters (Gardner et al.,

1994; Amon and Benner, 1996; Hedges et al., 1997; Twardowski and Donaghay, 2001;

Heres and Benner, 2002; Zimmerman-Timm, 2002; Dagg et al., 2004; Oberosterer and

Benner, 2004). Examples include photochemical processes and microbial degradation.

However, flocculation of DOM has been shown to occur in estuarine systems where fresh

water meets salt water (Scholkovitz, 1976; Fox, 1983; Mannino and Harvey, 2000;

Sondergaard et al., 2003) and may result in the formation of organic aggregates of a

suitable size and quality for filter- and suspension-feeding organisms, such as clams and

oysters. The DOM, from which flocs are formed in the Suwannee River estuary has a

high nitrogen component as a result of fertilizers and animal wastes present in the system

(Asbury and Oaksford, 1997; Katz et al., 2001).

Laboratory produced organic aggregates have historically been difficult to produce,

even though flocculation of DOM has been shown to occur in many estuarine systems








(Fox, 1983; Eisma, 1986; de Souza Sierra et al., 1997; Del Castillo et al., 2000; Thill et

al., 2001; Sondergaard et al., 2003). Sholkovitz et al. (1976) presented a classic study

where organic aggregates were produced at various salinities by mixing filtered river

water (Glen Burn, Water of Luce, River Cree, and River Stinchar in Scotland) with

filtered seawater (collected off the coast of southeast Scotland). The amounts of

flocculated material increased as salinity increased from 0 to -15%o. Above 15%o, little

removal of the dissolved organic matter occurred. Studies following Sholkovitz's

methods have been less successful in creating flocs (Fox, 1983; de Souza Sierra et al.,

1997; Thill et al., 2001).

The mechanisms underlying the formation of organic aggregates have often been

debated, and it has not been proven that flocculation is solely induced by salt or bacteria,

physically induced, or a combination of these processes. Fox (1983) repeated, with

minor differences, the Sholkovitz et al. (1976) study with unfiltered river water and

filtered seawater from the Delaware Bay and its tributaries. After analysis of the

dissolved humic acid carbon, it was determined that salt-induced removal of dissolved

humic acid was insignificant. Humic substances from different environments are

compositionally different, and therefore, their response to changes in ionic strength and

removal mechanisms may be different (Fox, 1983). De Souza Sierra et al. (1997) used

filtered river water from the Scheldt estuary (Holland) and artificial seawater in an

attempt to produce organic aggregates in the laboratory. No flocculation was noticed and

it was ascertained that under natural conditions, the removal of humic material may

proceed slowly by aggregation through various chemical, physical, and biological

interactions or by adsorption onto suspended matter which was not present in their








samples due to filtering. Thill et al. (2001) included analysis of particle size distribution

along the mixing zone of the Rhone river estuary, France, during high and low flow

regimes to determine if salt induced flocculation played an important role. No obvious

instantaneous change in particle size of the natural river particle size occurred and it was

determined that salt induced aggregation did not play an important role concerning

increased particle size.

Eisma (1986), in a review of observations of flocculated material in European

coastal waters and along the US east coast found that salt-induced mechanisms play only

a minor role in organic aggregate formation, and that organic aggregates are formed more

by a combination of forces including viscous flow, gravity, and Brownian motion.

Bacteria have also been shown to be a major factor in the production of flocculated

material, either by direct colonization or through excretions of mucous which enhances

the stickiness of particle surfaces (Zimmermann-Timm, 2002). Rivers supply inorganic

and organic nutrients that can be used by bacteria as determined in the Hudson River

(USA) by Findlay et al. (1992). Gardner et al. (1994) found that most bacterial

production was supported by dissolved organic matter rather than by particulate materials

during microcosm experiments with filtered and unfiltered water from the northern Gulf

of Mexico near the main delta of the Mississippi River. Also in the Mississippi River

Delta, it was determined that the bioreactivity of DOM increased with increasing size of

the organic matter (Amon and Benner, 1996). Womer et al. (2000) found that bacteria

colonized laboratory-produced aggregates, using the aggregates as a haven in the water

column, over a period of 14 days using water from the Elbe Estuary (Germany). The

aggregates were largest after 9 days because large omnivorous and carnivorous ciliates








colonized the aggregates (W6rner et al., 2000). The combination of physical and

bacterial influences can combine to produce flocculated materials from DOM.

Del Castillo et al. (2000) were able to produce organic aggregates in a laboratory

experiment using Peace River water (a colored river with high concentrations of

dissolved organic matter; west coast of Florida, USA). The Suwannee River (west coast

of Florida, USA) similarly has large concentrations of colored dissolved organic matter

(CDOM), and organic aggregates have been observed in the water column at the salt and

freshwater interface (personal observation). Regardless of exactly how organic

aggregates are formed, it is important to understand what happens to the organic

aggregates once they are produced. It has been hypothesized that organic aggregates are

used as a food source by estuarine organisms (Alber and Valiela, 1994; Zimmerman-

Timm, 2002). Alber and Valiela (1994b) determined that macrophyte-derived aggregates

are more readily consumed than detritus by bay scallops. The DOM released by primary

producers in an aggregate detrital pathway is transformed into organic aggregates, and

then ingested by bivalves, e.g., bay scallops. The aggregates were shown to meet a

substantial portion of the nutritional requirements of the bay scallops because they had

lower C:N ratios and higher protein content than detritus (Alber and Valiela, 1994b). In a

review of river-born aggregates, Zimmerman-Timm (2002) suggests that aggregates

support growth and production of riverine protozoa and metazoa as a long term food

supply.

The major source of terrestrial-derived DOM is vascular plants, which are confined

largely to land and characteristically contain high concentrations of recalcitrant, nitrogen-

free biomacromolecules such as lignin and tannin (Hedges et al., 1997). These plants








have distinct stable carbon isotope ( 3C) compositions which can be used as a biomarker

indicating a terrestrial origin (Fry and Sherr, 1984; Hedges et al., 1997). Most terrestrial

plants have 8'3C values of -28 to -25%0, versus -22 to -19%0 for temperate marine

phytoplankton, whereas sea grasses have heavier "3C values near -12%o (Fry and Sherr,

1984). The f15N values of vascular land plants and marine plankton can also be

sufficiently different (Hedges et al., 1997). Terrestrial plants typically have average 815N

values of 3%, whereas phytoplankton have heavier average 515N values ranging from 6

to 10%o (Owens, 1987). There is a prevalence of nitrogen fixation on land, and therefore

the light organic '5N compositions have been suggested as being typical of terrestrial

origin (Peters et al., 1987), however blue green algae also present light '5N values

because of the capability to fix nitrogen.

Here, it is proposed that DOM in the fresh water of the Suwannee River flocculates

when mixed with salt water from the Gulf of Mexico, and that the organic aggregates

may be consumed by clams and oysters in the estuary. A laboratory study was performed

to produce organic aggregates under varying salinity conditions and to determine if

natural abundances of stable nitrogen and carbon isotopes might be used as markers to

characterize organic aggregates and identify their potential role as a food source for fauna

in the Suwannee River estuary. Further, the study sought to determine if organic

aggregates maintain their stable isotope signature along the salinity gradient utilized in

the laboratory to simulate such gradients in the estuary.

Methods and Materials

Site

The Suwannee River is a blackwater, tidally influenced river with its principal

origin in the Okefenokee Swamp in Georgia. It flows southwest through Florida and








discharges into the Gulf of Mexico just north of Cedar Key. There is a delta region at the

mouth of the river characterized by a network of intertidal and subtidal oyster reefs

(Wolfe and Wolfe, 1985). The water quality of the upper Suwannee River is

characterized by low pH (around 4), low concentrations of dissolved inorganic solids, and

high concentrations of dissolved organic substances, especially fulvic acids (Malcolm et

al., 1989a). The lower Suwannee River maintains a higher pH (6 to 9) (Wolfe and Wolfe,

1985). The source of the humic substances in the water is predominantly litter, leaf and

root exudates, and leaf leachates. The concentration of these humic substances has been

shown to be an order of magnitude greater than that in most natural stream waters. The

dissolved organic carbon concentrations in the Suwannee River near the Okefenokee

Swamp are in excess of 25 mg/L (Malcolm et al., 1989b).

Methods

Laboratory experiments were designed to flocculate the dissolved organic matter

(predominantly humic substances) from the Suwannee River across a range of salinities.

Whole water samples were collected from one site in the upper Suwannee River fresh

water (August 2002 and September 2003) and one in the lower Suwannee River fresh

water (May 2003 and August 2003). When returned to the laboratory, samples were

shaken and 1-L aliquots were distributed to 6 beakers. Samples were not filtered because

it had been noted that filtering samples would remove suspended material that could be

involved in the flocculation and adsorption process (De Souza Sierra et al., 1997).

Instant Ocean Synthetic Sea SaltM (Aquarium Systems, Mentor, OH) was added as a

solid and mixed with the 1-L samples until dissolved and the desired salinity was

reached. The salinity varied from 0 to 30 ppt in increments of 0, 5, 10, 15, 20, and 30 ppt

and was determined with a YSI Conductivity and Salinity field monitor.








The samples were stirred (Phipps and Bird jar tester) for 6 to 10 consecutive days at

approximately 14 rpm. Samples were taken for DOC analyses daily for experiments I

and II, and initially for experiments III and IV (see below). At the end of each

experiment, organic aggregates were allowed to settle and the residual water was

decanted and the organic aggregates were collected onto a combusted (450* C, 4 hours)

GF/F filter. Samples were packed and frozen prior to stable nitrogen and carbon isotope

analysis.

DOC and Stable Isotope Analysis

Immediately after the organic aggregates were collected from each beaker, the

decanted water was filtered through a Millipore HNWP 0.45 um filter (pre-washed with

E-Pure water). The filtrate was analyzed with a Tekmar Dohrman Apollo 9000 HS

Combustion TOC Analyzer with an STS 8000 Autosampler. The reproducibility of the

DOC measurements was generally within 0.05%. 13C and 8'5N isotope ratios of the

organic aggregates on filters were analyzed with a Finnigan Delta-C continuous flow

mass spectrometer. Results are reported in standard 8 notation where:

i'5N (%o)= [('sN/14N)sampl(e5N/14N)sdard)-l] x 1000 (2-la)

and

13C (%) = [(13C/12C)smpd(13C/12C)standard)-l] x 1000 (2-1b)

Atmospheric nitrogen and carbon from the Pee Dee Belemnite served as reference

standards. The reproducibility of the stable 13C and 'SN isotopes was within 0.3%o.

Results

Organic aggregates were formed almost immediately after Instant OceanT was

added to the reaction beaker and stirring was initiated. The organic aggregate densities

increased, as observed visually, with increasing salinity.








Comparisons of DOC versus salinity are presented in Figure 2-1. All four of the

experiments showed that increasing the salinity from 0 to 30 ppt had undetectable or

minor effects on DOC concentrations. Only one experiment from the upper Suwannee

River showed a significant relationship (p < 0.0001); DOC decreased with increasing

salinity. There was some association for two of the other three experiments (p = 0.0396,

0.0188), and one showed no significant relationship (p = 0.3687). Continuous stirring for

longer than 24 hours showed no measurable changes in DOC concentrations for organic

Floe studies I and II (Figure 2-2).

The relationships between '5N and 6"3C signatures and salinity are presented in

Figures 2-3 and 2-4, respectively. Average stable isotope values for all four studies are

presented in Figures 2-5 and 2-6, respectively. The 615N of the laboratory produced

organic aggregates increased by approximately 4%o with increasing salinity using pooled

data from all four experiments. The upper Suwannee River organic aggregate

experiments showed significant relationships with a p-value < 0.0001 for both

experiments. One of the lower Suwannee River organic aggregate experiments also

showed significant relationship with a p-value = 0.0046 (Floe II). The second of the

lower Suwannee River organic aggregate studies did not show a significant relationship

(Floe IV, p = 0.3245). The 13C signature of aggregates decreased significantly in two of

the four experiments (Floe II, p = 0.0062 for the lower Suwannee and Floe IV, p = 0.0035

for the upper Suwannee) (Figure 2-4). The 13C of organic aggregates formed during one

experiment using upper Suwannee River water increased very slightly with increasing

salinity (Floe I, p = 0.0151). The average '15N and 6'3C for all the four of the floe studies

combined are given in Figures 2-5 and 2-6. Salinity had a significant effect on s15N and






38


Table 2-1. Analysis of Variance (ANOVA) Results for all of the Floc Studies.

Floc I Floe II Floc III Floc IV Average
Source of Variation Salinity Salinity Salinity Salinity Salinity Expriment
'15N F Ratio 10.59 23.46 8.30 1.2596 3.62 33.61
P <0.0001 0.0046 0.0450 0.3245 0.0240 <0.0001
613C F Ratio 2.41 10.52 0.30 38.29 0.97 24.58
P 0.0729 0.0062 0.6158 0.0035 0.4669 <0.0001
C:N F Ratio 14.91 7.34 n.d. n.d. 4.35 5.80
P <0.0001 0.0154 n.d. n.d. 0.0120 0.0077
DOC F Ratio 108.14 4.88 6.76 1.32 n.d. n.d.
P <0.0001 0.0396 0.0188 0.3687 n.d. n.d.

*P Values at the 95% confidence level. Analyzed with JMP. (n.d. = not determined)











Floc Study I (Upper Suwannee)


0 5 10 15 20 25 30 35
Salinity


Floc Study IV (Upper Suwannee)

90
80o
70 "- "-
60


Floe Study II (Lower Suwannee)

16.8

16.2
16.21 .o 1,1
ax 16.0
4 15.816 c
15.6
o 15.4
15.2
15.0
14.8


0 5 10 15 20 25 30 35
Salinity


Floe Study III (Lower Suwannee)


13.0
2 12.5
CL
- 12.0
g 11.5
11.0
Insn


0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Salinity Salinity


Figure 2-1. Salinity versus Dissolved Organic Carbon in the Upper and Lower Suwannee River Floe Studies.


S


.









Floc Study I


0 1 2 3 4 5 6 7 8 9 10
Time (Days)


Floc Study II


19

18 ......::
';K ....--------
17 -

16 IK

S15

14

13
12
0 1 2 3 4
Time (Days)


-- 0 Salinity
- 15 Salinity
-- 30 Salinity
--x .-- 5 Salinity
--*x--- 10 Salinity
- 0-.--- 20 Salinity


5 6 7


Figure 2-2. Time versus Dissolved Organic Carbon for Floc Studies I and II.


70
60
E 50
, 40
o 30
0
0 20
10
0


~z z2 Z2


-*- 0 Saliniy
-a- 5 Saliniry
- 10 Salinlry
- 15 Saliniry










Upper Suwannee


Floc Study I



Floc Study IV




S 5 10 15 20 25 30 35
Salinity


Lower Suwannee


0 5 10 15 20 25 30 35
Salinity


Figure 2-3. Salinity versus 85N for the Upper and Lower Suwannee River Flocculated
Organic Aggregates.


7
6
5
4
3
z 2
S1
S0
-1
-2
-3
-4
-5


8

6

z 4
2

0


Floc Study II



Floc Study III










Upper Suwannee

-20

-22

-24

-26 Floc Study I

-28
-30 'Floc Study IV
0 5 10 15 20 25 30 35
Salinity




Lower Suwannee

-20

-22

o-24
b -26
S. Floc Study III
-28
Floc Study II
-30
0 5 10 15 20 25 30 35
Salinity


Figure 2-4. Salinity versus t13C for the Upper and Lower Suwannee River Flocculated
Organic Aggregates.

















5



4



3



2



1



0



-1
-5 0 5 10 15 20 25 30 35
Salinity

Figure 2-5. Salinity versus Average 615N Signatures of the Upper and Lower Suwannee River Floc Studies Including Standard
Error Bars.











-27.3


-27.4


-27.5


-27.6


-27.7


-27.8


-27.9


-28.0


-28.1


-28.2
-5 0 5 10 15 20 25 30 35
Salinity

Figure 2-6. Salinity versus Average 6t3C Signatures of the Upper and Lower Suwannee River Floc Studies Including Standard
Error Bars.











18



16



14



S12


z
10



8-



6-


10 15
Salinity


20 25 30 35


Figure 2-7. Salinity versus Average C:N Ratios of the Flocculated Organic Aggregates from the Upper and Lower Suwannee
River Floc Studies Including Standard Error Bars.


I ( I








no significant effect on 13C (Table 2-1).

The C:N ratios of the filtered organic aggregates are presented in Figure 2-7. C:N

ratios of the organic aggregates averaged between 10 and 12 and were highest at the

highest salinities (Figure 2-7). Salinity had a significant effect on the C:N ratios (p <

0.05).

Discussion

It was necessary to determine if organic aggregates could be formed by mixing

Suwannee River water with salt (Instant OceanTM) so that organic aggregates could be

analyzed for stable nitrogen and carbon isotopes. Salt-induced organic aggregate

formation has been shown to be optimal for salinities between 1 and 7 ppt (Thill et al.,

2001), however, in our experiments, organic aggregates formed almost instantly (within

the first half hour of mixing) in each salinity treatment (0 to 30 ppt). The initial idea for

determining organic aggregate formation was to measure DOC throughout the duration of

a 10-day experiment, given the hypothesis that DOC would decrease each day as the

organic aggregates formed. The results showed, however, that DOC did not change

significantly throughout the 10-day experiment (Figure 2-2). During this study, the

Suwannee River exhibited very high levels of DOC in the upper and lower portions of the

river (ranging from 13 to greater than 50 ppm). Because there was such a high

concentration of DOC in this system, it is likely that only a small percentage of the DOC

was transformed into an aggregate form, and as a result, no substantial loss of DOC was

observed. Sondergaard et al. (2003) also found that fast aggregation of DOC was not a

major removal process of DOC in highly colored rivers. Therefore, a different approach

had to be taken to be able to quantitatively model the behavior of the organic aggregates.








Stable nitrogen and carbon isotope ratios have been used to model theoretically the

behavior of particulate organic material (Montoya et al., 1991; Kendall et al., 2001; De

Brabandere et al., 2002), but not organic aggregates, per se. In each of the four

experiments, the change in the S15N signatures of organic aggregates was consistent from

0 to 30 ppt (Figure 2-3), indicating that i'5N could be used as markers of organic

aggregates as they are formed and move throughout the Suwannee River and estuary.

The 6i5N of the organic aggregates followed a pattern showing a transition from a

terrestrial signature (i.e., near 0) to a higher, more marine signature as the salinity

increased. It is likely that the change in pH, induced by increased salinity, might

selectively drive the precipitation of DOC, and based on the 15N and 13C values of the

flocculated organic aggregates, a trend is observed.

The formation of the organic aggregates can be biological, chemical, and/or

physical. Bacteria have been shown to have a major influence on organic aggregates and

particulate organic nitrogen (PON) formed in an estuarine environment (Kemp, 1990;

Hoch et al., 1992; Alber and Valiela, 1994; Stumm and Morgan, 1996; Sondergaard et

al., 2003). The samples taken from these laboratory experiments were not filtered prior

to the addition of salt, allowing the organic aggregates to include particulate material

already in the water which may have included suspended sediment, bacteria, plant debris,

and fecal matter. Bacterial incorporation of ammonia has been shown to be a mechanism

for producing isotopically light particles (near 1.1%o), whereas microbially degraded

material tends to have signatures closer to 8%o (Voss et al., 1997). This implies that

degradation of PON (or the organic aggregates in these experiments) can result in an

increase of 6 1N. In these experiments, samples were stirred in the beakers for up to 10








days at room temperature, and not protected from light, allowing formation of organic

aggregates which could have included growth of bacterial communities and

remineralization of isotopically light nitrogen.

Salt induced flocculation is caused by electrolytic interactions between negatively

charged functionalities in humic substances and cations in seawater (Eckert and

Sholkovitz, 1976; Stumm and Morgan, 1996), especially calcium and magnesium.

Positive salt ions neutralize the negatively charged humic substances, and Van der Waals

forces form attraction forces between the neutral molecules, forming organic aggregates.

Hydrogen bonding also contributes to aggregation of humic substances, especially when

the molecules include hydroxyl or amine groups (Stumm and Morgan, 1996). Slow

mixing encourages collision of the particles. The stability of colloids in the dissolved

organic matter pool is mainly determined by the pH and ionic strength of solution as well

as the presence of specific ions (Tombicz et al., 1999). Increasing the salt content

increases the pH and the ionic strength, and humic substances exposed to salt ions will

flocculate (Stumm and Morgan, 1996). Isotopic fractionation can occur in the process of

ion exchange reactions. For example, the process of ammonium adsorption at the site of

clay minerals (or possibly humic substances) plays a primary role in determining '5N

abundance, and the heavier isotopic species is preferentially adsorbed on clay colloids

(Delwiche and Steyn, 1970).

Ammonium is found in humic substances in the Suwannee River (Malcolm et al.,

1989b). Therefore, a possible chemical explanation for the steady increase in 685N with

increasing salinity is that some fraction of the NH4+ (associated with humic substances) is

transformed to NH3 as pH increases resulting in a heavier isotopic composition of the








residual NH4+ on the organic aggregates. Ammonia volatization leads to the enrichment

of 5SN in inorganic nitrogen (Wada and Hattori, 1991).

The 63C of the organic aggregates did not show a consistent trend as did the 1s5N

data. The data, in fact, exhibited little change across the broad range of salinities (< 1%o)

and aggregates maintained a terrestrial signature (-25 to -30%o) (Figure 2-4). Therefore,

513C measures can be a good tool for determining the source of flocculated particles.

Guo et al. (1997) studied the 613C signatures of colloidal organic carbon in the

Chesapeake Bay and also determined that stable carbon isotope signatures were good

indicators of the origin of organic particles.

The C:N ratios help to characterize the laboratory-produced organic aggregates.

For example, Middleburg and Nieuwenhuize (1998) distinguished terrestrial sources of

particulate organic material (C:N =21) from riverine, estuarine, and marine material

(C:N =7.5 to 8). In our experiments, C:N ranged from 6 to 17, indicative of relatively

high quality food source based on findings by Alber and Valiela (1994a). The large

range in the C:N ratios may be explained by different environmental causes. For the

upper Suwannee River experiments, water was collected for floc study II during a

drought and for floc study VI during more normal flow conditions. During floc study II,

the water levels were extremely low in the river, and less carbon was entering the system

(groundwater inputs dominate during low flow periods). Therefore, C:N ratios were

lower than during floc study VI when water levels were higher, and higher C:N ratios of

the material were entering the river (Figure 2-7).








It is important to determine if the organic aggregates are being consumed by filter

feeders or other fauna in the estuary. In a later chapter, the possibility that bivalves in the

Suwannee River are consuming organic aggregates will be presented.

Summary

A laboratory study was performed to determine if natural abundance measures of

stable carbon and nitrogen isotope ratios might be used as markers to characterize organic

aggregates to identify their potential role as a food source for fauna in the Suwannee

River estuary. The 8i5N values of laboratory produced aggregates increased significantly

with salinity, however the 6 3C values did not change significantly with increasing

salinity. These findings indicate that the 6S5N signatures might be used as a tracer of

organic aggregate development as they are formed as a result of increasing salinity.

These findings also indicate that 6'3C signatures might be used to quantify their role as a

food source for estuarine fauna.

Conclusions

The following conclusions may be drawn from the research discussed in this

chapter:

* Formation of organic aggregates, i.e. floes, can be induced by mixing salts with
Suwannee River water rich in dissolved organic material.

* s15N signatures of aggregates increased significantly with salinity, but exhibited
pronounced variability.

* 3C signatures did not change significantly with increasing salinity indicating that
stable carbon isotope ratios might be used as a tracer of terrestrial derived dissolved
organic matter in estuarine and coastal food webs.

* The C:N ratios increased significantly with increasing salinity, but did not exceed
values of 17 indicating that salinity induced aggregates are a potentially high
quality food source for suspension feeding organisms in the Suwannee River
estuary and associated nearshore coastal waters.













CHAPTER 3
SPATIAL GRADIENTS IN THE STABLE CARBON AND NITROGEN ISOTOPE
COMPOSITION OF SUSPENDED PARTICLES IN THE SUWANNEE RIVER
ESTUARY DURING DIFFERENT FLOW REGIMES

Introduction

River discharge provides a significant source of nutrients to estuaries. Increased

nutrient input into estuaries and marine environments, whether from point or non-point

sources, can lead to increased primary production and changes in trophic structure

(Ryther and Dunstan, 1971; Smith et al., 1999; White et al., 2004). Nitrate

concentrations in many of Florida's spring-fed rivers are rapidly increasing (Mytyk and

Delfino, 2004), especially in the Big Bend region of the northeast Gulf of Mexico (Ham

and Hatzell, 1996; Jones et al., 1997, Katz et al., 2001), where it has long been

recognized as relatively unaffected by anthropogenic forces (Bass and Cox, 1988). In

particular, the Suwannee River has such high levels of nitrate and carbon that it may alter

the biological character of the Suwannee River estuary.

Distinct seasonal patterns of the distribution of nutrients (specifically nitrate and

ammonium) occur in the Suwannee River and estuary. With the second highest mean

annual discharge in Florida (301 m3/s), the Suwannee River has its peak flows typically

in the early spring and low flows typically in the fall (Crandall et al., 1999). Nitrate

concentrations in the estuary are lower during periods of high flow than during periods of

low flow. This is a karst system where groundwater interacts with surface water, and

during the fall (low flow period), the main source of freshwater for the river is

groundwater which has high nitrate concentrations (Pittman et al., 1997; Crandall et al.,








1999). During the spring (high flow period), overland surface flow is the dominant

source of water for the river. High color in the system limits nutrient uptake and

assimilation by phytoplankton (due to light limitation). Thus, much of the otherwise

available nutrients are discharged directly to the estuary (Bledsoe, 1998). Nitrogen is the

limiting nutrient in the Suwannee River estuary (Bledsoe and Phlips, 2000), and

eutrophication is a potential problem of concern (Ryther and Dunstan, 1971; Bledsoe et

al., 2004).

Nitrogen loading can have a significant impact on biological productivity and

ecosystem structure in coastal and nearshore marine systems; however the mechanisms

and pathways involved may be difficult to resolve with traditional methods (e.g.

hydrographic and mass balance studies) because of the complexity of the nitrogen cycle

and relatively large spatial and temporal scales of interest (Owens, 1987; Peterson and

Fry, 1987; Horrigan et al., 1990a, Horrigan et al., 1990b; Montoya et al., 1990; Montoya

and McCarthy, 1995). The stable isotopic signature of inorganic and organic nitrogen

provides an integrative tool for studying the sources of nitrogen supporting production in

an ecosystem as a whole (Valiela et al., 1997). Stable carbon isotope ratios also provide

a means for determining the source of organic matter supporting production in these

ecosystems.

Spatial gradients in nutrient concentrations, particularly of nitrate and/or

ammonium, are characteristic of estuarine systems and can occur as a result of physical

mixing processes and uptake and assimilation by phytoplankton and other autotrophs

(e.g. attached macroalgae, epiphytic microalgae, and seagrasses). Isotopic fractionation

associated with the uptake and assimilation of nitrate and/or ammonium can generate








spatial gradients in the stable nitrogen isotope composition of the residual pool of

dissolved inorganic nitrogen. This will also be reflected in the isotopic composition of

nitrogen sequestered in particulate forms (Montoya and McCarthy, 1995). In essence,

stable nitrogen isotopes can serve as in situ tracers of nitrogen as it moves through an

estuarine system. Stable carbon isotopes are also used as in situ tracers of the source of

carbon in estuarine systems.

Here, data are presented from the Suwannee River and estuary in Northwest Florida

during two different high and low flow periods, hypothesizing that distinct spatial and

temporal patterns will be seen in the stable nitrogen isotopes of suspended particulate

organic matter (SPOM), and that stable carbon isotopes will allow determination of the

source of organic matter fueling production in higher-level consumers. Stable nitrogen

and carbon isotopic data for oysters and zooplankton collected in the same area are

presented to determine the relationship between oysters, zooplankton, and SPOM.

Methods, Materials, and Site Description

Site Description

The historic Suwannee River is a blackwater, tidally influenced river with its main

origin in the Okefenokee Swamp in Georgia. The river is approximately 394 km in

length and flows southwest through Florida. It discharges into the Gulf of Mexico just

north of Cedar Key, draining a watershed of approximately 25,640 km2 (Nordlie, 1990).

Main tributaries include the Alapaha, Withlacoochee, and Santa Fe Rivers. At the mouth

of the river there is a delta region which is characterized by a network of intertidal and

subtidal oyster reefs that are subject to harvest periodically throughout the year (Wolfe

and Wolfe, 1985).








Periods of peak flow in the Suwannee River occur typically in early spring and

periods of low flow occur in the fall. There is much less land development and point

source pollution in this watershed than in most other coastal regions in Florida (Bass and

Cox, 1988). Major land uses in the watershed include silviculture and agriculture (row

crops, dairy, poultry, and swine) (Katz et al., 2001). The land immediately surrounding

the river is predominantly used for pine forestry operations. Fertilizer from pine forestry

operations and waste material from dairy practices are thought to be a significant source

of non-point source nutrient loading to the river (Ashbury and Oaksford, 1997). Spring

and groundwater discharge contribute significantly to nitrate concentrations in the river,

particularly during periods of low flow. The upper part of the estuary, comprising both

oligohaline and mesohaline zones, is bordered by brackish marsh habitat and is

dominated by emergent grasses and rushes. Submerged aquatic vegetation (SAV) is less

abundant. The lower portion of the nearshore estuary is a mosaic of saltmarsh, tidal

creeks, mudflats and oyster habitats. Seagrasses are much less abundant within this

estuary when compared to other areas of Florida's Big Bend coast, as a consequence of

highly colored surface water and low light levels (Bledsoe, 1998). The main pathway of

nitrogen transfer to higher trophic levels likely occurs directly through the pelagic

compartment (i.e. phytoplankton production in the surface water) (Frazer et al., 1998;

Bledsoe et al., 2004).

Methods

Surface water samples were collected from the Suwannee River and its estuary in

November, 1996 (low flow period), March, 1997 (high flow period), May, 2003 (high

flow period), and December, 2003 (low flow period). During the 1996/1997 sampling

event, water was collected at 10 stations along a transect (stations marked with A, see








Figure 3-1). The initial sampling station was located in the main river approximately

5km from the mouth and subsequent sampling stations progressed seaward at

approximately 3.7km intervals (Figure 3-1). During the 2003 sampling event, water was

collected at 10 stations along a salinity transect (stations marked with B and C), ranging

from 0 ppt to approximately 30 ppt (Figure 3-1, Table 3-1). Conductivity, dissolved

oxygen, pH, salinity, and temperature were measured with a YSI field meter. Water

samples were held on ice and returned to the lab for processing.

Water samples collected at each station during each sampling event were filtered

through precombusted glass fiber filters (Whatman GF/F, 4500C, 4h) and the filtrate was

frozen for subsequent analyses (within 24h) of nitrate and ammonium in the laboratory.

Filtered particles were placed on ice and transported to the laboratory where they were

dried at 600C (>48h) in preparation for isotope analysis. The filtrate from the 2003

sampling trips was preserved with concentrated sulfuric acid (resulting in a pH<2)

(Holmes et al., 1998) and stored prior to analysis of the stable nitrogen isotope

composition of dissolved inorganic nitrogen (DIN). Additional water was collected at

each station and filtered on site for subsequent analysis of chlorophyll a concentration.

Water was also collected during the 96/96 and 2003 sampling trips to be analyzed for

DOC (2003 only), color, TN, TP, and phosphate. Zooplankton were collected with a

202um ring-net (diameter = 0.5m). Samples were placed on ice and returned to the

laboratory where they were immediately sorted by taxon (i.e., copepod, chaetognath, and

ctenophore) and prepared for stable isotope analysis. Oysters were collected along the

transect during low tide in December, 2003. They were stored on ice and transported to



































Figure 3-1. Map of the Sampling Sites in the Suwannee River and its Estuary.









Table 3-1. Location and Site Names for Sampling Sites in the Suwannee River and its
Estuary.

Sample Date Sample GPS Coordinates
ID Latitude Longitude
Nov. 1A 29.328012 -83.103267
1996 and 2A 29.306664 -83.147504
March 1997 3A 29.281708 -83.164847
4A 29.279032 -83.166859
5A 29.279264 -83.166504
6A 29.274404 -83.167420
7A 29.258845 -83.176053
8A 29.245006 -83.194144
9A 29.246172 -83.234362
10A 29.251276 -83.284666
May 2003 1B 29.327136 -83.103301
2B 29.307044 -83.148037
3B 29.279506 -83.165490
4B 29.275151 -83.169196
5B 29.266446 -83.170751
6B 29.266037 -83.171514
7B 29.260041 -83.176243
8B 29.251779 -83.189391
9B 29.243944 -83.198380
10B 29.199541 -83.251848
Dec. 2003 1C 29.328012 -83.103267
2C 29.306664 -83.147504
3C 29.281708 -83.164847
4C 29.279032 -83.166859
5C 29.279264 -83.166504
6C 29.274404 -83.167420
7C 29.258845 -83.176053
8C 29.245006 -83.194144
9C 29.246172 -83.234362
10C 29.251276 -83.284666








the laboratory where they were shucked, dried at 600C (>48h), ground to a fine powder

with a mortar and pestle, and stored in a desiccant cabinet prior to isotope analyses.

Concentrations of nitrate (NO3"+N02), ammonium (NH4+), and total nitrogen (TN)

in surface water samples were measured with a Bran+Lubbe AutoAnalyzer II within two

days of sampling. The limit of detection for each nutrient was <0.001 mg-N/L. Analyses

of phosphate (PO4) and total phosphorus (TP) were analyzed with a Perkin Elmer

Lambda 2 spectrophotometer (Greenberg et al., 1992). Color was analyzed using

platinum cobalt standards also using a Perkin Elmer Lambda 2 spectrophotometer and a

Spectronic 401 spectrophotometer. Chlorophyll a was measured on a Hitachi U-2000

spectrophotometer after extraction with hot ethanol. Total nitrogen and total phosphorus

were determined using the persulfate digestion method (Greenberg et al., 1992). Samples

for DOC analysis were filtered through 0.45 Am nylon filters (Millipore HNWP) and

measured with a Tekmar Dohrman Apollo 9000 HS Combustion Analyzer with a STS

8000 TOC Autosampler. The reproducibility of the DOC measurements was within

0.05%.

All samples for isotope analysis were analyzed with a Finnigan Delta-C

continuous-flow mass spectrometer. Results are reported in standard 6 notation where:

5"SN (%o)= [(("N/l'N)sample/(lN/'4N)standard)-l] x 1000 (3-la)

and

I3C (%o) = [(('3C/'C)sample/('1C/l1C)standard)-l] x 1000 (3-lb)

Atmospheric nitrogen and Pee Dee belemnite limestone served as reference standards.

The reproducibility of the stable carbon and nitrogen isotope measures was within 0.3%o.








Results

Physical Parameters

Salinities in the Suwannee River (station 1: 1996 and 1997 and stations 1 and 2:

2003; Table 3-2) were at or less than 0.2 ppt during all sampling periods. The two

sampling stations furthest offshore (stations 9 and 10: 1996 and 1997) showed salinities

near 35 ppt, and the station furthest offshore (station 10) during the 2003 sampling

periods showed a salinity near 30 ppt. Salinities at the other stations were less than these

higher values and varied with sampling date during the 1996 and 1997 sampling events,

whereas the salinities were at more regularly spaced intervals during the 2003 sampling

periods.

Color in the Suwannee River estuary showed considerable variation. Values for

color were greatest within the river and decreased along the transect from the river to the

Gulf of Mexico during the 1996 and 1997 sampling events (Table 3-2). During the 2003

sampling events, color was highest in the river and decreased steadily with distance from

the river's mouth. Color values were highest during periods of high river discharge

(April 1997 and May 2003).

In March 1997 and May 2003, the observed high flows were approximately 400

m3/s and 320 m3/s respectively. In November 1996 and December 2003, recorded flows

were approximately 130 m'/s and 157 m3/s, respectively. Average monthly streamflows

for 1996, 1997, and 2003 are presented in Figure 3-2.

Chemical Parameters

Nitrate concentrations (Table 2-3) were highest in the river during periods of low

discharge (November, 1996 and December, 2003). Beyond the river, nitrate






60


Table 3-2. Chemical and Biological Parameters in the Suwannee River and its Estuary
for Each Sampling Event.
Station
1 2 3 4 5 6 7 8 9 10
SALINITY (ppt)
Nov-96 0.0 21 23 25 30 31 33 33 35 35
Mar-97 0.0 22 22 23 28 30 31 33 34 35
May-03 0.1 0.1 3.5 6.5 9.0 16 17 21 25 30
Dec-03 0.2 0.2 3.8 6.1 10 13 17 22 25 30
COLOR (mg pt/L)
Nov-96 110 27 29 32 22 19 32 27 10 8
Mar-97 150 44 46 34 19 12 14 21 12 12
May-03 188 187 163 148 122 97 84 65 46 22
Dec-03 63 66 57 54 45 41 36 25 17 9
DISSOLVED ORGANIC CARBON (ppm)
May-03 12.1 12.4 14.8 13.8 13.6 10.4 9.6 7.8 7.2 4.5
Dec-03 5.5 5.8 6.8 6.6 6.1 5.8 5.8 4.7 5.0 2.6
CHLOROPHYLL A (mg/m3)
Nov-96 0.4 2.3 2.1 2.9 9.8 9.9 7.8 2.9 1.2 0.9
Mar-97 0.2 4.2 5.6 3.7 3.0 2.0 2.2 1.3 1.5 0.7
May-03 0.3 0.3 2.2 6.1 9.9 13.9 18.9 13.7 9.8 2.8
Dec-03 0.1 BDL 1.3 2.7 5.1 3.7 11.8 4.3 5.3 2.5











600



tI ----1996
500 / --*-1997

19
S\ 2003


S400 i





4200 ;
.o- \






100




0
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Time


Figure 3-2. Monthly Streamflow Data for the Suwannee River near Wilcox, Florida (USGS, 2004).








concentrations decreased rapidly along the transect during the 1996 and 1997 sampling

events. Further offshore, during the 1996 and 1997 sampling events, nitrate

concentrations were generally below the limit of analytical detection (Table 3-3). During

the May and December 2003 sampling events, nitrate concentrations also declined with

distance offshore.

Ammonium levels mirrored nitrate patterns with the exception of the December,

2003 sampling event (Table 3-3). During this event, ammonium remained in the narrow

range of about 46 to 56 jg/L with the exception of 72 gg/L at station 5C and exhibited a

peak concentration at station 6C, i.e. 111 ig/L. In November, 1996, the concentration of

ammonium in the river and nearshore of the estuary varied considerably (Table 3-3), but

was undetectable seaward of station 3A.

Total nitrogen (TN) was highest in or near the river mouth for all sampling dates

(Table 3-3). During the 1996 and 1997 sampling events, TN concentrations decreased

substantially outside the river mouth. During the 2003 sampling event, TN

concentrations declined steadily with distance offshore (Table 3-3).

Total phosphorus (TP) and soluble reactive phosphorus (SRP) were highest in or

near the mouth of the river for all sampling dates (Table 3-4). Total phosphorus

concentrations decreased markedly beyond the river mouth (station 2A) during the 1996

and 1997 sampling events. During the 2003 sampling period, TP concentrations

decreased steadily with distance offshore (Table 3-4). Higher concentrations of TP and

SRP were observed during periods of high river flow (March 1997 and May 2003). SRP

was not detectable beyond station 6 during the 1996 and 1997 sampling events.









Table 3-3. Concentrations of Nitrogen Components (pg/L) in the Suwannee River and its
Estuary for Each Sampling Event.
Station
Nov-96 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A
N-N03 810 60 180 180 BDL* BDL BDL BDL BDL BDL
N-NH4* 40 320 20 BDL BDL BDL BDL BDL BDL BDL
Total N 1190 380 480 430 340 300 320 200 160 120

Mar-97 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A
N-N03 360 80 80 60 BDL BDL BDL BDL BDL BDL
N-NH4' 40 320 20 BDL BDL BDL BDL BDL BDL BDL
Total N 850 380 290 350 280 170 170 100 130 150

May-03 1B 2B 3B 4B 5B 6B 7B 8B 9B 10B
N-NO3- 514 513 598 587 490 369 314 185 129 60
N-NH4' 47 52 79 73 63 60 37 29 36 BDL
Total N 1170 1170 1270 1050 1150 945 825 660 510 245

Dec-03 1C 2C 3C 4C 5C 6C 7C 8C 9C 10C
N-N03 1300 1275 935 860 640 520 450 250 115 BDL
N-NH4' 47 53 56 56 72 111 54 54 55 46
Total N 1320 1325 1100 1015 875 780 735 515 500 265


*BDL below detection limit






64


Table 3-4. Concentrations of Phosphorus Components (qg/L) in the Suwannee River and
its Estuary for each Sampling Event.
Station
Nov-96 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A
SRP 50 10 BDL BDL BDL BDL BDL BDL BDL BDL
Total P 130 10 30 30 20 10 BDL BDL 10 BDL

Mar-97 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A
SRP 80 20 10 10 BDL BDL BDL BDL BDL BDL
Total P 90 20 10 10 BDL BDL BDL BDL BDL BDL

May-03 1B 2B 38 4B 5B 6B 7B 8B 9B 10B
SRP 91 89 81 63 45 28 18 8 3 BDL
Total P 122 116 134 105 99 68 49 33 24 11

Dec-03 1C 2C 3C 4C 5C 6C 7C 8C 9C 10C
SRP 79 78 61 57 40 30 24 12 3 BDL
Total P 84 80 70 68 59 47 52 33 32 18








Dissolved organic carbon (DOC) was only determined for the two 2003 sampling

events. DOC concentrations decreased steadily with increasing salinity after reaching

their highest values at station 3 on both 2003 sampling dates (Table 3-2). Dissolved

organic carbon concentrations exhibited a slight increase from station 1 to station 3.

Biological Indicator

Chlorophyll a concentrations in the river were consistently low (<1 mg/m3) during

the 1996 and 1997 sampling events (Table 3-2). During the 2003 sampling period,

chlorophyll a concentrations were low near the river mouth and increased to a

chlorophyll maximum near stations 6 and 7 (Table 3-2). Chlorophyll maxima were also

observed during the 1996/1997 sampling periods. A maximum value (9.9 mg/m3) was

observed at station 6A in November 1996 and a maximum value (5.6 mg/m3) was

observed at station 3A in March 1997.

Stable Isotope Analyses

Spatial Gradients in the stable nitrogen isotope composition (6'5N) of suspended

particulate organic matter (SPOM) collected from the surface waters of the Suwannee

River and its estuary were apparent during both low and high flow regimes (Figures 3-3

and 3-4, Table 3-5). During the November 1996 sampling event, there was an initial

decrease in the 61SN signature from station 1 to station 3 with a sharp drop at station 4.

The 5isN signatures of SPOM during the March 1997 sampling event exhibited a sharp

decline at station 2A. The 1s5N signatures of SPOM were higher during the March 1997

sampling event than during the November 1996 sampling event. A similar pattern was

observed in May 2003; there was a sharp drop at stations 3B and 4B. The December

2003 sampling event showed a more uniform, increasing pattern for the SPOM (Figure 3-

4).












*--*-Mar-97
-| Nov-96


B.

i.


High Flow

",


0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-3. 815N Signatures of Surface Suspended Particulate Organic Matter (SPOM)
for the 1996 and 1997 Sampling Events.


. .. -.. ...-- .






67



7


High Flow
6 *



o



4



3 '.



2 Low Flow












-1
0
-1.




-- +-- May-03
-- Dec-03

0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-4. 5' N Signatures of Surface Suspended Particulate Organic Matter (SPOM)
for the Two 2003 Sampling Events.









Table 3-5. Stable Isotope Data of Suspended Particulate Organic Matter (SPOM) and
Dissolved Inorganic Nitrogen (DIN) for the 1996, 1997, and Two 2003
Sampling Events.
Station
1 2 3 4 5 6 7 8 9 10
615N of SPOM (per mil)
Nov-96 3.80 3.51 3.43 2.37 4.77 4.90 5.33 5.55 5.24 4.92
Mar-97 9.75 6.68 7.31 7.63 7.51 7.64 7.33 6.65 ND ND
May-03 2.87 2.40 -0.69 0.24 2.96 3.79 5.42 5.77 5.29 5.99
Dec-03 1.94 1.96 1.72 2.92 2.23 2.46 3.99 3.35 2.13 5.57
613C of SPOM (per mil)
Nov-96 -26.70 23.87 24.46 23.71 22.85 22.74 22.65 22.70 22.44 22.05
Mar-97 -25.84 24.78 25.95 25.31 22.97 22.41 22.26 21.84 ND ND
May-03 -27.90 27.61 24.42 26.91 26.07 24.13 24.18 24.08 22.11 20.39
Dec-03 -27.53 25.79 25.78 25.90 26.61 25.49 28.03 23.02 23.53 22.26
6sN DISSOLVED INORGANIC NITROGEN (per mil)
Nov-96
(Nitrate) 2.2 4.1 3.4 2.8 4.7 5.4 3.8 3.5 1.8 4.9
Mar-97
(Ammon) 8.2 9.9 11.4 3.0 11.5 11.9 14.8 12.0 11.7 14.5
May-03
(Nitrate) 7.0 8.0 7.5 6.8 6.9 5.4 5.3 5.1 2.1 2.1
Dec-03
(Nitrate) 3.7 5.3 4.8 6.4 6.3 7.0 7.0 7.3 5.8 -0.8

ND Not Determined








Spatial gradients in the stable nitrogen isotope composition of dissolved inorganic

nitrogen were apparent during the March 1997 sampling event. A sharp dip was present

at station 4 for the 6tSN of the DIN-ammonium, and the 615N of the DIN-nitrate was

lower than the DIN-ammonium (Figure 3-5, Table 3-5). The N of the DIN-nitrate for

the 2003 sampling event showed a variation between the different flow regimes (Figure

3-6). During the low flow period, 1'5N values increased steadily, whereas during the

high flow period, "5N values decreased steadily.

Zooplankton were collected only at stations 3 through 10 during the 2003 sampling

events (Figures 3-7 and 3-8). Only calanoid copepods, chaetognaths, and ctenophores

were retained for stable isotope analysis. The 61 N signatures of the zooplankton were

very similar and ranged from ca. 8 to ca. 10%o chaetognathss and ctenophores) and from

ca. 5 to ca. 10%o copepodss) during the high and low flow periods (Figure 3-7 and 3-8).

Oysters were sampled opportunistically near the transect sampling sites where they could

be found, and exhibited a marrow range in their '5N signatures, ca. 7.5 to 8%o (Figure 3-

9).

Spatial gradients in the stable carbon isotope composition (13C) of SPOM

collected from the surface waters of the Suwannee River estuary were apparent during

the 96/97 and 2003 sampling periods irrespective of the flow regimes (Figures 3-10 and

3-11). The 13C signatures of the SPOM from the 96/97 sampling events were similar to

the 613C signatures of the SPOM during the 2003 sampling event, ranging from -28%o in

the river to ca. -21%o at the farthest offshore stations (Figures 3-10 and 3-11).

The range of 613C signatures of the zooplankton were similar during the May and

December 2003 sampling events, with the copepods exhibiting slightly lower signatures










16




14




12




10




z
8




6




4




2


-.- Deli5N Nitrate
- Del15N Amm


/ x
I -,


At
\ i
S\ i

4* /

\ I
\ I

'4


0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-5. 815N Signatures of Surface Dissolved Inorganic Nitrogen (DIN) for the
March 1997 Sampling Event.






71



9
--*-. May-03
--- Dec-03
8 .




Low Flow

6


5


High Flow
4


3



2






0


-1



-2
0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-6. 68'N Signatures of Surface Dissolved Inorganic Nitrogen (DIN-Nitrate) for
the 2003 Sampling Events.










10



9



8



7



6



S 5



4



3



2



1



0


--+-.COPE
- CHAET
-C- CTEN


0 1 2 3 4 5
Station


6 7 8 9 10


Figure 3-7. S15N Signatures of Zooplankton Collected during the May 2003 (High Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores).


rA











11



10






8



7
-----...

6



5



4



3



2



1 *-*- COPE
-- CHAET
-*- CTEN
0
0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-8. 685N Signatures ofZooplankton Collected during the December 2003 (Low
Flow) Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths,
Cten = Ctenophores).













10

8

6

4

2

0

-2

-4

-6

- -8

z -10

-12

-14

-16

-18

-20

-22

-24

-26

-28


** .. +-. -**-+- *+










S 1 2 3 4 5 6 7 8 9 10 1

DeI15N
L-U- DeMl3C
























-- U-----,


Station


Figure 3-9. Stable Carbon and Nitrogen Isotopes of Oysters Collected During the
December 2003 Sampling Event.






75


-20



-21


High Flow
-22



-23
Low Flow


-24



S-25 ,



-26



-27



-28



-29
Nov-96
"5-. Mar-97
-30
0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-10. 63C of the Suspended Particulate Organic Matter (SPOM) for the 1996 and
1997 Sampling Events.






76



-20



-21


High Flow
-22



-23


-24 Low Flow
-24 .



S-25



-26



-27



-28



-29

*- *- May-03
---Dec-03
-30
0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-11. 13C of the Suspended Particulate Organic Matter (SPOM) for the Two
2003 Sampling Events.








than the chaetognaths and ctenophores at any given sampling station (Figures 3-12 and 3-

13). Oysters maintained a 813C signature of approximately -24 to -25%o (Figure 3-9).

Statistics

Analysis of variance (ANOVA) was used to test for effects of salinity on stable

isotopic signatures (15 N and 6"C) of SPOM, DIN and other water quality parameters

(Tables 3-6 through 3-9). Values were determined to be significantly different if p-values

were less than 0.05.

Discussion

The results of this study suggest differences in the physical, chemical, and

biological parameters during high and low flow regimes. The Suwannee River

discharges high concentrations of nutrients into the coastal region of west Florida,

compared to other rivers in the same area (Suwannee River Water Management District,

2003). Outside the mouth of the river, chemical analyses show a decline in nutrients with

distance offshore (Tables 3-3 and 3-4). Samples collected in the river during periods of

low flow (November 1996 and December 2003) exhibited higher concentrations of

inorganic nitrogen relative to those collected during high flow periods (March 1997 and

May 2003). In other systems such as New York Harbor, nitrogen concentrations increase

during rainy seasons due to surface water exportation into the system from the watershed

(Ryther and Dunstan, 1971), however, the opposite occurred in the Suwannee River

system. Nitrate increased in the river during low flow periods and decreased during high

flow periods (Suwannee River Water Management District, 1995, 1996, 2003). The

Suwannee River is a karst, spring-fed river system, and groundwater contributes

significantly to the river discharge during low flow periods (Pittman et al., 1997; Crandall

et al., 1999). Springs discharge is prevalent in the middle reaches of the Suwannee River






78



-15




-17




-19




-21




I -23 -

/ /
A--




-25




-27




-29

--+-*COPE
--CHAET
CTEN
-31
0 1 2 3 4 5 6 7 8 9 10 11
Station


Figure 3-12. 8'3C of Zooplankton Collected During the May 2003 Sampling Event
(Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores).











-20




-21




-22




-23




-24




S-25




-26




-27




-28




-29




-30


r
I
I



I
I
I


I
I

I
I
I
I .,
I
1










r


--*--COPE
--CHAET
--- CTEN


0 1 2 3 4 5 6 7 8 9 10 11

Station



Figure 3-13. 86C of Zooplankton Collected During the December 2003 Sampling Event
(Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores).






80


Table 3-6. ANOVA Tables for the Effects of Salinity on the 86N and 6'C of Suspended
Particulate Organic Matter during Novermber 1996.
NOVEMBER 1996 Sampling Event

Oneway Analysis of SPOM 815N By Salinity
Mean
Source of Variation DF* Sum of Squares Square F Ratio Prob > F "
Salinity 7 19.3663 2.7666 16.8960 0.00002
Error 12 1.9649 0.1637
Total 19 21.3312

Oneway Analysis of SPOM 8"C By Salinity
Mean
Source of Variation DF Sum of Squares Square F Ratio Prob > F
Salinity 7 33.6221 4.8032 87.3301 2.44E-09
Error 12 0.6600 0.0550
Total 19 34.2821

Degrees of freedom
If the probability is less than 0.05 (95% confidence) then there is significant variance






81


Table 3-7. ANOVA Tables for the Effects of Salinity on the 15N and 6"tC of Suspended
Particulate Organic Matter during March 1997.
MARCH 1997 Sampling Event

Oneway Analysis of SPOM 815N By Salinity
Mean
Source of Variation DF Sum of Squares Square F Ratio Prob> F
Salinity 7 7.3362 1.0480 2.9228 0.1062
Error 6 2.1514 0.3586
Total 13 9.4876

Oneway Analysis of SPOM 613C By Salinity
Mean
Source of Variation DF Sum of Squares Square F Ratio Prob> F
Salinity 7 36.9084 5.2726 5.2498 0.0219
Error 7 7.0305 1.0044
Total 14 43.9388









Table 3-8. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during
December 2003.
DECEMBER 2003 Sampling Event

Oneway Analysis of SPOM 815N By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 9 25.7998 2.8666 2.4135 0.0931
Error 10 11.8777 1.1878
Total 19 37.6775
Oneway Analysis of SPOM 813C By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 65.5696 7.2855 24.1083 0.00001245
Error 10 3.0220 0.3022
Total 19 68.5916
Oneway Analysis of DIN 81N-NO3 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 172.1822 19.1314 3.5323 0.0310
Error 10 54.1615 5.4161
Total 19 226.3437
Oneway Analysis of N03 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 9 3723545 413727 3065 5.34E-16
Error 10 1350 135.0
Total 19 3724895
Oneway Analysis of NH4 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 6534.00 726.00 11.56 3.40E-04
Error 10 628.00 62.80
Total 19 7162.00
Oneway Analysis of Chi a By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 9 211.3423 23.4825 39.7049 1.18E-06
Error 10 5.9143 0.5914
Total 19 217.2566
Oneway Analysis of Color By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 9 6844.2000 760.4667 7604.6667 5.68E-18
Error 10 1.0000 0.1000
Total 19 6845.2000
Oneway Analysis of DOC by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 9 25.49718 2.83302 15.31693 9.88E-05
Error 10 1.8496 0.18496
Total 19 27.34678









Table 3-8 Continued. ANOVA Tables for the Effects of Salinity on the Physical,
Chemical, and Biological Indicators of Suspended Particulate Organic Matter
during December 2003.
Oneway Analysis of TN by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 2262920.0 251435.6 867.0 2.92E-13
Error 10 2900.0 290.0
Total 19 2265820.0
Oneway Analysis of TP by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 8707.4500 967.4944 152.3613 1.66E-09
Error 10 63.5000 6.3500
Total 19 8770.9500
Oneway Analysis of SRP By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 15495.2 1721.6889 1565.1717 1.53E-14
Error 10 11.0 1.1000
Total 19 15506.2
Oneway Analysis of C-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 135.2867 15.0319 19.6729 3.18E-05
Error 10 7.6409 0.7641
Total 19 142.9276
Oneway Analysis of N-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 2.3578 0.2620 28.6788 5.52E-06
Error 10 0.0914 0.0091
Total 19 2.4492
Oneway Analysis of C:N-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 42.4307 4.7145 96.5498 1.58E-08
Error 10 0.4883 0.0488
Total 19 42.9190
Oneway Analysis of N-DIN By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 9 102.2519 11.3613 484.8015 5.31E-12
Error 10 0.2344 0.0234
Total 19 102.4863









Table 3-9. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during May
2003.
MAY 2003 Sampling Event

Oneway Analysis of SPOM 81SN By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 118.7969 14.8496 3.7383 0.0234
Error 11 43.6950 3.9723
Total 19 162.4919
Oneway Analysis of SPOM 8"'C By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 103.4872 12.9359 40.4563 4.41E-07
Error 11 3.5173 0.3198
Total 19 107.0045
Oneway Analysis of DIN 851N-NO3 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 433.3482 54.1685 2.6594 6.76E-02
Error 11 224.0538 20.3685
Total 19 657.4020
Oneway Analysis of N03 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob> F
Salinity 8 691979.0500 86497.3813 917.0807 2.00E-14
Error 11 1037.5000 94.3182
Total 19 693016.5500
Oneway Analysis of NH4 By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 9718.5500 1214.8188 28.1771 2.88E-06
Error 11 474.2500 43.1136
Total 19 10192.8000
Oneway Analysis of Chi a By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 752.2718 94.0340 178.0946 1.56E-10
Error 11 5.8080 0.5280
Total 19 758.0798
Oneway Analysis of Color By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 62196.2000 7774.5250 2327.0687 1.20E-16
Error 11 36.7500 3.3409
Total 19 62232.9500
Oneway Analysis of DOC by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 199.7360 24.9670 48.9091 1.63E-07
Error 11 5.6153 0.5105
Total 19 205.3513









Table 3-9 Continued. ANOVA Tables for the Effects of Salinity on the Physical,
Chemical, and Biological Indicators of Suspended Particulate Organic Matter
during May 2003.
Oneway Analysis of TN by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 2028145.0000 253518.1250 369.3642 2.92E-12
Error 11 7550.0000 686.3636
Total 19 2035695.0000
Oneway Analysis of TP by Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 35881.8000 4485.2250 573.6916 2.62E-13
Error 11 86.0000 7.8182
Total 19 35967.8000
Oneway Analysis of SRP By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 23486.8000 2935.8500 949.8338 1.65E-14
Error 11 34.0000 3.0909
Total 19 23520.8000
Oneway Analysis of C-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 159.4177 19.9272 4.2376 1.51E-02
Error 11 51.7277 4.7025
Total 19 211.1454
Oneway Analysis of N-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 5.7842 0.7230 11.9665 1.96E-04
Error 11 0.6646 0.0604
Total 19 6.4488
Oneway Analysis of C:N-SPOM By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 77.4207 9.6776 37.4608 6.60E-07
Error 11 2.8417 0.2583
Total 19 80.2624
Oneway Analysis of N-DIN By Salinity
Source of Variation DF Sum of Squares Mean Square F Ratio Prob > F
Salinity 8 136.5347 17.0668 227.3580 4.14E-11
Error 11 0.8257 0.0751
Total 19 137.3604








and many of those springs have elevated concentrations of nitrate (up to 8.0 mgfL)

(Suwannee River Water Management District, 1995, 1996, 2003). During high flow

periods, precipitation and surface flow dilute the concentration of nitrates coming into the

river through the springs.

Concentrations of nutrients (nitrogen and phosphorus), chlorophyll a (estimation of

phytoplankton biomass in the water column), dissolved organic carbon, and color

contribute to light attenuation in the Suwannee River (Bledsoe, 1998). High

concentrations of nutrients (especially nitrate) enter the middle reaches of the Suwannee

River (Suwannee River Water Management District, 2003). Phytoplankton in the river

are light limited Bledsoe, 1998) and otherwise available nitrate is not utilized extensively

by phytoplankton (low chlorophyll a levels within the river). Near the mouth of the river

and in the estuary, color and DOC decrease as seawater mixes with river water, and it is

at this point that phytoplankton are no longer light-limited. Phytoplankton numbers

increase in the estuary (based on chlorophyll a concentrations, Table 3-2), and

eutrophication of this system as a consequence of increased nutrient loading is a

legitimate concern (see Frazer et al., 1998).

Natural abundance measures of stable nitrogen and carbon isotope ratios can

contribute to the study of nutrient pollution by determining the source material fueling

production in a system. Temporal and spatial patterns in 6'5N and 13C can provide

additional information on transformation processes. Temporal variation in the stable

nitrogen signature of suspended particles in the Suwannee River is reflective of relative

differences in the abundance of nitrogen sources in the river during low flow and high

flow periods (Figures 3-3 and 3-4, Table 3-5). The 65N signatures of SPOM during








March 1997 (high flow) were higher than those collected during November 1996. During

low flow periods, much of the river is being fed by springs with high nitrate

concentrations. The source of nitrate is often from synthetic fertilizers (as opposed to

remineralized organic matter) within the Suwannee River watershed (Asbury and

Oaksford, 1997; Katz et al., 2001). Typical 5i5N values of fertilizers are low, or close to

zero (Freyer and Aly, 1974; Flipse and Bonner, 1985; Macko and Ostrom, 1994; Fry et

al., 2001). This is because most fertilizers are produced by the Haber process which

converts atmospheric nitrogen to ammonium. In this process, the fertilizers retain the

isotopic signature of atmospheric nitrogen (f'5N = 0%o) (Macko and Ostrom, 1994).

During high flow periods, the river is also being fed by overland flow, and this results in

the addition of organic nitrogen from animal waste material. Nitrate produced from

animal waste typically exhibit '6SN values greater than fertilizer 6'5N (Peterson and Fry,

1987; Karr et al., 2001; Karr et al., 2003). During the two 2003 sampling events, 61sN

signatures of SPOM were nearly the same (starting at 2-3%o in the river stations and

increasing to 5-6%0 at station 10) during the high and low flow regimes. The low initial

i65N signatures of the May 2003 sampling event indicate that the source of nitrogen

coming into the system was likely from a source similar to that of synthetic fertilizers.

Differences in the 815N of SPOM in the river between 96/97 and 2003 could indicate that

input of fertilizer to the river is increasing, or the relative contribution of DIN from

animal waste is decreasing.

Spatial gradients in the '15N of SPOM collected from surface waters were present

during low and high flow regimes (Figures 3-3 and 3-4, Table 3-5). The 65N of SPOM

decreased near the mouth of the river at stations 2 (March 1997), 4 (November 1996),








and 3 (May 2003), then leveled out to a signature closer to that typical of marine

phytoplankton (6%o) (Owens, 1987). The decrease near stations 2 through 4 did not

occur during the December 2003 sampling event. It did, however, slowly increase to a

signature near 6%o by station 10.

Most reactions in which bonds with a nitrogen atom are formed or broken tend to

discriminate against the heavier isotope, resulting in a product depleted in '5N relative to

the substrate (Figure 3-14). There is a progressive increase in the 815N of the residual

pool of reactant as the reaction proceeds. If a reaction goes to completion and the entire

pool of reactants is converted to product (e.g., in a closed system), then conservation of

mass requires that the final product have the same isotopic composition as the initial pool

of reactants (Peterson and Fry, 1987; Montoya and McCarthy, 1995). In an ecological

context, the isotopic fractionation associated with the uptake and assimilation of

dissolved inorganic nitrogen (DIN) by phytoplankton and other autotrophs (i.e. attached

macroalgae, seagrasses, and epiphytic algae) should result in the production of autotroph

biomass depleted in 15N relative to the available substrate, primarily NO3- in the case of

the Suwannee River and its estuary. This, in turn, will create a spatial gradient in the

stable nitrogen isotope composition of suspended particles in the Suwannee River estuary

(Figure 3-15). Our findings are consistent with this scenario (excluding the December

2003 sampling event) and provide critical information for the interpretation of naturally

occurring variations in 15N in these and other river and estuarine systems.

The stable nitrogen isotope ratio of DIN had not been measured previously in the

Suwannee River and its estuary. These measurements are needed for a more complete

test of the spatial gradient theory. Distinct spatial gradients in the 6'SN were expected to








































100%o


Figure 3-14. Model of Spatial Gradients in the "1N Signatures of a Hypothetical Closed
System (redrawn from Montoya and McCarthy, 1995).




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TRANSFORMATION AND FATE OF DISSOLVED ORGANIC MATTER
ORIGINATING IN THE SUWANNEE RIVER WATERSHED: A STABLE ISOTOPE
APPROACH
By
EMILY R. HALL
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
2004

ACKNOWLEDGMENTS
Financial support for this work was provided in part, by the USDA (Grant # 2001-
35102-09857), NSF (Grant # OCE0240187), the University of Florida Women’s Club,
and the University of Florida.
Everyone who I have had contact with in any way throughout my time at the
University of Florida has influenced my life in some way. I thank them all from the
bottom of my heart, even though I know simple thanks are not enough. I must
acknowledge them to the best of my ability on paper, but know that they all mean the
world to me.
First I must start with my family. My parents have been through thick and thin
with me, and I could not have done well without their support, both financially and
emotionally. My sister has been an ear for me to talk to, and she has taught me to live
free. My brother has been a source of energy, and he has taught me to enjoy life while
still working hard.
My mentors have been crucial in my academic journey. Dr. Brian Rood gave me
the first opportunity to pursue a career in environmental science. His enthusiasm and
love for the environment as well as his energy guided me towards this field of science.
Dr. Joseph Delfino, my committee chair for the past five and a half years, took over
where Dr. Rood left off. He guided me through tough times, scientifically and
administratively, and he has had continued faith in my abilities. Dr. Tom Frazer, my co¬
chair, willingly provided me with a project without prior knowledge of my capabilities.

He allowed me to learn from my mistakes and he pushed me to become a better scientist.
I also acknowledge my committee members Dr. Jean-Claude Bonzongo and Dr. Mark
Brenner for their mentoring and involvement in my graduate education.
My peers have also had a large influence during my time at the University of
Florida. Unfortunately (but fortunately) this group is the largest, and I cannot mention
everyone individually. First I will start with my research groups in Black Hall and at the
Department of Fisheries and Aquatic Sciences. They provided me with friendships that I
will never forget as well as inspiration to work hard in science and in life. I also thank
the University of Florida Club Soccer program. It gave me an opportunity to continue to
play the sport I love, and to have some of the best friendships. Lastly, I thank Jason
Heggerick for being my strength and support dining demanding times. He was a
shoulder to cry on and a friend to laugh with.
“The sea lies all about us. The commerce of all lands must cross it. The very
winds that move over the lands have been cradled on its broad expanse and seek ever to
return to it. The continents themselves dissolve and pass to the sea, in grain after grain of
eroded land. So the rains that rose from it return again in rivers. In its mysterious past it
encompasses all the dim origins of life and receives in the end, after, it may be, many
transmutations, the dead husks of that same life. For all at last returns to the sea-to
Oceanus, the ocean river, like the ever-flowing stream of time, the beginning and the
end” (Rachel Carson, The Sea Around Us). There are no limits for journeys of the mind.

TABLE OF CONTENTS
Eage
ACKNOWLEDGMENTS ii
LIST OF TABLES vi
LIST OF FIGURES vii
ABSTRACT x
CHAPTER
1 INTRODUCTION 1
Background 1
Suwannee River and Estuary 1
Nutrient Loading, Especially Nitrogen 4
Clam and Oyster Ecology 6
Humic Substances 8
Flocculation 11
Stable Carbon and Nitrogen Isotopes as Tracers of Material Transfer and Energy
Flow 19
Proposed Research 29
2 STABLE CARBON AND NITROGEN ISOTOPE COMPOSITION OF ORGANIC
AGGREGATES PRODUCED BY SALINITY INDUCED FLOCCULATION OF
DISSOLVED ORGANIC MATTER FROM THE SUWANNEE RIVER 30
Introduction 30
Methods and Materials 34
Site 34
Methods 35
DOC and Stable Isotope Analysis 36
Results 36
Discussion 46
Summary 50
Conclusions 50
3 SPATIAL GRADIENTS IN THE STABLE CARBON AND NITROGEN ISOTOPE
COMPOSITION OF SUSPENDED PARTICLES IN THE SUWANNEE RIVER
ESTUARY DURING DIFFERENT FLOW REGIMES 51
iv

Introduction 51
Methods, Materials, and Site Description 53
Site Description 53
Methods 54
Results 59
Physical Parameters 59
Chemical Parameters 59
Biological Indicator 65
Stable Isotope Analyses 65
Statistics 77
Discussion 77
Summary 94
Conclusions 95
4 STABLE ISOTOPES AS TRACERS IN FOOD WEB INVESTIGATIONS OF THE
SUWANNEE RIVER ESTUARY 96
Introduction 96
Methods and Materials 99
Site Description 99
Sampling 100
Stable Isotope Analyses 101
Results 101
Discussion 103
Stable Carbon Isotopes 103
Stable Nitrogen Isotopes 112
Multiple Stable Isotopes and Food Source 112
Summary 118
Conclusions 118
5 SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS 120
Summary 120
Conclusions 121
Recommendations for Further Research 122
APPENDIX
A SUPPLEMENTAL STABLE CARBON AND NITROGEN ISOTOPE DATA 123
B SUPPLEMENTAL SIZE AND WEIGHT DATA OF CLAMS 133
C SUPPLEMENTAL SIZE AND WEIGHT DATA OF OYSTERS 140
LIST OF REFERENCES 143
BIOGRAPHICAL SKETCH 158
v

LIST OF TABLES
Table page
2-1. Analysis of Variance (ANOVA) Results for all of the Floe Studies 38
3-1. Location and Site Names for Sampling Sites in the Suwannee River and its Estuary.57
3-2. Chemical and Biological Parameters in the Suwannee River and its Estuary for Each
Sampling Event 60
3-3. Concentrations of Nitrogen Components (jag/L) in the Suwannee River and its
Estuary for Each Sampling Event 63
3-4. Concentrations of Phosphorus Components (/tg/L) in the Suwannee River and its
Estuary for each Sampling Event 64
3-5. Stable Isotope Data of Suspended Particulate Organic Matter (SPOM) and
Dissolved Inorganic Nitrogen (DIN) for the 1996, 1997, and Two 2003 Sampling
Events 68
3-6. ANOVA Tables for the Effects of Salinity on the SI5N and 6I3C of Suspended
Particulate Organic Matter during Novermber 1996 80
3-7. ANOVA Tables for the Effects of Salinity on the 5I5N and 5I3C of Suspended
Particulate Organic Matter during March 1997 81
3-8. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during December
2003 82
3-9. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during May 2003.84
A-l. Stable Carbon and Nitrogen Isotopes of Clams, Oysters, and Suspended Particulate
Organic Matter (SPOM) 123
B-l. Size (mm) and Weight (g) Data of Clams 133
C-1. Size (mm) and Weight (g) of Oysters 140
vi

LIST OF FIGURES
Figure page
2-1. Salinity versus Dissolved Organic Carbon in the Upper and Lower Suwannee River
Floe Studies 39
2-2. Time versus Dissolved Organic Carbon for Floe Studies I and II 40
2-3. Salinity versus 8I5N for the Upper and Lower Suwannee River Flocculated Organic
Aggregates 41
2-4. Salinity versus 813C for the Upper and Lower Suwannee River Flocculated Organic
Aggregates 42
2-5. Salinity versus Average S15N Signatures of the Upper and Lower Suwannee River
Floe Studies Including Standard Deviation Error Bars 43
2-6. Salinity versus Average 513C Signatures of the Upper and Lower Suwannee
River Floe Studies Including Standard Deviation Error Bars 44
2-7. Salinity versus C:N Ratios of the Flocculated Organic Aggregates from the Upper
and Lower Suwannee River Floe Studies Including Standard Deviation Error
Bars 45
3-1. Map of the Sampling Sites in the Suwannee River and its Estuary 56
3-2. Monthly Streamflow Data for the Suwannee River near Wilcox, Florida (USGS,
2004) 61
3-3. 8I5N Signatures of Surface Suspended Particulate Organic Matter (SPOM) for the
1996 and 1997 Sampling Events 66
3-4. 8ISN Signatures of Surface Suspended Particulate Organic Matter (SPOM) for the
Two 2003 Sampling Events 67
3-5. SlsN Signatures of Surface Dissolved Inorganic Nitrogen (DIN) for the March 1997
Sampling Event 70
3-6. 8I5N Signatures of Surface Dissolved Inorganic Nitrogen (DIN-Nitrate) for the 2003
Sampling Events 71

3-7. S15N Signatures of Zooplankton Collected during the May 2003 (High Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores) 72
3-8. 8ISN Signatures of Zooplankton Collected during the December 2003 (Low Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores) 73
3-9. Stable Carbon and Nitrogen Isotopes of Oysters Collected During the December
2003 Sampling Event 74
3-10. 8I3C of the Suspended Particulate Organic Matter (SPOM) for the 1996 and 1997
Sampling Events 75
3-11. 813C of the Suspended Particulate Organic Matter (SPOM) for the Two 2003
Sampling Events 76
3-12. 813C of Zooplankton Collected During the May 2003 Sampling Event (Cope =
Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores) 78
3-13. SI3C of Zooplankton Collected During the December 2003 Sampling Event (Cope
= Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores) 79
3-14. Model of Spatial Gradients in the 515N Signatures of a Hypothetical Closed System
(redrawn from Montoya and McCarthy, 1995) 89
3-15. Theoretical Curves Illustrating Spatial Variation in the 5I5N of Phytoplankton
along an Onshore/Offshore Gradient. Losses in the Bottom Panel Occur as a
Consequence of Grazing and Sedimentation Processes 90
3-16. S15N vs. S,3C of Oysters, Zooplankton, and SPOM for the December 2003
Sampling Event 91
3-17. 615N vs. 6l1C of Oysters, Zooplankton, and SPOM for the May 2003
Sampling Event 92
4-1. Map of Sampling Sites for Clams, Oysters, and Suspended Particulate Organic
Matter (SPOM) in the Suwannee River Estuary 102
4-2. 513C of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River
Estuary Sites 104
4-3. ói5N of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River
Estuary Sites 105
4-4. S13C of Clams from Two Suwannee River Estuary Sites.
viii
106

4-5. SI3C of Oysters from Two Suwannee River Estuary Sites 107
4-6. S15N of Clams from Two Suwannee River Estuary Sites 109
4-7. 615N of Oysters from Two Suwannee River Estuary Sites 110
4-8. o13C vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary
Sites 113
4-9. 5I3C vs. Dry Body Weight (g) of Oysters from Two Suwannee River Estuary
Sites 114
4-10. 615N vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary
Sites 115
4-11. oi5N vs. Dry Body Weight (g) of Oysters from Two Suwannee River Estuary
Sites 116
4-12. The Suwannee River Estuary Food Web Structure Using S13C and olsN 117
ix

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
TRANSFORMATION AND FATE OF DISSOLVED ORGANIC MATTER
ORIGINATING IN THE SUWANNEE RIVER WATERSHED: A STABLE ISOTOPE
APPROACH
By
Emily R. Hall
December 2004
Chair: Joseph J. Delfino
Cochair: Thomas K. Frazer
Major Department: Environmental Engineering Sciences
Anthropogenic activities in a watershed can have significant impacts on the
ecology of downstream coastal environments. Surface runoff and groundwater inputs
from the Suwannee River watershed contribute high concentrations of nutrients (nitrates
>1 mg/L) to this blackwater river before it discharges into the Gulf of Mexico. High
concentrations of nutrients have the potential to affect the sustainability, productivity, and
growth of the oyster and clam aquaculture industries in the estuary. In determining
detrimental effects, it is important to establish a link between dissolved carbon and
nitrogen, suspended particulate organic matter (SPOM), and production of clam and
oyster biomass in the Suwannee River estuary.
Organic aggregates (a possible food source for the bivalves in the Suwannee River
estuary) were produced in the laboratory by adding salts to unfiltered fresh organic-
enriched Suwannee River surface water. They were analyzed for stable carbon and
nitrogen isotopes and the results indicate that the 615N signatures can be used as a tracer
x

of organic aggregate development. More importantly, however, the results suggest that
5I3C signatures of organic aggregates can be used to quantify their role as a food source
for estuarine fauna.
Spatial gradients in nutrient concentrations, particularly nitrate, are characteristic of
estuarine systems. These gradients occur as a result of mixing processes and uptake and
assimilation by phytoplankton. Isotopic fractionation associated with this uptake and
assimilation can generate strong spatial gradients in the stable nitrogen isotope
composition of particulate nitrogen. In essence, stable nitrogen isotopes serve as in situ
tracers of the processing of nitrogen as it moves through an estuarine system.
Clams and oysters were seeded in the Suwannee River estuary near the river
mouth. Clams, oysters, and SPOM were sampled monthly for approximately one year
and subsequently analyzed for stable carbon and nitrogen isotopes. The results indicate
that the clams consumed the same source of organic material throughout the year (marine
SPOM), while the oysters’ food source changed consistently with hydrologic patterns in
the river (e.g., more terrestrial origin during high flow and more marine origin during low
flow). Neither clams nor oysters consumed flocculated organic aggregates as a dominant
food source.
xt

CHAPTER 1
INTRODUCTION
Background
Anthropogenic activities in a watershed can have significant impacts on the
ecology of downstream coastal environments. The Suwannee River drains 28,000 km2 of
southern Georgia and north central Florida (Wolfe and Wolfe, 1985). Surface runoff and
groundwater inputs contribute high levels of nutrients to this blackwater river before it
discharges into the region of the Gulf of Mexico known as the Big Bend. This region of
Florida has a relatively low population density; however, there have been significant
increases in a variety of agricultural activities in the river basin. Nitrogen-enriched run¬
off from these agricultural areas filters into the groundwater because of the porous nature
of the karst sediments characteristic of the region. Ultimately, these increases in
groundwater nitrogen are manifested as higher nitrate concentrations in the river, due to
numerous spring inflows. Nitrate levels within the Suwannee River are increasing and
concentrations near the mouth and in the upper reaches of the estuary now regularly
exceed 1 mg/L (Phlips and Bledsoe, 1997). This has brought on widespread concern
about the potential consequences of cultural eutrophication of the region on the
ecological health of the river and the coastal waters of the Big Bend.
Suwannee River and Estuary
The Suwannee River is a blackwater, tidally influenced river with its origin in the
Okefenokee Swamp in Georgia. The river is approximately 394 km in length, flows
southwest through Florida, and discharges into the Gulf of Mexico just north of Cedar
1

2
Key. Tributaries include the Alapaha, Withlacoochee, and Santa Fe Rivers. At the
mouth of the river there is a delta region which is characterized by a network of intertidal
and subtidal oyster reefs (Wolfe and Wolfe, 1985).
The geographical features of the Suwannee River and the Okefenokee Swamp
include flat terrace, the Trail Ridge sand barrier, and the Hawthorne Formation (Malcom
et al., 1989a). There are also shallow clay lenses near the headwaters of the river. Much
of the river and its watershed are underlain by karst limestone, allowing nutrients to leach
into the aquifer and ultimately enter the Suwannee River through the groundwater springs
along its banks (Crandall et al., 1999; Bledsoe and Phlips, 2000). Water is mixed
between the river and aquifer primarily through springs and diffuse groundwater seepage
(Pittman et al., 1997).
The water quality of the upper Suwannee River is indicated by low pH, low
concentration of dissolved inorganic solids, and high concentration of dissolved organic
substances, especially fulvic acids (Malcolm et al., 1989a). The lower Suwannee River
maintains a higher pH (6 to 9) (Wolfe and Wolfe, 1985). The source of the humic
substances in the water is predominantly fresh litter, leaf, and root exudates, and leaf
leachates. Very little of the colored dissolved organic matter (CDOM) is due to older and
more slowly decaying peat (Malcolm et al., 1989a). The concentration of these humic
substances has been shown to be an order of magnitude greater than that in most natural
stream waters. The dissolved organic carbon concentrations are in excess of 25 mg/L
(Malcolm et al., 1989b). High nutrient concentrations are also present in the river due to
the large amounts of fertilizer entering the system through groundwater and overland
flow (Suwannee River Water Management District, 2003).

3
The climate along the river is characterized by long, warm summers and short, mild
winters (Malcolm et ah, 1989a; Crandall et ah, 1999; Katz et ah, 2001). Peak mean daily
discharge in the river usually occurs in March or April, and September due to continental
frontal systems (Crandall et ah, 1999); however, discharge rates are generally fairly
uniform throughout much of the year (Malcolm et ah, 1989b). A large source of water
for the Okefenokee Swamp, and hence the Suwannee River, is rainfall. Overland flow
and groundwater (via numerous springs) also contribute to the amount of water flowing
through this system (Wolfe and Wolfe, 1985; Crane, 1986). During the months of heavy
rains, the river flows more rapidly, and there is generally a higher organic content as a
result of drainage from the swamp and watershed to the river. When precipitation is low,
water is contributed to the river through springs and diffuse seepage fed by the Floridan
Aquifer (Crane, 1986).
There is much less land development and point source pollution in this river and its
plume than in most other coastal regions in Florida (Bass and Cox, 1988). Major land
uses in the watershed include forestry and agriculture (row crops, dairy, poultry, swine
farming operations, and pasture) (Katz et al., 2001). In 1995, wetlands comprised about
2% to 36% of the land use in Suwannee and Lafayette Counties (Katz et al., 2001).
Asbury and Oaksford (1997) characterized the watershed in the Suwannee basin as
50.4% forested, 15.9% wetland, 31.2% agriculture, and 0.8% residential. The land
immediately surrounding the river is predominantly used for pine forestry operations.
Fertilizer from pine forestry operations and waste material from dairy practices are
thought to be a significant source of non-point source nutrient loading to the river
(Asbury and Oaksford, 1997). The Suwannee River could potentially be highly

4
influenced by these large amounts of nitrogen coming into the system. The clam beds
and oyster reefs at the mouth of the river and in the estuary are harvested periodically
throughout the year. Increased nutrient loads may negatively affect these and other
species, although elevated nutrient concentrations can lead to high production of
phytoplankton. This production can lead to low dissolved oxygen concentrations, and, in
turn affect production and survivorship.
Nutrient Loading, Especially Nitrogen
River discharge provides a significant source of nutrients to estuaries; however this
can be considered contamination as well as a pathway for increased productivity. The
potential impact of a contaminant such as nitrogen in the environment depends not only
on the concentration and mobility of the species, but also on its bioavailability (Suffet
and MacCarthy, 1989). Increased nutrient loads can lead to the eutrophication of surface
waters, and high nitrate concentrations (>10 mg/L) especially pose a possible health risk
in drinking water (Asbury and Oaksford, 1997). Other possible effects include harmful
cause algal blooms and low dissolved oxygen concentrations, which can have detrimental
effects on the entire ecosystem.
Sources of nutrients in the Suwannee River include atmospheric deposition,
fertilizer, animal waste, and septic discharge, with nitrogen from fertilizer and animal
wastes predominating (Asbury and Oaksford, 1997). Asbury and Oaksford (1997)
estimated the nitrogen stream load per year in the Suwannee River as 9,700,000 kg/yr and
476 (kg/yr)/km2, and found that organic nitrogen was the most abundant nitrogen
compound. Nitrogen exists in the river largely in the form of NO3'; however, nitrogen is
also a trace constituent in aquatic humic substances. According to Thurman and
Malcolm (1989), the nitrogen content of fulvic acids varies from 0.5 to 1.5 percent;

5
however aquatic humic acid has twice as much nitrogen as fulvic acid. In the Suwannee
River, the concentration of nitrogen in fulvic acid is 0.56 percent, and in humic acid it is
1.08 percent (Thurman and Malcolm, 1989). Frazer et al. (2002) found that nitrate
discharged from the lower Suwannee River was quickly diluted and/or assimilated as it
entered the Gulf of Mexico.
Agricultural activities and other land uses have impaired the quality of spring
waters by contributing large quantities of nutrients to groundwater recharge in many parts
of the world (Katz et al., 2001). During the past 50 years, nitrate-N concentrations in
groundwater discharging from several springs in the middle Suwannee River Basin have
increased from near background concentrations (less than 0.1 mg/L) in groundwater to
more than 5 mg/L (Katz et al., 2001). However, nitrate concentrations in the water from
four springs in Suwannee County generally have remained constant or have decreased
slightly in the last few decades following a decrease in the use of fertilizers (Katz et al.,
2001).
Many different factors in an ecosystem such as the Suwannee River impact the
nutrients once they enter the system, and nutrient concentrations can change with time.
Rates of change are a function of mixing and transport, emission rate, sinks, and
reactivity (Suffet and MacCarthy, 1989). Chemical influences on nutrients include
physiochemical reactions of the compounds (e.g., sorption, coagulation, acid-base
interactions, and complexation reactions), and chemical changes (e.g., oxidation,
reduction, hydrolysis, and photochemical reactions). Physical influences include
transport and dispersal. Biological influences include uptake and mineralization by
organisms and metabolic changes associated with receptor organisms and food web

6
interactions (Suffet and MacCarthy, 1989; Horrigan et al., 1990). Nutrients from
fertilizers will be taken up and used by organisms, such as algae, which will, in turn, be
consumed by higher trophic levels in river and estuarine systems. Nutrient flows through
these types of ecosystems have been studied in great detail (e.g., Kaul and Froelich, 1984;
Horrigan et al., 1990; Wada and Hattori, 1991; Schelske and Hodell, 1995).
Nitrate and ammonium are taken up by microbes, algae, and macrophytes, but
organic particles are generally consumed by organisms such as clams and oysters in
estuarine environments. As previously stated, there is a small amount of nitrogen present
in humic substances. Clams and oysters can readily consume phytoplankton (a known
source of good quality food), but organic nitrogen aggregates that are formed from
dissolved compounds have also been found to be an important source of nitrogen for
these consumers (Alber and Valiela, 1996).
Clam and Oyster Ecology
At the mouth of the Suwannee River and in the estuary oyster reefs are common.
In addition, there are a number of lease sites where hard clams are allowed to grow for
harvest. The predominant species are Crassostrea virginica and Mercenaria mercenaria.
The oysters, Crassostrea virginica, are well suited to estuarine conditions. They can
tolerate wide ranges of temperatures, salinity, turbidity, and dissolved oxygen. They can
also generate their own substrate by producing their own shells to which they attach (Day
et al., 1989; Ruppert and Bames, 1994). These organisms are typically limited by space
(Day et al., 1989). Oysters are suspension feeders (pump and filter a large quantity of
water to obtain sufficient food of the proper quality), and it is important that the quality
(nutrient content) of the food be very high to achieve maximal growth. Adult oysters
actively pump (through ciliary action) several liters of water per hour across their gills

7
(Day et al., 1989; Ruppert and Barnes, 1994). Therefore, dense populations of
suspension feeders can become limited by food in areas with a lack of circulation (Day et
al., 1989). Ammonia and phosphorus are regenerated by these organisms as a
consequence of excretion and fecal production (as subsequent remineralization). Oyster
harvesting is an important industry for Florida’s economy, and oysters also provide a
source of food for birds and several aquatic organisms (e.g., sea anemone, crabs,
flatworms, etc.) (Dunning and Adams, 1995; Colson and Sturmer, 2000; Newell et al.,
2000).
The clam, Mercenaria mercenaria, is also an important food source for humans,
some birds, and aquatic organisms. It is one of the most important commercial bivalve
species on the eastern coast of the United States, and the Suwannee River estuary is the
most economical area to grow these clams in the natural environment (Pfeiffer et al.,
1999; Colson and Sturmer, 2000). They feed in a similar manner to the oysters
(suspension feeders), and as clams grow and population numbers increase, food
requirements grow exponentially (Ruppert and Barnes, 1994; Pfeiffer et al, 1999).
There are three trophic pathways by which clams and oysters might ingest and
subsequently assimilate detritus: (1) via direct uptake of dissolved organic matter (which
is released by both live and decaying producers), (2) ingestion of particulate detritus, and
(3) ingestion of organic aggregates (Alber and Valiela, 1994a). Alber and Valiela
(1994a) have also found that bivalves are capable of taking up bacteria. In a study by
Crosby et al. (1990), the oyster, Crassostrea virginica, was found to assimilate refractory
Spartina alternijlora-derived detritus with an efficiency of 2.7 percent, whereas material

8
that was colonized by bacteria was assimilated with an efficiency of 10.3 percent. These
findings suggest that bacteria can actually enhance the quality of food for the consumers.
Suspension feeders encounter food supplies of varying nutrient quality, quantity,
and size. Many bivalves are able to alter their capture rates and strategies to account for
lower quality food. Ward et al. (1997), for example, showed that oysters can select living
particles from non-living detritus on the gills. Ward et al. (1998), in a subsequent study,
determined that in the oyster, Crassostrea virginica, the ctenidia are responsible for
particle sorting while the labial palps have an accessory role in particle selection. There
have been several studies with bivalves demonstrating the ability to sort particles based
on size (e.g., Vahl, 1972; Stenton-Dozey and Brown, 1992; Defossez and Hawkins, 1997;
Raby et al., 1997; Brillant and MacDonald, 2000).
Humic Substances
Organics within a river system can be allochthonous (produced outside of the
system) or autochthonous (produced within the system). Allochthonous organic
materials include humic substances. The dissolved organic matter (DOM) in an average
river is typically composed of about 50% humic substances; however DOM is highly
variable depending on source of organic matter, temperature, ionic strength, pH, major
cation composition of the water, sorption processes, and microbial degradation processes
(Leenheer and Croué, 2003; Schwarzenbach et al., 2003). In the case of the Suwannee
River, a blackwater river, there are high concentrations of dissolved humic substances in
the water, ranging up to 60 mg/L at its source. The water in the Suwannee River is dark
and acidic due to the high amounts of humic substances from decomposition of swamp
vegetation (Malcolm et al., 1989a). Much of this humic material originates in the

9
Okeefenokee Swamp. Along the river channel there are many pine forests which also
contribute to the high concentration of dissolved humic acids.
Humic substances are ubiquitous organic materials in the environment that result
from the decomposition of plant and animal residues (Suffet and MacCarthy, 1989;
MacCarthy, 2001). They can be expressed as dissolved organic carbon (aqueous
materials that pass through a 0.45-^m filter); however, some of these materials may be in
colloidal form rather than in solution. Humic substances can assist with the transport of
metals through complexation and ion-exchange mechanisms, depending on the redox
state of the metal ions, leading to either solubilization or immobilization of the metals.
Humic substances also interact with nonionic compounds (pesticides and other river
contaminants) via sorption, causing the immobilization of such compounds in
sedimentary organic matter (Schwarzenbach et ah, 2003). Humic substances in solution
consist of amino acids, sugars, various aliphatic and aromatic acids, and a variety of more
complex organic compounds. They can be somewhat polar in that they contain numerous
oxygen-containing functional groups including carboxy-, phenoxy-, hydroxy-, and
carbonyl- substituents (Stumm and Morgan, 1996; MacCarthy, 2001; Schwarzenbach et
ah, 2003). This allows them to interact with water-soluble compounds. However, they
also consist of nonpolar constituents which allow them to interact with water-insoluble
compounds (Calace et ah, 1999). In soils, sediments, and suspensions, humic substances
are often bound with inorganic materials (i.e., clays and metals) (Suffet and MacCarthy,
1989; Meier et ah, 1999; Schwarzenbach et ah, 2003).
Humic substances are typically fractionated into the following groups: humic acid -
the fraction of humic substances that is not soluble in water under acidic conditions

10
(pH<2) but is soluble at higher pH values; fulvic acid - the fraction of humic substances
that is soluble in water under all pH conditions; and humin - the fraction of humic
substances that is not soluble in water at any pH value. There are different concentrations
of each of these groups in different river systems. Studies show that typically 90% of
dissolved humic substances is fulvic acid and 10% is humic acid (Suffet and MacCarthy,
19S9; Hautala et al., 1998). In the Suwannee River, fulvic acids are most dominant
(Malcolm et ah, 1989a).
Humic substances can be a food source for organisms in river and estuarine
environments. Detritus (humic substances) is generally a year-round source of food and
may be more abundant than phytoplankton at times (Alber and Valiela, 1996). However,
it is also found to be very recalcitrant to biological and chemical degradation (Wang et
ah, 2000). Therefore, humic substances are often poor quality food (Alber and Valiela,
1994a). Before many humic substances can be eaten, some detritivores depend on
microbes to decompose and alter the quality of the detritus by increasing both its
available nitrogen content (see below) and availability to consumers (Alber and Valiela,
1994a). The dissolved organic matter is, therefore, a growth substrate for bacteria (Sun et
ah, 1997). It has been shown that bacteria use dissolved organic matter at specific size
ranges (small>medium>large); however higher molecular weight dissolved organic
matter (as humic substances) is generally most available (Engelhaupt et ah, 2002). Sun et
ah (1997) found that bacterial growth was positively correlated with H:C and N:C ratios,
and negatively correlated with 0:0 ratios. Colonization by bacteria can enhance the
quality of the food for consumers through metabolism of larger nitrogen containing
molecules to smaller, more available forms.

11
The dissolved organic carbon concentration in colored surface waters is extremely
variable and typically ranges from about five to more than 50 mg of carbon/L (Suffet and
MacCarthy, 1989). The fraction of the total dissolved organic carbon that is in the form
of humic substances varies considerably and can be up to 80% (Suffet and MacCarthy,
1989). According to Wang et al. (2000), the nitrogen contained in humic substances can
be released as low molecular weight species through photochemical processes or
reactions, and therefore becomes more readily available for biological use. They found
that solar irradiation of dissolved organic matter results in conversion of recalcitrant
dissolved organic nitrogen to ammonium, which is more readily assimilated by microbes.
These photochemical reactions may play a significant role in the cycling of the nitrogen
through the ecosystem.
Flocculation
The terms flocculant and aggregate, often used interchangeably refer to “fragile,
amorphous, macroscopic or microscopic particles consisting of organic and inorganic
material” (Zimmerman-Timm, 2002; p. 197). Aggregates are ubiquitous in moving
surface water (rivers, tidally-influenced rivers, and estuaries); however, they have been
found to be more concentrated in an estuarine environment where fresh water meets salt
water, and where there is wave influence and turbulence. The main characteristics that
affect organic aggregates in moving water have been presented by Zimmerman-Timm
(2002) as hydrological regime, waves, shipping, channel deepening, precipitation,
stagnation, transport, aggregate composition, organic content, size, sedimentation,
saltwater interaction, and resuspension.
The hydrological regime affecting aggregates includes current velocity, horizontal
transport, wave action, and discharge rate. According to Berger et al. (1996) and

12
Zimmerman (1997), increasing current velocity and freshwater discharge rate result in a
large amount of aggregates in the water column. With a higher density of aggregates in
the water column, however, the probability of particle contact is more likely, and an
increase in the number of aggregates is unlikely. Horizontal transport and water
residence times are other hydrological factors that can affect aggregates in most running
surface water systems. The water residence times in estuaries are influenced by
interactions between tides and water flow, and circulation patterns (Day et al., 1989;
Zimmerman-Timm, 2002). Wave action also influences the generation of aggregates, as
waves can stir up the bottom sediment, causing particles to interact with each other and
aggregate. In areas of stagnation, however, low amounts of aggregates are generally
present (Zimmerman-Timm, 2002). In these locations, particles settle to the bottom as
there are few physical disturbances to bring them back into the water column.
The composition of aggregates can be made up of organic and inorganic,
allochthonous and autochthonous materials. According to Zimmerman-Timm (2002), the
composition of aggregates may include non-living geologic components (clays, mica,
quartz, etc.), anthropogenic components (organic and inorganic contaminants), non-living
biogenic material (silica, calcite, etc.), attached organisms (algae, bacteria, fungi, etc.),
macrophytes, detritus (dead and dying organic material), and fecal pellets. Conners and
Naiman (1984) have shown that 85-97 percent of the particulate organic carbon in large
rivers is autochthonous in nature. Suffet and MacCarthy (1989) found that, in most
cases, higher humic substance concentrations correspond to higher concentration of
aggregates. The aggregates in the Suwannee River consist predominantly of humic
substances brought into the system from the Okefenokee Swamp. However, clays and

13
bacteria, as well as salinity, might have a strong influence on the formation of the
aggregates (Meier et al., 1999). Algae and bacteria hold the aggregates together with
sticky mucous substances. Kepkay and Johnson (1988) found that after 15 minutes of
bubbling coastal seawater, DOC was reduced by 43% and the production of organic
particles increased after surface coagulation initiated a rapid bacterial response. Alber
and Valiela (1994b) showed that aggregates from dissolved organic matter released by
macrophytes are biotic in nature and contain large numbers of bacteria. Alber and
Valiela (1994b), in studying the carbohydrate, protein, lipid, carbon, and nitrogen
composition of aggregates, macrophytes, and bacteria, showed also that the biochemical
composition of the aggregates is closer to that of bacteria than the macrophytes.
Flocculated organic aggregates have different forms and sizes, all of which are
greater than or equal to 0.45 ¡im. Size is important when determining transport properties
(settling and movement through a system) (Jackson and Burd, 1998). Three size classes
of these flocculants have been determined by Alldredge and Silver (1988) and Perret et
al. (1994) and include macroscopic aggregates (>150 ftm), microaggregates (<150 /xm),
and submicron particles (<1 /mi). Typical sizes of aggregates are 5,000 /xm and smaller
(Zimmerman-Timm, 2002). Size of the aggregates influences how quickly they will
settle out. Aggregates in the 2,400 to greater than 5,000 nm size range settle at an
average of 25 times more rapidly than single algal cells (Alldredge and Gotschalk, 1988).
Larger size aggregates can be easily broken down by mechanical disruption (waves,
wind, mixing, etc.), consumer interaction, and microbial decomposition. Physical motion
breaks down aggregates near the surface in rivers (Argaman and Kaufman, 1970; Parker
et al., 1972). In the Elbe, the River Rhine, and the Zaire River Estuary, a decrease in

14
aggregate size has been found to occur with an increase in salinity due to decreased
colonization by microbes and bacteria (Zimmerman-Timm, 2002). Larger size
aggregates are also more accessible to larger consumers that are less efficient at
consuming small particles (Alber and Valiela, 1994).
The mechanisms underlying the formation of aggregates are often debated.
Although flocculation of dissolved organic matter has been shown to occur in many
estuarine ecosystems, it has not been proven if the cause of this flocculation is solely salt
induced, bacteria induced, physically induced, or a mixture of these. Many argue that it
is a complex process controlled by several variables (O’Melia, 1987; Eisma, 1993;
Stumm and Morgan, 1996) including particle concentration, stickiness of the particle
surface, velocities, and probability of attachment. The higher the concentration of
particles, the more aggregates will be formed. If the concentration is too low,
flocculation will be less likely to occur because the collision frequency will be too low
(Zimmerman-Timm, 2002).
Physical and chemical processes that have been found to produce aggregates
include Brownian motion, shear forces, differential settling, filtration, bubbling surface
coagulation, precipitation, adsorption, attractive and repulsive properties, bridging with
divalent cations, and spontaneous coagulation of dissolved organic matter. Brownian
motion is the movement and collision of particles smaller than 8 jum under the influence
of heat energy induced motion of water molecules (Eisma, 1986; Zimmerman-Timm,
2002; Schwarzenbach, 2003). Shear forces refers to the strength of laminar and turbulent
shear which determines the frequency and the push of particles (Jackson and Burd, 1998;
Zimmerman-Timm, 2002). Differential settling is a mechanism that is dependent on

15
aggregate composition, size, and abundance. Larger particles are formed as the larger
and more rapidly sinking particles interact with the smaller particles during vertical
transport (Zimmerman-Timm, 2002). Gas bubbles can be released from sediments or
formed by waves breaking at the surface. They will rise through the water column until
they burst or collapse. Particles can concentrate along the border of the bubble, and can
then be transported as aggregates (Johnson, 1976; Kepkay and Johnson, 1988).
Attractive and repulsive surface properties refer to the charge on particles and depend on
the size, composition, and chemical coating on the particle. Most particles are negatively
charged at their surface because the organic material has many carboxyl or hydroxyl
groups associated with it (especially humic substances) (Suffet and MacCarthy, 1989;
Zimmerman-Timm, 2002). Positive cations (such as those found in saline waters) can act
as chemical bridging agents, enhancing the attraction properties of electronegatively
charged particles. This is why salt-induced flocculation is one explanation for the
aggregates found in rivers where fresh water enters salt water.
Schwarzenbach et al. (2003) presented a discussion on how the presence of the
predominant inorganic ionic species found in natural waters generally decrease the
aqueous solubility, or increase the aqueous activity coefficient, of nonpolar or weakly
polar organic compounds. The magnitude of this effect is termed “salting-out”. An
empirical formula established by Setschenow (1889) (as cited by Schwarzenbach et al.,
2003) is presented to support this idea. This formula relates organic compound
solubilities in saline aqueous solutions to those in pure water by relating the effectiveness
of a particular salt or combination of salts to the change in solubility of a given

16
compound (in terms of a salting constant). It shows that the “salting-out” effect increases
exponentially with increasing salt concentration (see below).
r,sat. _ r,sat * 1 n-K*¡[salt]total /i , X
^ twjsalt iw ^1*1J
In the above equation, Csat¡w,sait is the organic compound solubility in saline aqueous
solutions, C^'iw is the organic compound solubility in pure water, [salt]totai is the total
molar salt concentration, and Ks¡ is the Setschenow, or salting constant (Schwarzenbach
et al., 2003). This can also be presented in terms of activity coefficients:
Yiw, salt = 10+^S^Sal,^°t (1-2)
This equation shows that ym, salt increases exponentially with increasing salt
concentration. Essentially, predominant ionic species, such as salts from sea water,
generally decreases the solubility of nonpolar or weakly polar, such as natural dissolved
organic matter.
Some experiments have been performed to produce aggregates in a laboratory
setting. Sholkovitz (1976), in a classic study, produced aggregates at varying salinities
from 0%o (parts per thousand) to 30%o by mixing filtered river water and sea water. He
found that no more changes were noticeable in color or concentration of flocculants after
about 15%o to 20%o, naming this the salinity of maximum removal of dissolved organic
carbon. Other elements were present in his river water sample that could have had an
effect on the flocculants, including aluminum and calcium. Fox (1983) attempted to
repeat (with minor differences) the study by Sholkovitz. In two of three estuaries studied,
he found that salt-induced removal of dissolved humic acid was insignificant. Eisma
(1986) also determined that salt induced flocculation plays only a minor role, and that
floes are formed more by a combination of forces including viscous flow, gravity, and

17
Brownian motion. Alber and Valiela (1994) produced aggregates in the laboratory using
dissolved organic matter from different macrophyte species. They bubbled the samples
and the formed aggregates ranged in size from a few micrometers to 500 /tm across.
Esteves et al. (1999) concluded that mixing freshwater and seawater in a laboratory
setting removes 5% to 10% of dissolved organic matter as particulate matter. Thill et al.
(2001), in studying water from Rhone River, France, found that particle aggregation and
adsorption are not an instantaneous process. The Rhone river particulate matter had a
poor average reactivity regarding salt induced flocculation. Reaction kinetics depend on
the electrostatic repulsion between particles, which is dependent on the salinity.
However, when shear collision dominates a system, the kinetics are proportional to the
particle volume fraction. They also stated that higher particle concentrations favor the
faster formation of aggregates (Thill et al., 2001).
Field studies have also shown the production of aggregates. A study by Del
Castillo et al. (2000) found that flocculation of dissolved organic matter in the Peace
River, Florida occurred at the mixing interface of salt and fresh water. Del Castillo and
colleagues hypothesized that the importance of the salt induced flocculation might be
overshadowed by large concentrations of CDOM in the mouth of the river. To test this
hypothesis, the possible effects of flocculation were modeled, and it was found that 11%
of the dissolved organic matter was lost and 20% of the color was removed during
flocculation as reported by Sholkovitz et al. (1976). Milligan et al. (2001) found that in
the ACE Basin, South Carolina, suspended material was dominated by high
concentrations of flocculated sediment. They stated that this was probably due to a
suppression of turbulence and salinity gradients. In the Rhone River, France, salt induced

18
flocculation was found to be a minor factor unless mixing conditions were adequate for
the formation of floes (Thill et al., 2001).
The use of organic aggregates as a food resource by consumers has been
hypothesized by several investigators (e.g., Alber and Valiela, 1994; Zimmerman-Timm,
2002). However, this hypothesis has not been adequately addressed. Alber and Valiela
(1996) found that in the aggregate detritus pathway, dissolved organic matter released by
primary producers is transformed into organic aggregates, which are then ingested by
consumers (in this case, bivalves). They also found that the aggregates could meet a
substantial portion of the nutritional requirements of bay scallops (Argopecten irradians)
in the field. Other experiments have also shown that benthic organisms are able to ingest
aggregates as a food source. The food quality of the aggregates can be characterized by
their composition. Alber and Valiela (1994) found that aggregates have lower C:N
values and are higher in protein than the macrophyte-derived detritus in their study,
explaining why aggregates are more readily consumed. The ingestion of aggregates as a
food source forms a link between the microbial food web and the higher trophic levels.
As bivalves consume the aggregates, they are also consuming the bacteria associated with
the aggregates, thus repackaging the smaller microbial particles.
Collection of aggregates can be troublesome. Filtration and centrifugation have
been shown to destroy the typical structure of the fragile aggregates, producing an
amorphous mass of organic and inorganic material (Thill et al., 2001; Zimmerman-Timm,
2002). It can be difficult to analyze aggregates as well. Laboratory produced aggregates
are often different from field aggregates because the conditions of their formation are
somewhat different. In the natural environment, there are higher numbers of organisms

19
and larger size classes than those produced in the lab, and the physical parameters are not
completely representative. However, it is worthwhile to construct laboratory experiments
to mimic field conditions to get an understanding of different mechanisms that may cause
the formation of aggregates.
Stable Carbon and Nitrogen Isotopes as Tracers of Material Transfer and Energy
Flow
Anthropogenic perturbations can alter the pathways of material transfer and energy
flow through an ecosystem. For example, excess fertilization in a watershed can alter the
abundance and flow of elements such as nitrogen in a stream within that watershed.
Stable carbon and nitrogen isotope ratios (51SN) can be used to follow the changes caused
by excessive fertilization and show which processes or components are altered (i.e.
foodweb, trophic changes, etc.), as well as determine the source of carbon and nitrogen
fueling production of consumers (Mariotti et al., 1984; Owens, 1985; Peterson and Fry,
1987; Fry, 1988; D’Avanzo et ah, 1991; Wada et ah, 1991; Holmes et ah, 1996; Riera,
1998; Fry, 1999; Hamilton et ah, 2001; Lehmann et ah, 2001; McKinney et ah, 2002).
Owens (1987) collected data available on the distribution of 15N for various
environments. In estuarine systems, the average oI5N value of all collected materials was
4.6 ± 2.0 for 199 observations. The average stable nitrogen isotope signature for all
materials in freshwater was 4.3 ± 2.7 for 64 observations, and the terrestrial average was
3.9 ±3.1. Differences in ecosystems provide a possible reason for using 15N as a tracer.
The use of stable isotopes to address issues related to energy flow is increasing because
stable isotope data can contribute both source-sink data (tracer) and process information
(Peterson and Fry, 1987; Fry, 1988; Montoya et ah, 1990; D’Avanzo et ah, 1991; Holmes

20
et al., 1996; Riera, 1998; Hamilton et al., 2001; Lehmann et al., 2001; McKinney et al.,
2002).
The stable isotopic signature of inorganic and organic nitrogen provides an
integrative tool for studying the sources of nitrogen supporting production in an
ecosystem (Valiela et al., 1997). The stable carbon isotope signature provides a tool for
determining the source of organic matter in these ecosystems. Most systems have several
inputs of organic carbon as a food source, e.g. C3 terrestrial plant material (o13C = -23 to
-30%o), seagrasses (-3 to -15%o), macroalgae (-8 to -27%o), C3 marsh plants (-23 to -
26%o), C4 marsh plants (-12 to -14%o), benthic algae (-10 to -20%o), and marine
phytoplankton (-18 to -24%o) (Fry and Sherr, 1984; Michener and Schell, 1994). The
major source of terrestrial-derived DOM is vascular plants, which are confined
essentially to land and characteristically contain high concentrations of recalcitrant,
nitrogen-free biomacromolecules such as lignin and tannin (Hedges et al., 1997). These
plants have distinct stable carbon isotope compositions and can be used as a biomarker of
terrestrial origin (Fry and Sherr, 1984; Hedges et al., 1997). There can be, however,
some overlap of stable isotope signatures (e.g., C3 terrestrial plants, C3 marsh plants, and
marine phytoplankton). Detailed investigations of individual ecosystems should be
studied to differentiate sources of organic carbon.
The implications for the use of stable nitrogen and carbon isotopes in food web
investigations are also significant (DeNiro and Epstein, 1981; Fry, 1988; Wada et al.,
1991; Canuel et al., 1995; Cabana and Rasmussen, 1996; Vander Zanden and Rasmussen,
1999; Jepsen and Winemiller, 2002). DeNiro and Epstein (1981) found that the 515N of
organisms reflects the SI5N signature of the diet; however, the animal is generally

21
enriched in 15N, and 6I5N values are approximately 3 to 5%o greater than the diet. This is
mainly due to excretion of isotopically light nitrogen in urine (Minagawa and Wada,
1984; Owens, 1987; Peterson and Fry, 1987; Fry, 1988; Wada et al., 1991; Lajtha and
Michener, 1994; Cabana and Rasmussen, 1996; Gue et al., 1996). Stable carbon isotopes
of animals reflect those of the diet within approximately l%o (DeNiro and Epstein, 1978;
Peterson and Fry, 1987; Michener and Schell, 1994; O’Donnell et al., 2003). Animals
may be isotopically enriched relative to their diet as a consequence of the preferential loss
of 12C02 during respiration, the preferential uptake of 13C compounds during digestion, or
metabolic fractionation during synthesis of different tissue types (DeNiro and Epstein,
1978; Rau et al, 1983; Tieszen et al., 1983; Fry et al., 1984). A determination of an
organisms trophic status can be facilitated by the simultaneous measure of 5I5N and 513C
signatures (Peterson et al., 1985). Stable carbon and nitrogen isotopes are a useful
method for following the flow of energy in a system such as the Suwannee River and its
estuary.
Many chemical and physical processes are accompanied by significant isotopic
fractionation which results in an enrichment or depletion of the heavy isotope (Peterson
and Fry, 1987; Wada et al., 1991; Lajtha and Michener, 1994). Fractionation can occur
during kinetic and equilibrium processes. Equilibrium isotope effects are common where
chemical exchange occurs between two molecules, whereas kinetic isotope effects are
involved with more complex reactions (Peterson and Fry, 1987). In biochemical
processes involving nutrient uptake, the substrate is enriched and the product is depleted
in heavy isotopes when the substrate pool is infinite (Montoya et al., 1990). This is due
to the fact that autotrophs, e.g. phytoplankton, preferentially assimilate lighter nitrogen.

22
In the process of nitrogen fixation, however, the 51SN values are near 0%o. In the
processes of nitrification and denitrification, residual ammonium-N and nitrate-N,
respectively, are enriched with heavy nitrogen. According to Owens (1987), there is a
large fractionation effect associated with denitrification. The residual nitrate substrate
exhibits isotopic enrichment in situ, however, a large pool of dissolved N2 can preclude
any significant depletion of the accumulated product (Owens, 1987). With regard to
animals, preferential excretion of 15N-depIeted nitrogen has been found, generally in the
form of urea and ammonia, resulting in and isotopic enrichment of the animal tissue
(Minagawa and Wada, 1984).
Most nitrogen is present as N2 gas in the atmosphere with an isotopic composition
essentially constant at 0%o (Peterson and Fry, 1987). Nitrogen in the rest of the biosphere
has a typical isotopic composition around 0%o as well (ranging from -10 to 10%o). The
nitrogen cycle, however, involves processes with notable fractionation effects that affect
SI5N signatures of nitrogen pools. For example, there is a cumulative faster loss of l4N
than l5N during particulate nitrogen decomposition in soil and water, resulting in 51SN
increases of 5 to 10%o with increasing depth (Peterson and Fry, 1987). Nitrification and
denitrification in the oceans involve substantial isotope effects. As animals are on
average 3 to 5%o heavier than dietary nitrogen (Minagawa and Wada, 1984; Owens,
1987; Peterson and Fry, 1987; Fry, 1988; Wada et al., 1991; Lajtha and Michener, 1994;
Cabana and Rasmussen, 1996; Gu et al., 1996), nitrogen isotopic values may increase by
10 to 15%o in many food webs, due to the presence of three to five successive trophic
transfers (Peterson and Fry, 1987). Volatization of nitrogen also causes fractionation
effects because the lighter isotope (14N) is more volatile than the heavier isotope (l5N).

23
For example, Flipse and Bonner (1985) found that the average ol5N values of fertilizers
was 0.2%o (potato farm) and -5.9%o (golf course), and the average 5ISN values of the
groundwater nitrate in these systems were 6.2%o and 6.5%o, respectively. It was
determined that higher 51SN values of groundwater nitrate were caused by isotopic
fractionation during the volatile loss of ammonia from nitrogen applied in reduced forms.
The elements carbon, nitrogen, sulfur, hydrogen, and oxygen all have more than
one stable isotope and their relative abundances can be measured with a mass
spectrometer (Peterson and Fry, 1987). The isotopic compositions of different materials
will change in predictable ways as elements cycle through the biosphere and also as a
consequence of isotopic fractionation (Owens, 1987; Peterson and Fry, 1987; Lajtha and
Michener, 1994). According to Owens (1987), however, these changes aren’t always
apparent due to a degree of overlap between different types of samples. Therefore, a
combination of elements (e.g. carbon, nitrogen, and sulfur) and their isotopes are often
used. For example, Peters et al. (1978) found a high correlation between 515N and ál3C
values in sedimentary organic matter. Peterson et al. (1985) found that the use of a
combination of the stable isotopes of sulfur, carbon, and nitrogen helped to delineate food
sources and characterize the trophic structure in an estuary where there was more than
one source of food for the ribbed mussel (Geukensia demissa). Gu et al. (1996) used
stable carbon and nitrogen isotopes to identify food sources and describe trophic transfer
pathways within a lake ecosystem. Vander Zanden and Rasmussen (1999) also used
stable carbon and nitrogen isotopes as indicators of trophic structure within a freshwater
lake system, and determined that SI5N values of higher consumers could not be used
alone because of the high variability of SI5N values of primary consumers. Carbon and

24
nitrogen element ratios might also assist in understanding ol5N values. For example, Guo
and Santschi (1997) studied the elements carbon, nitrogen, and sulfur, as well as isotopic
composition of colloidal organic matter to investigate sources and turnover rates of
dissolved organic matter in Chesapeake Bay and Galveston Bay, USA.
A number of studies have been done on nitrogen isotopes in freshwater, estuarine,
and marine ecosystems. Wada et al. (1981) studied highly enriched algal felt in saline
and non-saline lakes in the Antarctic. The epibenthic algae in this system were depleted
in 1SN as a result of isotopic fractionation associated with slow growth rates in low light
and a high nitrate environment. The source of nitrogen for the algae was avian excreted
ammonium, which had a large fractionation effect during volatization of ammonium.
Therefore the nitrogen available to the algae was likely to be highly enriched (Wada et
al., 1981). Owens (1987) presented data from numerous studies and found that the ol5N
signature of phytoplankton ranges from 3%o to 12%o. It was predicted that phytoplankton
in the field would tend to exhibit a lower l5N content because of fractionation effects
(Owens, 1987). In the turbidity maximum (area where material is periodically
resuspended from the surface sediments) of the Tamar River estuary, Britain, Owens
(1985) showed a distinction between at least two different populations of particles using
1SN analyses. In the marine end of the estuary (salinity 33.8%o), the S15N values were
4.96 ± 1.03%o, in the freshwater end, the 6I5N values were 2.29 ± 2.23%o, and
intermediate SI5N values ranged from 1.79 ± 1.63%o to 14.73 ± 0.7%o. The highest values
were found in the turbidity maximum, due to the longer residence time (and thus,
increased microbial decomposition) of the particles at this site (Owens, 1985). The low
S15N values (close to 0%o) were similar to values typical of terrestrial material, which

25
reflects the dominance of atmospheric nitrogen (Owens, 1985). Wada et al. (1991) also
found this to be the case for particulate organic matter in Otsuchi River and its receiving
waters. Low 615N values (0.2 to 0.7%o) were found in the particulate matter of the upper
reaches of the river, while high 51SN values (6.4 ± 1,8%o) were found in the bay (Wada et
al., 1991). Sigleo and Macko (1985) also reported similar findings for suspended
particulate material in the Patuxent Estuary, Maryland.
Mariotti et al. (1984) found substantial spatial differences in the 15N content of
ammonium and nitrate in particulate material in the Scheldt Estuary, France. The
upstream zone was depleted in dissolved oxygen and was a site of denitrification (low
concentration of nitrate and high concentration of ammonium). In this zone, the 615N of
ammonium was 10%o and the 51SN of nitrate was 18%o. However, in the lower estuary,
where dissolved oxygen was high and nitrification was active, the 61SN values were
reversed (nitrate 2 to 5%o and ammonium 29%o) (Mariotti et al., 1984). This indicates
that the nitrogen cycle is very important when interpreting l5N data. Katz et al. (2001)
studied nitrate-N flowing out of springs into the Suwannee River using SI5N as well as
other tracers. Water discharging from springs in Suwannee County had lower 5I5N
values (2.7-6.2 %o) than Lafayette County (4.5-9. l%o). The average concentration of
nitrate in Suwannee County springs was higher (1.5-37 mg/L) than the average
concentration of nitrate in Lafayette County springs (1.7-5.5 mg/L). These differences
were attributed to local differences in land use and nitrate source. The springs with the
highest concentration of nitrate (and lowest 6I5N values) were near cropland farming
areas that were intensively fertilized and irrigated, and the springs with the lowest
concentration of nitrate (and highest 5I5N values) were near recharge areas with

26
concentrated animal feeding operations (animal waste sources of nitrate) (Katz et al.,
2001).
A number of studies have been done with l5N being used as a food web tracer as
well. DeNiro and Epstein (1980) found through studying animals raised in the laboratory
on diets of known and constant o15N values, that the isotopic composition of nitrogen in
an animal reflects the nitrogen isotopic composition of its diet. In general, the 8I5N value
of an organism is greater than the ol5N of its diet (DeNiro and Epstein, 1980; Owens,
1987, Wada et al., 1991). According to Peterson and Fry (1987), stable nitrogen isotopes
in animals average 3-5 %o heavier than dietary nitrogen. Alber and Valiela (1994) found
that two different species of mussels incorporated l5N-labelled nitrogen when fed
aggregates derived from dissolved organic matter released by labeled macrophytes,
demonstrating that nitrogen can be transferred from decomposing macrophytes to
suspension-feeding consumers through the aggregate detrital pathway. They also showed
that both species of mussels incorporated significantly more nitrogen when they were fed
aggregates than when they were fed either dissolved organic matter or particulate detrims
(Alber and Valiela, 1994; Alber and Valiela, 1996). However, the nitrogen incorporation
rate of scallops that were fed phytoplankton was significantly greater than that of scallops
fed aggregates (Alber and Valiela, 1996). Fry (1999) studied the clam, Potamocorbula
amurensis, in San Francisco Bay and found that nitrogen isotopic compositions of clams
were representative of watershed nutrient loading. Higher 5I5N values were found in the
South Bay, where there was a stronger input of anthropogenic nitrogen than in the North
Bay. In the freshwater end of the North Bay, however, a discrepancy was noted between
the 8I5N values of the filter-feeders and seston (seston 5%o and large zooplankton 9 to

27
14%o), and three possible explanations were presented: (1) there was an intermediate
trophic linkage in the microbial component of the food web leading to higher 3,5N values
in filter-feeders, (2) detrital river material colonized by bacteria immobilize enriched l5N
from the water column, and filter-feeders consuming these bacteria have higher S15N
values, and (3) a large quantity of riverine seston (which is largely terrestrial and
refractory to food web use) masked a relatively minor 15N-enriched river/estuarine
phytoplankton component that was selectively used by filter-feeders (Fry, 1999).
51SN values have also been used to provide insight into the source of nitrogen
supporting autotrophic production in a system. For example, Frazer et al. (2002) found
that the ol5N values of submerged aquatic vegetation were low in the Chassahowitzka
River. This was consistent with the idea that fertilizers have contributed significantly to
nitrate pollution of the system. Fry et al. (2001) determined that nitrogen isotope assays
were useful for detecting watershed nitrogen loading in four National Estuarine Research
Reserve (NERR) sites on the west coast of the United States. Isotope values of
ammonium and nitrate (ranging from -0.3 to 19.6%o) showed a trend towards higher
values in those estuaries associated with higher watershed nitrogen loading (Fry et al.,
2001). Some studies have even broken the 6I5N values of each organism down to
individual tissues and excretory products because isotopic variation can exist among
different tissues and metabolites of different animals (DeNiro and Epstein, 1981;
Peterson and Fry, 1987). For example, Alber and Valida (1994) found that whatever 15N
was present in the guts of two species of mussels was released after 48 hours. Excretory
products are consistently depleted in 1SN relative to the diets, which also explains why
315N values are higher in the organism compared to its diet (DeNiro and Epstein, 1981;

28
Owens, 1987; Peterson and Fry, 1987; Alber and Valiela, 1994). Another problem to
consider is that there could be variations in the 6I5N values of food sources over time.
For example, a study by Zieman et al. (1984) showed that while the 15N content of sea
grasses did not change as they degraded over time, the 1SN content of mangrove leaves
varied by up to 10%o.
Studies have also been done using 5ISN values as indicators of trophic level.
Nitrogen isotopes are assumed to increase progressively with each trophic transfer (Wada
et al., 1981). Minagawa and Wada (1984) found, in a study on marine and freshwater
animals from the East China Sea, the Bering Sea, Lake Ahinoko, and the Usujiri
intertidal zone, that all consumers, zooplankton, fish, and birds exhibited stepwise
enrichment of 15N with increasing trophic level. Fry (1988) found a general trend of
increasing o15N and ol 5C with increasing trophic levels; however, he also found that S13C
and 51SN were not correlated. ISN increases were more consistent indicating that 615N is a
more reliable trophic indicator than ol3C (Fry, 1988). Gu et al. (1996) found that
enriched S15N values in medium and large fish in Lake Apopka, Florida resulted from
diets consisting of other fishes occupying high trophic levels. Riera (1998) found
through analysis of SI5N of Crassostrea gigas in Marennes-Oléron Bay, France, that the
oysters exhibited direct utilization of benthic diatoms as a food source near intertidal
mudflats. Flowever, in the upper estuarine reaches, they were also found to utilize
terrestrial detritus as a food source. It was suggested that o15N can be a useful tool in
characterizing trophic levels in an estuarine food web as long as different feeding habitats
are considered (Riera, 1998).

29
Proposed Research
The overall goal of this research is to study the transformation and fate of dissolved
organic matter (DOM) originating in the Suwannee River using stable carbon and
nitrogen isotopes. This includes three main objectives: (1) determining if flocculated
organic aggregates could be produced in the laboratory and if they maintained a
terrestrial isotopic signature, (2) characterizing the spatial pattern of stable isotope
signatures in particulate organic matter in the Suwannee River and its estuary during two
different flow regimes, and (3) using stable isotope ratios to investigate aspects of the
food web in the Suwannee River estuary.

CHAPTER 2
STABLE CARBON AND NITROGEN ISOTOPE COMPOSITION OF ORGANIC
AGGREGATES PRODUCED BY SALINITY INDUCED FLOCCULATION OF
DISSOLVED ORGANIC MATTER FROM THE SUWANNEE RIVER
Introduction
Terrestrial dissolved organic matter (DOM) discharged by rivers into estuarine and
marine systems represents a significant source of carbon and other elements (e.g.,
McCarthy et al., 1996; Opsahl and Benner, 1997; Dagg et al., 2004) and is a potentially
important source of energy for consumers in coastal ecosystems. Much of the DOM
originating in terrestrial systems is degraded by a broad suite of physical, chemical, and
biological processes as it is transported to and mixed with ocean waters (Gardner et al.,
1994; Amon and Benner, 1996; Hedges et al., 1997; Twardowski and Donaghay, 2001;
Hemes and Benner, 2002; Zimmerman-Timm, 2002; Dagg et al., 2004; Obemosterer and
Benner, 2004). Examples include photochemical processes and microbial degradation.
However, flocculation of DOM has been shown to occur in estuarine systems where fresh
water meets salt water (Scholkovitz, 1976; Fox, 1983; Mannino and Harvey, 2000;
Sondergaard et al., 2003) and may result in the formation of organic aggregates of a
suitable size and quality for filter- and suspension-feeding organisms, such as clams and
oysters. The DOM, from which floes are formed in the Suwannee River estuary has a
high nitrogen component as a result of fertilizers and animal wastes present in the system
(Asbury and Oaksford, 1997; Katz et al., 2001).
Laboratory produced organic aggregates have historically been difficult to produce,
even though flocculation of DOM has been shown to occur in many estuarine systems
30

31
(Fox, 1983; Eisma, 1986; de Souza Sierra et al., 1997; Del Castillo et al., 2000; Thill et
al., 2001; Sondergaard et al., 2003). Sholkovitz et al. (1976) presented a classic study
where organic aggregates were produced at various salinities by mixing fdtered river
water (Glen Bum, Water of Luce, River Cree, and River Stinchar in Scotland) with
filtered seawater (collected off the coast of southeast Scotland). The amounts of
flocculated material increased as salinity increased from 0 to ~15%o. Above 15%o, little
removal of the dissolved organic matter occurred. Studies following Sholkovitz’s
methods have been less successful in creating floes (Fox, 1983; de Souza Sierra et al.,
1997; Thill et al., 2001).
The mechanisms underlying the formation of organic aggregates have often been
debated, and it has not been proven that flocculation is solely induced by salt or bacteria,
physically induced, or a combination of these processes. Fox (1983) repeated, with
minor differences, the Sholkovitz et al. (1976) study with unfiltered river water and
filtered seawater from the Delaware Bay and its tributaries. After analysis of the
dissolved humic acid carbon, it was determined that salt-induced removal of dissolved
humic acid was insignificant. Humic substances from different environments are
compositionally different, and therefore, their response to changes in ionic strength and
removal mechanisms may be different (Fox, 1983). De Souza Sierra et al. (1997) used
filtered river water from the Scheldt estuary (Holland) and artificial seawater in an
attempt to produce organic aggregates in the laboratory. No flocculation was noticed and
it was ascertained that under natural conditions, the removal of humic material may
proceed slowly by aggregation through various chemical, physical, and biological
interactions or by adsorption onto suspended matter which was not present in their

32
samples due to filtering. Thill et al. (2001) included analysis of particle size distribution
along the mixing zone of the Rhone river estuary, France, during high and low flow
regimes to determine if salt induced flocculation played an important role. No obvious
instantaneous change in particle size of the natural river particle size occurred and it was
determined that salt induced aggregation did not play an important role concerning
increased particle size.
Eisma (1986), in a review of observations of flocculated material in European
coastal waters and along the US east coast found that salt-induced mechanisms play only
a minor role in organic aggregate formation, and that organic aggregates are formed more
by a combination of forces including viscous flow, gravity, and Brownian motion.
Bacteria have also been shown to be a major factor in the production of flocculated
material, either by direct colonization or through excretions of mucous which enhances
the stickiness of particle surfaces (Zimmermann-Timm, 2002). Rivers supply inorganic
and organic nutrients that can be used by bacteria as determined in the Hudson River
(USA) by Findlay et al. (1992). Gardner et al. (1994) found that most bacterial
production was supported by dissolved organic matter rather than by particulate materials
during microcosm experiments with filtered and unfiltered water from the northern Gulf
of Mexico near the main delta of the Mississippi River. Also in the Mississippi River
Delta, it was determined that the bioreactivity of DOM increased with increasing size of
the organic matter (Amon and Benner, 1996). Womer et al. (2000) found that bacteria
colonized laboratory-produced aggregates, using the aggregates as a haven in the water
column, over a period of 14 days using water from the Elbe Estuary (Germany). The
aggregates were largest after 9 days because large omnivorous and carnivorous ciliates

33
colonized the aggregates (Womer et al., 2000). The combination of physical and
bacterial influences can combine to produce flocculated materials from DOM.
Del Castillo et al. (2000) were able to produce organic aggregates in a laboratory
experiment using Peace River water (a colored river with high concentrations of
dissolved organic matter; west coast of Florida, USA). The Suwannee River (west coast
of Florida, USA) similarly has large concentrations of colored dissolved organic matter
(CDOM), and organic aggregates have been observed in the water column at the salt and
freshwater interface (personal observation). Regardless of exactly how organic
aggregates are formed, it is important to understand what happens to the organic
aggregates once they are produced. It has been hypothesized that organic aggregates are
used as a food source by estuarine organisms (Alber and Valiela, 1994; Zimmerman-
Timm, 2002). Alber and Valiela (1994b) determined that macrophyte-derived aggregates
are more readily consumed than detritus by bay scallops. The DOM released by primary
producers in an aggregate detrital pathway is transformed into organic aggregates, and
then ingested by bivalves, e.g., bay scallops. The aggregates were shown to meet a
substantial portion of the nutritional requirements of the bay scallops because they had
lower C:N ratios and higher protein content than detritus (Alber and Valiela, 1994b). In a
review of river-bom aggregates, Zimmerman-Timm (2002) suggests that aggregates
support growth and production of riverine protozoa and metazoa as a long term food
supply.
The major source of terrestrial-derived DOM is vascular plants, which are confined
largely to land and characteristically contain high concentrations of recalcitrant, nitrogen-
free biomacromolecules such as lignin and tannin (Hedges et al., 1997). These plants

34
have distinct stable carbon isotope (513C) compositions which can be used as a biomarker
indicating a terrestrial origin (Fry and Sherr, 1984; Hedges et al., 1997). Most terrestrial
plants have S13C values of -28 to -25%>, versus -22 to -19%o for temperate marine
phytoplankton, whereas sea grasses have heavier SI3C values near -12%o (Fry and Sherr,
1984). The 61SN values of vascular land plants and marine plankton can also be
sufficiently different (Hedges et al., 1997). Terrestrial plants typically have average 515N
values of 3%>, whereas phytoplankton have heavier average S15N values ranging from 6
to 10%o (Owens, 1987). There is a prevalence of nitrogen fixation on land, and therefore
the light organic 51SN compositions have been suggested as being typical of terrestrial
origin (Peters et al., 1987), however blue green algae also present light S15N values
because of the capability to fix nitrogen.
Here, it is proposed that DOM in the fresh water of the Suwannee River flocculates
when mixed with salt water from the Gulf of Mexico, and that the organic aggregates
may be consumed by clams and oysters in the estuary. A laboratory study was performed
to produce organic aggregates under varying salinity conditions and to determine if
natural abundances of stable nitrogen and carbon isotopes might be used as markers to
characterize organic aggregates and identify their potential role as a food source for fauna
in the Suwannee River estuary. Further, the study sought to determine if organic
aggregates maintain their stable isotope signature along the salinity gradient utilized in
the laboratory to simulate such gradients in the estuary.
Methods and Materials
Site
The Suwannee River is a blackwater, tidally influenced river with its principal
origin in the Okefenokee Swamp in Georgia. It flows southwest through Florida and

35
discharges into the Gulf of Mexico just north of Cedar Key. There is a delta region at the
mouth of the river characterized by a network of intertidal and subtidal oyster reefs
(Wolfe and Wolfe, 1985). The water quality of the upper Suwannee River is
characterized by low pH (around 4), low concentrations of dissolved inorganic solids, and
high concentrations of dissolved organic substances, especially fulvic acids (Malcolm et
al., 1989a). The lower Suwannee River maintains a higher pH (6 to 9) (Wolfe and Wolfe,
1985). The source of the humic substances in the water is predominantly litter, leaf and
root exudates, and leaf leachates. The concentration of these humic substances has been
shown to be an order of magnitude greater than that in most natural stream waters. The
dissolved organic carbon concentrations in the Suwannee River near the Okefenokee
Swamp are in excess of 25 mg/L (Malcolm et ah, 1989b).
Methods
Laboratory experiments were designed to flocculate the dissolved organic matter
(predominantly humic substances) from the Suwannee River across a range of salinities.
Whole water samples were collected from one site in the upper Suwannee River fresh
water (August 2002 and September 2003) and one in the lower Suwannee River fresh
water (May 2003 and August 2003). When returned to the laboratory, samples were
shaken and 1-L aliquots were distributed to 6 beakers. Samples were not filtered because
it had been noted that filtering samples would remove suspended material that could be
involved in the flocculation and adsorption process (De Souza Sierra et ah, 1997).
Instant Ocean Synthetic Sea Saltâ„¢ (Aquarium Systems, Mentor, OH) was added as a
solid and mixed with the 1-L samples until dissolved and the desired salinity was
reached. The salinity varied from 0 to 30 ppt in increments of 0, 5, 10, 15,20, and 30 ppt
and was determined with a YSI Conductivity and Salinity field monitor.

36
The samples were stirred (Phipps and Bird jar tester) for 6 to 10 consecutive days at
approximately 14 rpm. Samples were taken for DOC analyses daily for experiments I
and II, and initially for experiments III and IV (see below). At the end of each
experiment, organic aggregates were allowed to settle and the residual water was
decanted and the organic aggregates were collected onto a combusted (450° C, 4 hours)
GF/F filter. Samples were packed and frozen prior to stable nitrogen and carbon isotope
analysis.
DOC and Stable Isotope Analysis
Immediately after the organic aggregates were collected from each beaker, the
decanted water was filtered through a Millipore HNWP 0.45 um filter (pre-washed with
E-Pure water). The filtrate was analyzed with a Tekmar Dohrman Apollo 9000 HS
Combustion TOC Analyzer with an STS 8000 Autosampler. The reproducibility of the
DOC measurements was generally within 0.05%. S13C and 51SN isotope ratios of the
organic aggregates on filters were analyzed with a Finnigan Delta-C continuous flow
mass spectrometer. Results are reported in standard S notation where:
6I5N (%>) = [('WV^e/^N/'VWdardH] x 1000 (2-la)
and
8I3C (%o) = [(13C/13C)sample/(13C/12C)standard)-l] X 1000 (2-lb)
Atmospheric nitrogen and carbon from the Pee Dee Belemnite served as reference
standards. The reproducibility of the stable l3C and 1SN isotopes was within 0.3%o.
Results
Organic aggregates were formed almost immediately after Instant Oceanâ„¢ was
added to the reaction beaker and stirring was initiated. The organic aggregate densities
increased, as observed visually, with increasing salinity.

37
Comparisons of DOC versus salinity are presented in Figure 2-1. All four of the
experiments showed that increasing the salinity from 0 to 30 ppt had undetectable or
minor effects on DOC concentrations. Only one experiment from the upper Suwannee
River showed a significant relationship (p < 0.0001); DOC decreased with increasing
salinity. There was some association for two of the other three experiments (p = 0.0396,
0.0188), and one showed no significant relationship (p = 0.3687). Continuous stirring for
longer than 24 hours showed no measurable changes in DOC concentrations for organic
Floe studies I and II (Figure 2-2).
The relationships between 615N and 513C signatures and salinity are presented in
Figures 2-3 and 2-4, respectively. Average stable isotope values for all four studies are
presented in Figures 2-5 and 2-6, respectively. The S15N of the laboratory produced
organic aggregates increased by approximately 4%o with increasing salinity using pooled
data from all four experiments. The upper Suwannee River organic aggregate
experiments showed significant relationships with a p-value < 0.0001 for both
experiments. One of the lower Suwannee River organic aggregate experiments also
showed significant relationship with a p-value = 0.0046 (Floe II). The second of the
lower Suwannee River organic aggregate studies did not show a significant relationship
(Floe IV, p = 0.3245). The 513C signature of aggregates decreased significantly in two of
the four experiments (Floe II, p = 0.0062 for the lower Suwannee and Floe IV, p = 0.0035
for the upper Suwannee) (Figure 2-4). The 513C of organic aggregates formed during one
experiment using upper Suwannee River water increased very slightly with increasing
salinity (Floe I, p = 0.0151). The average S15N and o13C for all the four of the floe studies
combined are given in Figures 2-5 and 2-6. Salinity had a significant effect on 61SN and

38
Table 2-1. Analysis of Variance (ANOVA) Results for all of the Floe Studies.
Floe I
Floe II
Floe III
Floe IV
Average
Source of Variation
Salinity
Salinity
Salinity
Salinity
Salinity
Experiment
¿15n
F Ratio
10.59
23.46
8.30
1.2596
3.62
33.61
P
<0.0001
0.0046
0.0450
0.3245
0.0240
<0.0001
¿13C
F Ratio
2.41
10.52
0.30
38.29
0.97
24.58
P
0.0729
0.0062
0.6158
0.0035
0.4669
<0.0001
C:N
F Ratio
14.91
7.34
n.d.
n.d.
4.35
5.80
P
<0.0001
0.0154
n.d.
n.d.
0.0120
0.0077
DOC
F Ratio
108.14
4.88
6.76
1.32
n.d.
n.d.
P
<0.0001
0.0396
0.0188
0.3687
n.d.
n.d.
*P Values at the 95% confidence level. Analyzed with JMP. (n.d. = not determined)

Floe Study I (Upper Suwannee)
Floe Study IV (Upper Suwannee)
Floe Study II (Lower Suwannee)
Floe Study III (Lower Suwannee)
U)
vo
Figure 2-1. Salinity versus Dissolved Organic Carbon in the Upper and Lower Suwannee River Floe Studies.

40
Floe Study I
—*— 0 Salinity
5 Salinity
—10 Salinity
-x— 15 Salinity
Floe Study II
—«— 0 Salinity
—■— 15 Salinity
—*— 30 Salinity
---x--- 5 Salinity
10 Salinity
------- 20 Salinity
Figure 2-2. Time versus Dissolved Organic Carbon for Floe Studies I and II.

41
Upper Suwannee
Lower Suwannee
Figure 2-3. Salinity versus 815N for the Upper and Lower Suwannee River Flocculated
Organic Aggregates.

42
Upper Suwannee
Lower Suwannee
Figure 2-4. Salinity versus 5I3C for the Upper and Lower Suwannee River Flocculated
Organic Aggregates.

Figure 2-5. Salinity versus Average 815N Signatures of the Upper and Lower Suwannee River Floe Studies Including Standard
Error Bars.
35

-27.3
-27.4
-27.5
-27.6
-27.7
O
Tío
-27.8
-27.9
-28.0
-28.1
-28.2 L
-5
0 5 10 15 20 25 30 35
Salinity
Figure 2-6. Salinity versus Average 513C Signatures of the Upper and Lower Suwannee River Floe Studies Including Standard
Error Bars.
4^

Figure 2-7. Salinity versus Average C:N Ratios of the Flocculated Organic Aggregates from the Upper and Lower Suwannee
River Floe Studies Including Standard Error Bars.

46
no significant effect on S13C (Table 2-1).
The C:N ratios of the filtered organic aggregates are presented in Figure 2-7. C:N
ratios of the organic aggregates averaged between 10 and 12 and were highest at the
highest salinities (Figure 2-7). Salinity had a significant effect on the C:N ratios (p <
0.05).
Discussion
It was necessary to determine if organic aggregates could be formed by mixing
Suwannee River water with salt (Instant Oceanâ„¢) so that organic aggregates could be
analyzed for stable nitrogen and carbon isotopes. Salt-induced organic aggregate
formation has been shown to be optimal for salinities between 1 and 7 ppt (Thill et al.,
2001), however, in our experiments, organic aggregates formed almost instantly (within
the first half hour of mixing) in each salinity treatment (0 to 30 ppt). The initial idea for
determining organic aggregate formation was to measure DOC throughout the duration of
a 10-day experiment, given the hypothesis that DOC would decrease each day as the
organic aggregates formed. The results showed, however, that DOC did not change
significantly throughout the 10-day experiment (Figure 2-2). During this study, the
Suwannee River exhibited very high levels of DOC in the upper and lower portions of the
river (ranging from 13 to greater than 50 ppm). Because there was such a high
concentration of DOC in this system, it is likely that only a small percentage of the DOC
was transformed into an aggregate form, and as a result, no substantial loss of DOC was
observed. Sondergaard et al. (2003) also found that fast aggregation of DOC was not a
major removal process of DOC in highly colored rivers. Therefore, a different approach
had to be taken to be able to quantitatively model the behavior of the organic aggregates.

47
Stable nitrogen and carbon isotope ratios have been used to model theoretically the
behavior of particulate organic material (Montoya et ah, 1991; Kendall et al., 2001; De
Brabandere et ah, 2002), but not organic aggregates, per se. In each of the four
experiments, the change in the S15N signatures of organic aggregates was consistent from
0 to 30 ppt (Figure 2-3), indicating that 5ISN could be used as markers of organic
aggregates as they are formed and move throughout the Suwannee River and estuary.
The SlsN of the organic aggregates followed a pattern showing a transition from a
terrestrial signature (he., near 0) to a higher, more marine signature as the salinity
increased. It is likely that the change in pH, induced by increased salinity, might
selectively drive the precipitation of DOC, and based on the ¿ISN and S13C values of the
flocculated organic aggregates, a trend is observed.
The formation of the organic aggregates can be biological, chemical, and/or
physical. Bacteria have been shown to have a major influence on organic aggregates and
particulate organic nitrogen (PON) formed in an estuarine environment (Kemp, 1990;
Hoch et al., 1992; Alber and Valiela, 1994; Stumm and Morgan, 1996; Sondergaard et
al., 2003). The samples taken from these laboratory experiments were not filtered prior
to the addition of salt, allowing the organic aggregates to include particulate material
already in the water which may have included suspended sediment, bacteria, plant debris,
and fecal matter. Bacterial incorporation of ammonia has been shown to be a mechanism
for producing isotopically light particles (near 1.1%0), whereas microbially degraded
material tends to have signatures closer to 8%o (Voss et al., 1997). This implies that
degradation of PON (or the organic aggregates in these experiments) can result in an
increase of oISN. In these experiments, samples were stirred in the beakers for up to 10

48
days at room temperature, and not protected from light, allowing formation of organic
aggregates which could have included growth of bacterial communities and
remineralization of isotopically light nitrogen.
Salt induced flocculation is caused by electrolytic interactions between negatively
charged functionalities in humic substances and cations in seawater (Eckert and
Sholkovitz, 1976; Stumm and Morgan, 1996), especially calcium and magnesium.
Positive salt ions neutralize the negatively charged humic substances, and Van der Waals
forces form attraction forces between the neutral molecules, forming organic aggregates.
Hydrogen bonding also contributes to aggregation of humic substances, especially when
the molecules include hydroxyl or amine groups (Stumm and Morgan, 1996). Slow
mixing encourages collision of the particles. The stability of colloids in the dissolved
organic matter pool is mainly determined by the pH and ionic strength of solution as well
as the presence of specific ions (Tombácz et al., 1999). Increasing the salt content
increases the pH and the ionic strength, and humic substances exposed to salt ions will
flocculate (Stumm and Morgan, 1996). Isotopic fractionation can occur in the process of
ion exchange reactions. For example, the process of ammonium adsorption at the site of
clay minerals (or possibly humic substances) plays a primary role in determining l5N
abundance, and the heavier isotopic species is preferentially adsorbed on clay colloids
(Delwiche and Steyn, 1970).
Ammonium is found in humic substances in the Suwannee River (Malcolm et ah,
1989b). Therefore, a possible chemical explanation for the steady increase in 5ISN with
increasing salinity is that some fraction of the NhL(+ (associated with humic substances) is
transformed to NH3 as pH increases resulting in a heavier isotopic composition of the

49
residual NFLt+ on the organic aggregates. Ammonia volatization leads to the enrichment
of 51SN in inorganic nitrogen (Wada and Hattori, 1991).
The SI3C of the organic aggregates did not show a consistent trend as did the 51SN
data. The data, in fact, exhibited little change across the broad range of salinities (< l%o)
and aggregates maintained a terrestrial signature (-25 to -30%o) (Figure 2-4). Therefore,
5i3C measures can be a good tool for determining the source of flocculated particles.
Guo et al. (1997) studied the S13C signatures of colloidal organic carbon in the
Chesapeake Bay and also determined that stable carbon isotope signatures were good
indicators of the origin of organic particles.
The C:N ratios help to characterize the laboratory-produced organic aggregates.
For example, Middleburg and Nieuwenhuize (1998) distinguished terrestrial sources of
particulate organic material (C:N —21) from riverine, estuarine, and marine material
(C:N *7.5 to 8). In our experiments, C:N ranged from 6 to 17, indicative of relatively
high quality food source based on findings by Alber and Valiela (1994a). The large
range in the C:N ratios may be explained by different environmental causes. For the
upper Suwannee River experiments, water was collected for floe study II during a
drought and for floe study VI during more normal flow conditions. During floe study II,
the water levels were extremely low in the river, and less carbon was entering the system
(groundwater inputs dominate during low flow periods). Therefore, C:N ratios were
lower than during floe study VI when water levels were higher, and higher C:N ratios of
the material were entering the river (Figure 2-7).

50
It is important to determine if the organic aggregates are being consumed by filter
feeders or other fauna in the estuary. In a later chapter, the possibility that bivalves in the
Suwannee River are consuming organic aggregates will be presented.
Summary
A laboratory study was performed to determine if natural abundance measures of
stable carbon and nitrogen isotope ratios might be used as markers to characterize organic
aggregates to identify their potential role as a food source for fauna in the Suwannee
River estuary. The 6I5N values of laboratory produced aggregates increased significantly
with salinity, however the 613C values did not change significantly with increasing
salinity. These findings indicate that the 6I5N signatures might be used as a tracer of
organic aggregate development as they are formed as a result of increasing salinity.
These findings also indicate that SI3C signatures might be used to quantify their role as a
food source for estuarine fauna.
Conclusions
The following conclusions may be drawn from the research discussed in this
chapter:
• Formation of organic aggregates, i.e. floes, can be induced by mixing salts with
Suwannee River water rich in dissolved organic material.
• SlsN signatures of aggregates increased significantly with salinity, but exhibited
pronounced variability.
• SI3C signatures did not change significantly with increasing salinity indicating that
stable carbon isotope ratios might be used as a tracer of terrestrial derived dissolved
organic matter in estuarine and coastal food webs.
• The C:N ratios increased significantly with increasing salinity, but did not exceed
values of 17 indicating that salinity induced aggregates are a potentially high
quality food source for suspension feeding organisms in the Suwannee River
estuary and associated nearshore coastal waters.

CHAPTER 3
SPATIAL GRADIENTS IN THE STABLE CARBON AND NITROGEN ISOTOPE
COMPOSITION OF SUSPENDED PARTICLES IN THE SUWANNEE RIVER
ESTUARY DURING DIFFERENT FLOW REGIMES
Introduction
River discharge provides a significant source of nutrients to estuaries. Increased
nutrient input into estuaries and marine environments, whether from point or non-point
sources, can lead to increased primary production and changes in trophic structure
(Ryther and Dunstan, 1971; Smith et al., 1999; White et al., 2004). Nitrate
concentrations in many of Florida’s spring-fed rivers are rapidly increasing (Mytyk and
Delfino, 2004), especially in the Big Bend region of the northeast Gulf of Mexico (Ham
and Hatzell, 1996; Jones et ah, 1997, Katz et ah, 2001), where it has long been
recognized as relatively unaffected by anthropogenic forces (Bass and Cox, 1988). In
particular, the Suwannee River has such high levels of nitrate and carbon that it may alter
the biological character of the Suwannee River estuary.
Distinct seasonal patterns of the distribution of nutrients (specifically nitrate and
ammonium) occur in the Suwannee River and estuary. With the second highest mean
annual discharge in Florida (301 m3/s), the Suwannee River has its peak flows typically
in the early spring and low flows typically in the fall (Crandall et ah, 1999). Nitrate
concentrations in the estuary are lower during periods of high flow than during periods of
low flow. This is a karst system where groundwater interacts with surface water, and
during the fall (low flow period), the main source of freshwater for the river is
groundwater which has high nitrate concentrations (Pittman et ah, 1997; Crandall et ah,
51

52
1999). During the spring (high flow period), overland surface flow is the dominant
source of water for the river. High color in the system limits nutrient uptake and
assimilation by phytoplankton (due to light limitation). Thus, much of the otherwise
available nutrients are discharged directly to the estuary (Bledsoe, 1998). Nitrogen is the
limiting nutrient in the Suwannee River estuary (Bledsoe and Phlips, 2000), and
eutrophication is a potential problem of concern (Ryther and Dunstan, 1971; Bledsoe et
al„ 2004).
Nitrogen loading can have a significant impact on biological productivity and
ecosystem structure in coastal and nearshore marine systems; however the mechanisms
and pathways involved may be difficult to resolve with traditional methods (e.g.
hydrographic and mass balance studies) because of the complexity of the nitrogen cycle
and relatively large spatial and temporal scales of interest (Owens, 1987; Peterson and
Fry, 1987; Horrigan et al., 1990a, Horrigan et al., 1990b; Montoya et al., 1990; Montoya
and McCarthy, 1995). The stable isotopic signature of inorganic and organic nitrogen
provides an integrative tool for studying the sources of nitrogen supporting production in
an ecosystem as a whole (Valiela et al., 1997). Stable carbon isotope ratios also provide
a means for determining the source of organic matter supporting production in these
ecosystems.
Spatial gradients in nutrient concentrations, particularly of nitrate and/or
ammonium, are characteristic of estuarine systems and can occur as a result of physical
mixing processes and uptake and assimilation by phytoplankton and other autotrophs
(e.g. attached macroalgae, epiphytic microalgae, and seagrasses). Isotopic fractionation
associated with the uptake and assimilation of nitrate and/or ammonium can generate

53
spatial gradients in the stable nitrogen isotope composition of the residual pool of
dissolved inorganic nitrogen. This will also be reflected in the isotopic composition of
nitrogen sequestered in particulate forms (Montoya and McCarthy, 1995). In essence,
stable nitrogen isotopes can serve as in situ tracers of nitrogen as it moves through an
estuarine system. Stable carbon isotopes are also used as in situ tracers of the source of
carbon in estuarine systems.
Here, data are presented from the Suwannee River and estuary in Northwest Florida
during two different high and low flow periods, hypothesizing that distinct spatial and
temporal patterns will be seen in the stable nitrogen isotopes of suspended particulate
organic matter (SPOM), and that stable carbon isotopes will allow determination of the
source of organic matter fueling production in higher-level consumers. Stable nitrogen
and carbon isotopic data for oysters and zooplankton collected in the same area are
presented to determine the relationship between oysters, zooplankton, and SPOM.
Methods, Materials, and Site Description
Site Description
The historic Suwannee River is a blackwater, tidally influenced river with its main
origin in the Okefenokee Swamp in Georgia. The river is approximately 394 km in
length and flows southwest through Florida. It discharges into the Gulf of Mexico just
north of Cedar Key, draining a watershed of approximately 25,640 km2 (Nordlie, 1990).
Main tributaries include the Alapaha, Withlacoochee, and Santa Fe Rivers. At the mouth
of the river there is a delta region which is characterized by a network of intertidal and
subtidal oyster reefs that are subject to harvest periodically throughout the year (Wolfe
and Wolfe, 1985).

54
Periods of peak flow in the Suwannee River occur typically in early spring and
periods of low flow occur in the fall. There is much less land development and point
source pollution in this watershed than in most other coastal regions in Florida (Bass and
Cox, 1988). Major land uses in the watershed include silviculture and agriculture (row
crops, dairy, poultry, and swine) (Katz et al., 2001). The land immediately surrounding
the river is predominantly used for pine forestry operations. Fertilizer from pine forestry
operations and waste material from dairy practices are thought to be a significant source
of non-point source nutrient loading to the river (Ashbury and Oaksford, 1997). Spring
and groundwater discharge contribute significantly to nitrate concentrations in the river,
particularly during periods of low flow. The upper part of the estuary, comprising both
oligohaline and mesohaline zones, is bordered by brackish marsh habitat and is
dominated by emergent grasses and rushes. Submerged aquatic vegetation (SAV) is less
abundant. The lower portion of the nearshore estuary is a mosaic of saltmarsh, tidal
creeks, mudflats and oyster habitats. Seagrasses are much less abundant within this
estuary when compared to other areas of Florida’s Big Bend coast, as a consequence of
highly colored surface water and low light levels (Bledsoe, 1998). The main pathway of
nitrogen transfer to higher trophic levels likely occurs directly through the pelagic
compartment (i.e. phytoplankton production in the surface water) (Frazer et al., 1998;
Bledsoe et al., 2004).
Methods
Surface water samples were collected from the Suwannee River and its estuary in
November, 1996 (low flow period), March, 1997 (high flow period), May, 2003 (high
flow period), and December, 2003 (low flow period). During the 1996/1997 sampling
event, water was collected at 10 stations along a transect (stations marked with A, see

55
Figure 3-1). The initial sampling station was located in the main river approximately
5km from the mouth and subsequent sampling stations progressed seaward at
approximately 3.7km intervals (Figure 3-1). During the 2003 sampling event, water was
collected at 10 stations along a salinity transect (stations marked with B and C), ranging
from 0 ppt to approximately 30 ppt (Figure 3-1, Table 3-1). Conductivity, dissolved
oxygen, pH, salinity, and temperature were measured with a YSI field meter. Water
samples were held on ice and returned to the lab for processing.
Water samples collected at each station during each sampling event were filtered
through precombusted glass fiber filters (Whatman GF/F, 450°C, 4h) and the filtrate was
frozen for subsequent analyses (within 24h) of nitrate and ammonium in the laboratory.
Filtered particles were placed on ice and transported to the laboratory where they were
dried at 60°C (>48h) in preparation for isotope analysis. The filtrate from the 2003
sampling trips was preserved with concentrated sulfuric acid (resulting in a pH<2)
(Holmes et al., 1998) and stored prior to analysis of the stable nitrogen isotope
composition of dissolved inorganic nitrogen (DIN). Additional water was collected at
each station and filtered on site for subsequent analysis of chlorophyll a concentration.
Water was also collected during the 96/96 and 2003 sampling trips to be analyzed for
DOC (2003 only), color, TN, TP, and phosphate. Zooplankton were collected with a
202um ring-net (diameter = 0.5m). Samples were placed on ice and returned to the
laboratory where they were immediately sorted by taxon (i.e., copepod, chaetognath, and
ctenophore) and prepared for stable isotope analysis. Oysters were collected along the
transect during low tide in December, 2003. They were stored on ice and transported to

56
Figure 3-1. Map of the Sampling Sites in the Suwannee River and its Estuary.

57
Table 3-1
Location and Site Names for Sampling Sites in the Suwannee River and its
Estuary.
Sample Date
Sample
ID
GPS Coordinates
Latitude Longitude
Nov.
1A
29.328012
-83.103267
1996 and
2A
29.306664
-83.147504
March 1997
3A
29.281708
-83.164847
4A
29.279032
-83.166859
5A
29.279264
-83.166504
6A
29.274404
-83.167420
7A
29.258845
-83.176053
8A
29.245006
-83.194144
9A
29.246172
-83.234362
10A
29.251276
-83.284666
May 2003
1B
29.327136
-83.103301
2B
29.307044
-83.148037
3B
29.279506
-83.165490
4B
29.275151
-83.169196
5B
29.266446
-83.170751
6B
29.266037
-83.171514
7B
29.260041
-83.176243
8B
29.251779
-83.189391
9B
29.243944
-83.198380
10B
29.199541
-83.251848
Dec. 2003
1C
29.328012
-83.103267
2C
29.306664
-83.147504
3C
29.281708
-83.164847
4C
29.279032
-83.166859
5C
29.279264
-83.166504
6C
29.274404
-83.167420
7C
29.258845
-83.176053
8C
29.245006
-83.194144
9C
29.246172
-83.234362
10C
29.251276
-83.284666

58
the laboratory where they were shucked, dried at 60°C (>48h), ground to a fine powder
with a mortar and pestle, and stored in a desiccant cabinet prior to isotope analyses.
Concentrations of nitrate (NO3 +NO2'), ammonium (NH4+), and total nitrogen (TN)
in surface water samples were measured with a Bran+Lubbe AutoAnalyzer II within two
days of sampling. The limit of detection for each nutrient was <0.001 mg-N/L. Analyses
of phosphate (PO4') and total phosphorus (TP) were analyzed with a Perkin Elmer
Lambda 2 spectrophotometer (Greenberg et al., 1992). Color was analyzed using
platinum cobalt standards also using a Perkin Elmer Lambda 2 spectrophotometer and a
Spectronic 401 spectrophotometer. Chlorophyll a was measured on a Hitachi U-2000
spectrophotometer after extraction with hot ethanol. Total nitrogen and total phosphorus
were determined using the persulfate digestion method (Greenberg et al., 1992). Samples
for DOC analysis were filtered through 0.45 pm nylon filters (Millipore HNWP) and
measured with a Tekmar Dohrman Apollo 9000 HS Combustion Analyzer with a STS
8000 TOC Autosampler. The reproducibility of the DOC measurements was within
0.05%.
All samples for isotope analysis were analyzed with a Finnigan Delta-C
continuous-flow mass spectrometer. Results are reported in standard 5 notation where:
31SN (%») = [((15N/,4N)sample/(15N/14N)standard)-l] x 1000 (3-la)
and
S13C (%») = [((13C/12C)sample/(13C/12C)standard)-1 ] x 1000 (3-lb)
Atmospheric nitrogen and Pee Dee belemnite limestone served as reference standards.
The reproducibility of the stable carbon and nitrogen isotope measures was within 0.3%o.

59
Results
Physical Parameters
Salinities in the Suwannee River (station 1: 1996 and 1997 and stations 1 and 2:
2003; Table 3-2) were at or less than 0.2 ppt during all sampling periods. The two
sampling stations furthest offshore (stations 9 and 10: 1996 and 1997) showed salinities
near 35 ppt, and the station furthest offshore (station 10) during the 2003 sampling
periods showed a salinity near 30 ppt. Salinities at the other stations were less than these
higher values and varied with sampling date during the 1996 and 1997 sampling events,
whereas the salinities were at more regularly spaced intervals during the 2003 sampling
periods.
Color in the Suwannee River estuary showed considerable variation. Values for
color were greatest within the river and decreased along the transect from the river to the
Gulf of Mexico during the 1996 and 1997 sampling events (Table 3-2). During the 2003
sampling events, color was highest in the river and decreased steadily with distance from
the river’s mouth. Color values were highest during periods of high river discharge
(April 1997 and May 2003).
In March 1997 and May 2003, the observed high flows were approximately 400
m3/s and 320 m3/s respectively. In November 1996 and December 2003, recorded flows
were approximately 130 m3/s and 157 m3/s, respectively. Average monthly streamflows
for 1996, 1997, and 2003 are presented in Figure 3-2.
Chemical Parameters
Nitrate concentrations (Table 2-3) were highest in the river during periods of low
discharge (November, 1996 and December, 2003). Beyond the river, nitrate

60
Table 3-2. Chemical and Biological Parameters in the Suwannee River and its Estuary
for Each Sampling Event.
Station
1
2
3
4
5
6
7
8
9
10
SALINITY (ppt)
Nov-96
0.0
21
23
25
30
31
33
33
35
35
Mar-97
0.0
22
22
23
28
30
31
33
34
35
May-03
0.1
0.1
3.5
6.5
9.0
16
17
21
25
30
Dec-03
0.2
0.2
3.8
6.1
10
13
17
22
25
30
COLOR (mg pt/L)
Nov-96
110
27
29
32
22
19
32
27
10
8
Mar-97
150
44
46
34
19
12
14
21
12
12
May-03
188
187
163
148
122
97
84
65
46
22
Dec-03
63
66
57
54
45
41
36
25
17
9
DISSOLVED ORGANIC CARBON (ppm)
May-03
12.1
12.4
14.8
13.8
13.6
10.4
9.6
7.8
7.2
4.5
Dec-03
5.5
5.8
6.8
6.6
6.1
5.8
5.8
4.7
5.0
2.6
CHLOROPHYLL A (mg/m3)
Nov-96
0.4
2.3
2.1
2.9
9.8
9.9
7.8
2.9
1.2
0.9
Mar-97
0.2
4.2
5.6
3.7
3.0
2.0
2.2
1.3
1.5
0.7
May-03
0.3
0.3
2.2
6.1
9.9
13.9
18.9
13.7
9.8
2.8
Dec-03
0.1
BDL
1.3
2.7
5.1
3.7
11.8
4.3
5.3
2.5

600
Time
Figure 3-2. Monthly Streamflow Data for the Suwannee River near Wilcox, Florida (USGS, 2004).

62
concentrations decreased rapidly along the transect during the 1996 and 1997 sampling
events. Further offshore, during the 1996 and 1997 sampling events, nitrate
concentrations were generally below the limit of analytical detection (Table 3-3). During
the May and December 2003 sampling events, nitrate concentrations also declined with
distance offshore.
Ammonium levels mirrored nitrate patterns with the exception of the December,
2003 sampling event (Table 3-3). During this event, ammonium remained in the narrow
range of about 46 to 56 /rg/L with the exception of 72 /rg/L at station 5C and exhibited a
peak concentration at station 6C, i.e. 111 fig/L. In November, 1996, the concentration of
ammonium in the river and nearshore of the estuary varied considerably (Table 3-3), but
was undetectable seaward of station 3A.
Total nitrogen (TN) was highest in or near the river mouth for all sampling dates
(Table 3-3). During the 1996 and 1997 sampling events, TN concentrations decreased
substantially outside the river mouth. During the 2003 sampling event, TN
concentrations declined steadily with distance offshore (Table 3-3).
Total phosphorus (TP) and soluble reactive phosphorus (SRP) were highest in or
near the mouth of the river for all sampling dates (Table 3-4). Total phosphorus
concentrations decreased markedly beyond the river mouth (station 2A) during the 1996
and 1997 sampling events. During the 2003 sampling period, TP concentrations
decreased steadily with distance off shore (Table 3-4). Higher concentrations of TP and
SRP were observed during periods of high river flow (March 1997 and May 2003). SRP
was not detectable beyond station 6 during the 1996 and 1997 sampling events.

63
Table 3-3. Concentrations of Nitrogen Components (/tg/L) in the Suwannee River and its
Estuary for Each Sampling Event.
Station
Nov-96
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
N-N03‘
810
60
180
180
BDL*
BDL
BDL
BDL
BDL
BDL
N-NH„*
40
320
20
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Total N
1190
380
480
430
340
300
320
200
160
120
Mar-97
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
N-NCV
360
80
80
60
BDL
BDL
BDL
BDL
BDL
BDL
n-nh4*
40
320
20
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Total N
850
380
290
350
280
170
170
100
130
150
May-03
1B
2B
3B
4B
5B
6B
7B
8B
9B
10B
n-no3-
514
513
598
587
490
369
314
185
129
60
n-nh4*
47
52
79
73
63
60
37
29
36
BDL
Total N
1170
1170
1270
1050
1150
945
825
660
510
245
Dec-03
1C
2C
3C
4C
5C
6C
7C
8C
9C
10C
N-N03'
1300
1275
935
860
640
520
450
250
115
BDL
n-nh4*
47
53
56
56
72
111
54
54
55
46
Total N
1320
1325
1100
1015
875
780
735
515
500
265
'BDL - below detection limit

64
Table 3-4. Concentrations of Phosphorus Components (ptg/L) in the Suwannee River and
its Estuary for each Sampling Event.
Station
Nov-96
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
SRP
50
10
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Total P
130
10
30
30
20
10
BDL
BDL
10
BDL
Mar-97
1A
2A
3A
4A
5A
6A
7A
8A
9A
10A
SRP
80
20
10
10
BDL
BDL
BDL
BDL
BDL
BDL
Total P
90
20
10
10
BDL
BDL
BDL
BDL
BDL
BDL
May-03
1B
2B
3B
4B
5B
6B
7B
8B
9B
10B
SRP
91
89
81
63
45
28
18
8
3
BDL
Total P
122
116
134
105
99
68
49
33
24
11
Dec-03
1C
2C
3C
4C
5C
6C
7C
8C
9C
10C
SRP
79
78
61
57
40
30
24
12
3
BDL
Total P
84
80
70
68
59
47
52
33
32
18

65
Dissolved organic carbon (DOC) was only determined for the two 2003 sampling
events. DOC concentrations decreased steadily with increasing salinity after reaching
their highest values at station 3 on both 2003 sampling dates (Table 3-2). Dissolved
organic carbon concentrations exhibited a slight increase from station 1 to station 3.
Biological Indicator
Chlorophyll a concentrations in the river were consistently low (<1 mg/m3) during
the 1996 and 1997 sampling events (Table 3-2). During the 2003 sampling period,
chlorophyll a concentrations were low near the river mouth and increased to a
chlorophyll maximum near stations 6 and 7 (Table 3-2). Chlorophyll maxima were also
observed during the 1996/1997 sampling periods. A maximum value (9.9 mg/m3) was
observed at station 6A in November 1996 and a maximum value (5.6 mg/m3) was
observed at station 3A in March 1997.
Stable Isotope Analyses
Spatial Gradients in the stable nitrogen isotope composition (51SN) of suspended
particulate organic matter (SPOM) collected from the surface waters of the Suwannee
River and its estuary were apparent during both low and high flow regimes (Figures 3-3
and 3-4, Table 3-5). During the November 1996 sampling event, there was an initial
decrease in the dlsN signature from station 1 to station 3 with a sharp drop at station 4.
The 515N signatures of SPOM during the March 1997 sampling event exhibited a sharp
decline at station 2A. The 5ISN signatures of SPOM were higher during the March 1997
sampling event than during the November 1996 sampling event. A similar pattern was
observed in May 2003; there was a sharp drop at stations 3B and 4B. The December
2003 sampling event showed a more uniform, increasing pattern for the SPOM (Figure 3-
4).

11
10
g
8
7
6
5
4
3
2
1
0
â– e 3-
66
[-•»•• Mar-97
♦ Nov-96
High Flow
123456789 10 11
Station
. 6I5N Signatures of Surface Suspended Particulate Organic Matter (SPOM)
for the 1996 and 1997 Sampling Events.

7
6
5
4
3
2
1
O
-1
-2
3-
67
High Flow
♦
* * ♦ • • May-03
—■— Dec-03
1 23456789 10 11
Station
. 515N Signatures of Surface Suspended Particulate Organic Matter (SPOM)
for the Two 2003 Sampling Events.

68
Table 3-5. Stable Isotope Data of Suspended Particulate Organic Matter (SPOM) and
Dissolved Inorganic Nitrogen (DIN) for the 1996, 1997, and Two 2003
Sampling Events.
Station
1
2
3
4
5
6
7
8
9
10
¿’5N of SPOM (per mil)
Nov-96
3.80
3.51
3.43
2.37
4.77
4.90
5.33
5.55
5.24
4.92
Mar-97
9.75
6.68
7.31
7.63
7.51
7.64
7.33
6.65
ND
ND
May-03
2.87
2.40
-0.69
0.24
2.96
3.79
5.42
5.77
5.29
5.99
Dec-03
1.94
1.96
1.72
2.92
2.23
2.46
3.99
3.35
2.13
5.57
<5,3C of SPOM (per mil)
Nov-96
-26.70
23.87
24.46
23.71
22.85
22.74
22.65
22.70
22.44
22.05
Mar-97
-25.84
24.78
25.95
25.31
22.97
22.41
22.26
21.84
ND
ND
May-03
-27.90
27.61
24.42
26.91
26.07
24.13
24.18
24.08
22.11
20.39
Dec-03
-27.53
25.79
25.78
25.90
26.61
25.49
28.03
23.02
23.53
22.26
Nov-96
(Nitrate)
2.2
4.1
3.4
2.8
4.7
5.4
3.8
3.5
1.8
4.9
Mar-97
(Ammon)
8.2
9.9
11.4
3.0
11.5
11.9
14.8
12.0
11.7
14.5
May-03
(Nitrate)
7.0
8.0
7.5
6.8
6.9
5.4
5.3
5.1
2.1
2.1
Dec-03
(Nitrate)
3.7
5.3
4.8
6.4
6.3
7.0
7.0
7.3
5.8
-0.8
ND - Not Determined

69
Spatial gradients in the stable nitrogen isotope composition of dissolved inorganic
nitrogen were apparent during the March 1997 sampling event. A sharp dip was present
at station 4 for the 615N of the DIN-ammonium, and the ol5N of the DIN-nitrate was
lower than the DIN-ammonium (Figure 3-5, Table 3-5). The 5ISN of the DIN-nitrate for
the 2003 sampling event showed a variation between the different flow regimes (Figure
3-6). During the low flow period, 515N values increased steadily, whereas during the
high flow period, 615N values decreased steadily.
Zooplankton were collected only at stations 3 through 10 during the 2003 sampling
events (Figures 3-7 and 3-8). Only calanoid copepods, chaetognaths, and ctenophores
were retained for stable isotope analysis. The 51SN signatures of the zooplankton were
very similar and ranged from ca. 8 to ca. 10%o (chaetognaths and ctenophores) and from
ca. 5 to ca. 10%o (copepods) during the high and low flow periods (Figure 3-7 and 3-8).
Oysters were sampled opportunistically near the transect sampling sites where they could
be found, and exhibited a marrow range in their 5ISN signatures, ca. 7.5 to 8%o (Figure 3-
9).
Spatial gradients in the stable carbon isotope composition (¿L1C) of SPOM
collected from the surface waters of the Suwannee River estuary were apparent during
the 96/97 and 2003 sampling periods irrespective of the flow regimes (Figures 3-10 and
3-11). The ol3C signatures of the SPOM from the 96/97 sampling events were similar to
the 5I3C signatures of the SPOM during the 2003 sampling event, ranging from -28%o in
the river to ca. -21%o at the farthest offshore stations (Figures 3-10 and 3-11).
The range of 513C signatures of the zooplankton were similar during the May and
December 2003 sampling events, with the copepods exhibiting slightly lower signatures

16
14
12
10
? 8
>o
6
4
2
0
igure 3'
70
- Del15N Nitrate
—■—Del15N Amm
123456789 10 11
Station
. 81SN Signatures of Surface Dissolved Inorganic Nitrogen (DIN) for the
March 1997 Sampling Event.

9
8
7
6
5
4
3
2
1
O
-1
-2
i
: 3
71
â–  May-03
—■— Dec-03
>
1 23456789 10 11
Station
i. 8I5N Signatures of Surface Dissolved Inorganic Nitrogen (DIN-Nitrate) for
the 2003 Sampling Events.

10
g
8
7
6
5
4
3
2
1
0
re 3'
72
■ ♦ - COPE
—■— CHAET
-â– *- CTEN
123456789 10
Station
S15N Signatures of Zooplankton Collected during the May 2003 (High Flow)
Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten =
Ctenophores).

11
10
9
8
7
6
5
4
3
2
1
0
â– e 3
73
■•♦■■COPE
—■— CHAET
CTEN
1 23456789 10 11
Station
!. 81SN Signatures of Zooplankton Collected during the December 2003 (Low
Flow) Sampling Event (Cope = Calanoid Copepods, Chaet = Chaetognaths,
Cten = Ctenophores).

10
8
6
4
2
0
-2
A
-6
-8
-10
-12
-14
-16
-18
-20
-22
-24
-26
-28
3-!
74
1 23456789 10 11
♦ Del15N
—■— Del13C
Station
. Stable Carbon and Nitrogen Isotopes of Oysters Collected During the
December 2003 Sampling Event.

75
Figure 3-10. 8I3C of the Suspended Particulate Organic Matter (SPOM) for the 1996 and
1997 Sampling Events.

76
Station
Figure 3-11. 8I3C of the Suspended Particulate Organic Matter (SPOM) for the Two
2003 Sampling Events.

77
than the chaetognaths and ctenophores at any given sampling station (Figures 3-12 and 3-
13). Oysters maintained a á13C signature of approximately -24 to -25%o (Figure 3-9).
Statistics
Analysis of variance (ANOVA) was used to test for effects of salinity on stable
isotopic signatures (S15N and o13C) of SPOM, DIN and other water quality parameters
(Tables 3-6 through 3-9). Values were determined to be significantly different if p-values
were less than 0.05.
Discussion
The results of this study suggest differences in the physical, chemical, and
biological parameters during high and low flow regimes. The Suwannee River
discharges high concentrations of nutrients into the coastal region of west Florida,
compared to other rivers in the same area (Suwannee River Water Management District,
2003). Outside the mouth of the river, chemical analyses show a decline in nutrients with
distance offshore (Tables 3-3 and 3-4). Samples collected in the river during periods of
low flow (November 1996 and December 2003) exhibited higher concentrations of
inorganic nitrogen relative to those collected during high flow periods (March 1997 and
May 2003). In other systems such as New York Flarbor, nitrogen concentrations increase
during rainy seasons due to surface water exportation into the system from the watershed
(Ryther and Dunstan, 1971), however, the opposite occurred in the Suwannee River
system. Nitrate increased in the river during low flow periods and decreased during high
flow periods (Suwannee River Water Management District, 1995, 1996,2003). The
Suwannee River is a karst, spring-fed river system, and groundwater contributes
significantly to the river discharge during low flow periods (Pittman et al., 1997; Crandall
et al., 1999). Springs discharge is prevalent in the middle reaches of the Suwannee River

78
Figure 3-12. 8I3C of Zooplankton Collected During the May 2003 Sampling Event
(Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores).

79
Figure 3-13. 8I3C of Zooplankton Collected During the December 2003 Sampling Event
(Cope = Calanoid Copepods, Chaet = Chaetognaths, Cten = Ctenophores).

80
Table 3-6. ANOVA Tables for the Effects of Salinity on the 615N and S13C of Suspended
Particulate Organic Matter during November 1996.
NOVEMBER 1996 Sampling Event
Onewav Analysis of SPOM 615N By Salinity
Source of Variation
DF*
Sum of Squares
Mean
Square
F Ratio
Prob > F **
Salinity
7
19.3663
2.7666
16.8960
0.00002
Error
12
1.9649
0.1637
Total
19
21.3312
Oneway Analysis of SPOM 813C By Salinity
Mean
Source of Variation
DF
Sum of Squares
Square
F Ratio
Prob > F
Salinity
7
33.6221
4.8032
87.3301
2.44E-09
Error
12
0.6600
0.0550
Total
19
34.2821
* Degrees of freedom
** If the probability is less than 0.05 (95% confidence) then there Is significant variance

81
Table 3-7. ANOVA Tables for the Effects of Salinity on the 815N and 513C of Suspended
Particulate Organic Matter during March 1997.
MARCH 1997 Sampling Event
Onewav Analysis of SPOM 815N By Salinity
Source of Variation
DF
Sum of Squares
Mean
Square
F Ratio
Prob > F
Salinity
7
7.3362
1.0480
2.9228
0.1062
Error
6
2.1514
0.3586
Total
13
9.4876
Oneway Analysis of SPOM S,3C By Salinity
Mean
Source of Variation
DF
Sum of Squares
Square
F Ratio
Prob > F
Salinity
7
36.9084
5.2726
5.2498
0.0219
Error
7
7.0305
1.0044
Total
14
43.9388

82
Table 3-8. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during
December 2003.
DECEMBER 2003 Sampling Event
Oneway Analysis of SPOM 815N By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
25.7998
2.8666
2.4135
0.0931
Error
10
11.8777
1.1878
Total
19
37.6775
Oneway Analysis of SPOM 5,3C By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
65.5696
7.2855
24.1083
0.00001245
Error
10
3.0220
0.3022
Total
19
68.5916
Oneway Analysis of DIN 815N-N03 By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
172.1822
19.1314
3.5323
0.0310
Error
10
54.1615
5.4161
Total
19
226.3437
Oneway Analysis of NOn By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
3723545
413727
3065
5.34E-16
Error
10
1350
135.0
Total
19
3724895
Oneway Analysis of NH4 By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
6534.00
726.00
11.56
3.40E-04
Error
10
628.00
62.80
Total
19
7162.00
Oneway Analysis of Chi a By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
211.3423
23.4825
39.7049
1.18E-06
Error
10
5.9143
0.5914
Total
19
217.2566
Oneway Analysis of Color By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
6844.2000
760.4667
7604.6667
5.68E-18
Error
10
1.0000
0.1000
Total
19
6845.2000
Oneway Analysis of DOC by Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
25.49718
2.83302
15.31693
9.88E-05
Error
10
1.8496
0.18496
Total
19
27.34678

83
Table 3-8 Continued. ANOVA Tables for the Effects of Salinity on the Physical,
Chemical, and Biological Indicators of Suspended Particulate Organic Matter
during December 2003.
Oneway Analysis of TN by Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
2262920.0
251435.6
867.0
2.92E-13
Error
10
2900.0
290.0
Total
19
2265820.0
Oneway Analysis of TP by Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
8707.4500
967.4944
152.3613
1.66E-09
Error
10
63.5000
6.3500
Total
19
8770.9500
Oneway Analysis of SRP By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
15495.2
1721.6889
1565.1717
1.53E-14
Error
10
11.0
1.1000
Total
19
15506.2
Oneway Analysis of C-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
135.2867
15.0319
19.6729
3.18E-05
Error
10
7.6409
0.7641
Total
19
142.9276
Oneway Analysis of N-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
2.3578
0.2620
28.6788
5.52E-06
Error
10
0.0914
0.0091
Total
19
2.4492
Oneway Analysis of C:N-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
42.4307
4.7145
96.5498
1.58E-08
Error
10
0.4883
0.0488
Total
19
42.9190
Oneway Analysis of N-DIN By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
9
102.2519
11.3613
484.8015
5.31E-12
Error
10
0.2344
0.0234
Total
19
102.4863

84
Table 3-9. ANOVA Tables for the Effects of Salinity on the Physical, Chemical, and
Biological Indicators of Suspended Particulate Organic Matter during May
2003.
MAY 2003 Sampling Event
Oneway Analysis of SPOM 8,5N By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
118.7969
14.8496
3.7383
0.0234
Error
11
43.6950
3.9723
Total
19
162.4919
Oneway Analysis of SPOM S13C By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
103.4872
12.9359
40.4563
4.41 E-07
Error
11
3.5173
0.3198
Total
19
107.0045
Oneway Analysis of DIN 815N-N03 By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
433.3482
54.1685
2.6594
6.76E-02
Error
11
224.0538
20.3685
Total
19
657.4020
Oneway Analysis of NOs By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
691979.0500
86497.3813
917.0807
2.00E-14
Error
11
1037.5000
94.3182
Total
19
693016.5500
Oneway Analysis of NFU By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
9718.5500
1214.8188
28.1771
2.88E-06
Error
11
474.2500
43.1136
Total
19
10192.8000
Oneway Analysis of Chi a By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
752.2718
94.0340
178.0946
1.56E-10
Error
11
5.8080
0.5280
Total
19
758.0798
Oneway Analysis of Color By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
62196.2000
7774.5250 2327.0687
1.20E-16
Error
11
36.7500
3.3409
Total
19
62232.9500
Oneway Analysis of DOC by Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
199.7360
24.9670
48.9091
1.63E-07
Error
11
5.6153
0.5105
Total
19
205.3513

85
Table 3-9 Continued. ANOVA Tables for the Effects of Salinity on the Physical,
Chemical, and Biological Indicators of Suspended Particulate Organic Matter
during May 2003,
Oneway Analysis of TN by Salinity
Source of Variation
OF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
2028145.0000
253518.1250
369.3642
2.92E-12
Error
11
7550.0000
686.3636
Total
19
2035695.0000
Oneway Analysis of TP by Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
35881.8000
4485.2250
573.6916
2.62E-13
Error
11
86.0000
7.8182
Total
19
35967.8000
Oneway Analysis of SRP By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
23486.8000
2935.8500
949.8338
1.65E-14
Error
11
34.0000
3.0909
Total
19
23520.8000
Oneway Analysis of C-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
159.4177
19.9272
4.2376
1.51 E-02
Error
11
51.7277
4.7025
Total
19
211.1454
Oneway Analysis of N-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
5.7842
0.7230
11.9665
1.96E-04
Error
11
0.6646
0.0604
Total
19
6.4488
Oneway Analysis of C:N-SPOM By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
77.4207
9.6776
37.4608
6.60E-07
Error
11
2.8417
0.2583
Total
19
80.2624
Oneway Analysis of N-DIN By Salinity
Source of Variation
DF
Sum of Squares
Mean Square
F Ratio
Prob > F
Salinity
8
136.5347
17.0668
227.3580
4.14E-11
Error
11
0.8257
0.0751
Total
19
137.3604

86
and many of those springs have elevated concentrations of nitrate (up to 8.0 mg/L)
(Suwannee River Water Management District, 1995, 1996,2003). During high flow
periods, precipitation and surface flow dilute the concentration of nitrates coming into the
river through the springs.
Concentrations of nutrients (nitrogen and phosphorus), chlorophyll a (estimation of
phytoplankton biomass in the water column), dissolved organic carbon, and color
contribute to light attenuation in the Suwannee River (Bledsoe, 1998). High
concentrations of nutrients (especially nitrate) enter the middle reaches of the Suwannee
River (Suwannee River Water Management District, 2003). Phytoplankton in the river
are light limited Bledsoe, 1998) and otherwise available nitrate is not utilized extensively
by phytoplankton (low chlorophyll a levels within the river). Near the mouth of the river
and in the estuary, color and DOC decrease as seawater mixes with river water, and it is
at this point that phytoplankton are no longer light-limited. Phytoplankton numbers
increase in the estuary (based on chlorophyll a concentrations, Table 3-2), and
eutrophication of this system as a consequence of increased nutrient loading is a
legitimate concern (see Frazer et al., 1998).
Natural abundance measures of stable nitrogen and carbon isotope ratios can
contribute to the study of nutrient pollution by determining the source material fueling
production in a system. Temporal and spatial patterns in 6ISN and S13C can provide
additional information on transformation processes. Temporal variation in the stable
nitrogen signature of suspended particles in the Suwannee River is reflective of relative
differences in the abundance of nitrogen sources in the river dining low flow and high
flow periods (Figures 3-3 and 3-4, Table 3-5). The 615N signatures of SPOM during

87
March 1997 (high flow) were higher than those collected during November 1996. During
low flow periods, much of the river is being fed by springs with high nitrate
concentrations. The source of nitrate is often from synthetic fertilizers (as opposed to
remineralized organic matter) within the Suwannee River watershed (Asbury and
Oaksford, 1997; Katz et al., 2001). Typical 615N values of fertilizers are low, or close to
zero (Freyer and Aly, 1974; Flipse and Bonner, 1985; Macko and Ostrom, 1994; Fry et
al., 2001). This is because most fertilizers are produced by the Flaber process which
converts atmospheric nitrogen to ammonium. In this process, the fertilizers retain the
isotopic signature of atmospheric nitrogen (SI5N = 0%o) (Macko and Ostrom, 1994).
During high flow periods, the river is also being fed by overland flow, and this results in
the addition of organic nitrogen from animal waste material. Nitrate produced from
animal waste typically exhibit 51SN values greater than fertilizer 615N (Peterson and Fry,
1987; Karr et al., 2001; Karr et al., 2003). During the two 2003 sampling events, 51SN
signatures of SPOM were nearly the same (starting at 2-3%o in the river stations and
increasing to 5-6%o at station 10) during the high and low flow regimes. The low initial
5ISN signatures of the May 2003 sampling event indicate that the source of nitrogen
coming into the system was likely from a source similar to that of synthetic fertilizers.
Differences in the 61SN of SPOM in the river between 96/97 and 2003 could indicate that
input of fertilizer to the river is increasing, or the relative contribution of DIN from
animal waste is decreasing.
Spatial gradients in the 51SN of SPOM collected from surface waters were present
during low and high flow regimes (Figures 3-3 and 3-4, Table 3-5). The 6,5N of SPOM
decreased near the mouth of the river at stations 2 (March 1997), 4 (November 1996),

88
and 3 (May 2003), then leveled out to a signature closer to that typical of marine
phytoplankton (6%o) (Owens, 1987). The decrease near stations 2 through 4 did not
occur during the December 2003 sampling event. It did, however, slowly increase to a
signature near 6%o by station 10.
Most reactions in which bonds with a nitrogen atom are formed or broken tend to
discriminate against the heavier isotope, resulting in a product depleted in 15N relative to
the substrate (Figure 3-14). There is a progressive increase in the á15N of the residual
pool of reactant as the reaction proceeds. If a reaction goes to completion and the entire
pool of reactants is converted to product (e.g., in a closed system), then conservation of
mass requires that the final product have the same isotopic composition as the initial pool
of reactants (Peterson and Fry, 1987; Montoya and McCarthy, 1995). In an ecological
context, the isotopic fractionation associated with the uptake and assimilation of
dissolved inorganic nitrogen (DIN) by phytoplankton and other autotrophs (i.e. attached
macroalgae, seagrasses, and epiphytic algae) should result in the production of autotroph
biomass depleted in 1SN relative to the available substrate, primarily NO3' in the case of
the Suwannee River and its estuary. This, in turn, will create a spatial gradient in the
stable nitrogen isotope composition of suspended particles in the Suwannee River estuary
(Figure 3-15). Our findings are consistent with this scenario (excluding the December
2003 sampling event) and provide critical information for the interpretation of naturally
occurring variations in 15N in these and other river and estuarine systems.
The stable nitrogen isotope ratio of DIN had not been measured previously in the
Suwannee River and its estuary. These measurements are needed for a more complete
test of the spatial gradient theory. Distinct spatial gradients in the 615N were expected to

Isotopic Composition (%o)
89
0%o
100%o
Figure 3-14. Model of Spatial Gradients in the 515N Signatures of a Hypothetical Closed
System (redrawn from Montoya and McCarthy, 1995).

90
DISTANCE
Figure 3-15. Theoretical Curves Illustrating Spatial Variation in the 615N of
Phytoplankton along an Onshore/Offshore Gradient. Losses in the Bottom
Panel Occur as a Consequence of Grazing and Sedimentation Processes.

10
9
8
7
6
5
4
3
2
1
0
re 3-
o
► ^ ♦ o
, Y A.*
*x
-28
-27 -26 -25
-24
<513C
♦ Oysters
â–  SPOM
â–² Copepods
X Chaetognaths
o Ctenophores
-23 -22 -21 -20
16. úi5N vs. ói3C of Oysters, Zooplankton, and SPOM for the December 2003 Sampling Event.

9
8
7
6
5
4
3
2
1
O
7.
X
o
"X"
X A
X
X
o
'O
ro
-29
-28
-27
-26
-25
813C
-23
â–  SPOM
A Copepods
X Chaetognaths
o Ctenophores
-22 -21 -20
I5N vs. ó13C of Zooplankton and SPOM for the May 2003 Sampling Event.

93
occur in the surface water. During the March 1997 sampling event, 8ISN signatures of
DIN-nitrate and DlN-ammonium were analyzed. The 6I5N signatures of DIN-ammonium
were up to 10%o greater than the 815N signatures of DIN-nitrate. This could indicate that
nitrates are coming from fertilizers while ammonium is coming from animal wastes, and
that animal wastes may contribute more during high flow periods. This could also
indicate that nitrification is occurring (Peterson and Fry, 1987). In chemical processes
such as nitrification, light isotopes react more quickly than heavy isotopes leaving the
residual pool of reactants with a heavier signature than products (Peterson and Fry,
1987). During the 2003 sampling event, only DIN-nitrate was analyzed. Values in the
river were greater (ca. 7%o) during high flow than low flow (ca. 4%o).
Stable carbon isotopes can serve as in situ tracers of the source of organic matter
within aquatic systems. Most systems have several inputs of organic carbon that act as
potential energy sources, e.g., C3 terrestrial plant material (513C = -23 to -30%o),
seagrasses (-3 to -15%o), macroalgae (-8 to -27%o), C3 marsh plants (-23 to -26%o), C4
marsh plants (-12 to -14%o), benthic algae (-10 to -20%o), and marine phytoplankton (-18
to -24%o) (Fry and Sherr, 1984; Michener and Schell, 1994). The 5I3C signatures of
SPOM were fairly consistent throughout all four sampling events. Values ranged from -
28%o in the river (indicating a terrestrial source) to -20%o at the station farthest from the
shore (indicating a marine source).
The implications for the use of stable nitrogen and carbon isotopes in food web
investigations are also significant (DeNiro and Epstein, 1981; Fry, 1988; Wada et al.,
1991; Canuel et al., 1995; Cabana and Rasmussen, 1996; Vander Zanden and Rasmussen,
1999; Jepsen and Winemiller, 2002). DeNiro and Epstein (1981) found that the 815N of

94
organisms reflects the S15N signature of the diet; however, the animal is generally
enriched in l5N by approximately 3 to 5%o relative to the diet. This is mainly due to
excretion of isotopically light nitrogen in urine (Minagawa and Wada, 1984; Owens,
1987; Peterson and Fry, 1987; Fry, 1988; Wada et al., 1991; Lajtha and Michener, 1994;
Cabana and Rasmussen, 1996; Gu et al., 1996). Stable carbon isotopes of animals reflect
those of the diet within approximately l%o (DeNiro and Epstein, 1978; Peterson and Fry,
1987; Michener and Schell, 1994). Since isotopic fractionation leads to significant
spatial variation in the 515N of the primary producers at the base of the food web, spatial
variation in the 615N of heterotrophs may not necessarily imply a shift in trophic position
or a change in trophic behavior.
Oysters and zooplankton were collected during the December 2003 sampling event
for stable isotope analysis and are presented in Figure 3-16. Chaetognaths and
ctenophores, based on their 6I5N and 6I3C signatures, are clearly consuming food sources
with a marine signature. Consistent with their feeding ecology, they appear to occupy a
higher trophic position than copepods and oysters in this system. Oysters and copepods,
however, appear to comsume SPOM (on average, the 015N signatures of the oysters are
approximately 4%o greater than the SPOM and the 513C signatures of the oysters are
approximately l-2%o greater than the SPOM). Oysters were not collected during May
2003, but the relative trophic positions of the zooplankton were qualitatively similar
(Figure 3-17). In the next chapter, the possibility that bivalves in the Suwannee River
estuary are consuming organic aggregates with a terrestrial origin will be explained.
Summary
Surface water samples were collected along a salinity gradient and concentrations
of nitrate, ammonium, phosphate, total nitrogen, total phosphorus, color, chlorophyll a,

95
dissolved organic carbon, and stable nitrogen and carbon isotopes of suspended particles
(SPOM) were determined. Stable nitrogen isotopes serve as in situ tracers of the
processing of nitrogen as it moves through an estuarine system, and stable carbon
isotopes serve as in situ tracers of the source of organic matter within these systems.
Nitrate concentrations and dissolved organic carbon declined markedly with distance
offshore. Distinct spatial gradients in the stable nitrogen isotope composition of the
suspended particles were evident and consistent with expected patterns with the
exception of the December 2003 sampling event. Stable nitrogen and stable carbon
isotopes of SPOM, zooplankton, and oysters provide some food web insights and suggest
that both oysters and calanoid copepods feed on SPOM.
Conclusions
The following conclusions may be drawn from the research discussed in this
chapter:
• Nitrate concentrations in the river were greatest during the low flow periods.
• 51SN of the suspended particles exhibited distinct spatial gradients with distance
offshore consistent with a theoretical model incorporating fractionation effects.
• o15N signatures of dissolved inorganic nitrogen, however, did not exhibit spatial
patterns consistent with the theory.
• SUC signatures of the suspended particles showed an increasing trend with distance
offshore and indicated that the suspended particles had a terrestrial signature in the
river and upper estuary and a marine signature further offshore.
• Stable carbon and nitrogen isotope signatures of the oysters, zooplankton, and
suspended particles provide some food web insights and suggest that oysters and
calanoid copepods consume SPOM.

CHAPTER 4
STABLE ISOTOPES AS TRACERS IN FOOD WEB INVESTIGATIONS OF THE
SUWANNEE RIVER ESTUARY
Introduction
Anthropogenic activities in a watershed can have significant impacts on the
ecology of downstream coastal environments. For example, in the Suwannee River,
surface runoff and groundwater inputs contribute high levels of nutrients, nitrogen in
particular, from major land uses such as silviculture and agriculture (row crops, dairy,
poultry, and swine) (Asbury and Oaksford, 1997; Katz et al., 2001). Nitrate
concentrations within the Suwannee River are increasing, and concentrations near the
mouth and in the upper reaches of the estuary now regularly exceed 1 mg/L (Phlips and
Bledsoe, 1997). Eutrophication of the estuary is a serious concern, particularly for those
involved in the emerging clam aquaculture industry.
To gain insights into the ecological processes operating in the Suwannee River and
its estuary, spatial and temporal patterns of nutrients must be quantified and effects on
flora and fauna in the environment must be studied. Nitrogen, carbon, phytoplankton,
zooplankton, organic aggregates, oysters, and clams are all important components of the
food web in the Suwannee River estuary. However, the relative importance of terrestrial
derived organic matter and marine sources of organic matter in support of the food web
are, at present, poorly understood. Measures of stable carbon and nitrogen isotopes can
be an effective tool for following the flow of energy through an ecosystem such as the
96

97
Suwannee River estuary (Peterson et al., 1985), and may provide insight into the trophic
ecology of this system.
At the mouth of the river and in the estuary, there is a network of oyster reefs and
clam lease sites. The predominant species are the hard clam, Mercenaria mercenaria,
and the oyster, Crassostrea virginica, both of which are suspension feeders. Potential
sources of food include suspended particulate organic material (SPOM), organic
aggregates, and detritus. Alber and Valiela (1994) determined that there are three trophic
pathways by which bivalves might ingest and subsequently assimilate food material: (1)
via direct uptake of dissolved organic matter (which is released by both live and decaying
producers), (2) ingestion of particulate detritus, and (3) ingestion of organic aggregates.
In the Suwannee River estuary, it is possible that the clams and oysters are consuming
organic aggregates as there are often large concentrations of floes formed where the fresh
river water meets the salt water (personal observation). Flocculated material from the
Suwannee River has a high C:N ratio, and may be a quality food source for the clams and
oysters (Chapter 2).
Stable carbon isotopes can be a good indicator of food sources (Chapter 2 and 3,
this dissertation). Carbon isotopic compositions of animals reflect those of the diet to
within approximately l%o (DeNiro and Epstein, 1978; Peterson and Fry, 1987; Michener
and Schell, 1994; O’Donnell et al., 2003). Animals may be isotopically enriched relative
to their diet as a consequence of preferential loss of 12C02 during respiration, preferential
uptake of l3C compounds during digestion, or metabolic fractionation during synthesis of
different tissue types (DeNiro and Epstein, 1978; Rau et al, 1983; Tieszen et al., 1983;
Fry et al., 1984). Stephenson (1986) studied oysters from Nova Scotia, Canada, in a

98
laboratory setting and reported a 513C enrichment of approximately l%o in the oysters
relative to their diet. This finding suggests that carbon isotope ratios in bivalves may be
used to determine the primary food source for bivalves in the Suwannee River estuary.
Isotope signatures of laboratory-produced flocculated organic aggregates were
determined and data are presented in chapter 2. Briefly, the SI3C values of the organic
aggregates ranged from -26 to -28%o. Stable carbon isotope signatures of clams and
oysters should be within that range or about l%o greater (due to fractionation effects) if
they are consuming the flocculated organic aggregates. If the clams and oysters are
primarily consuming other sources of suspended particulate organic matter (SPOM)
originating offshore or in the estuary, then their signatures will be more reflective of the
613C signatures of the SPOM originating in the marine environment. Stable carbon
signatures of SPOM in the flow path of the river are described in Chapter 3. SPOM
exhibited a more terrestrial signature (-28%o) near the mouth of the river compared to a
more marine signature (-21%o) further away from the main influence of the river.
Stable nitrogen isotope ratios in animals can also be an indicator of source of food;
however, trophic fractionation results in a production of animal biomass with a 5ISN
signature significantly and predictably higher than that of the food source. On average,
an animal has a 5ISN signature 3.5%o higher than that of its food (Owens, 1987; Peterson
and Fry, 1987). The 6I5N signatures of laboratory-produced flocculated organic
aggregates range from -4 to 6%o (see chapter 2). The ol5N values of SPOM collected
along salinity-based transects in the Suwannee River estuary ranged from 6 to 10%o (high
flow, March 1997), 3 to 6%o (low flow, November 1996), 0 to 6%o (high flow, May
2003), and 1 to 6%o (low flow, December 2003), as described in Chapter 3. These

99
findings suggest that 615N values in key consumers, such as clams and oysters, may
exhibit a wide range in their stable nitrogen isotope signatures.
The isotopic composition of inorganic nutrients (such as nitrate and ammonium)
sets a baseline 515N for an ecosystem, but the actual distribution of isotopes is determined
by the fractionation effects associated with biological processes. In the presence of
abundant dissolved inorganic nitrogen (DIN), biological fractionation leads to a
production of autotrophic biomass depleted in lsN relative to the available DIN, with
animal biomass SlsN values increasing with trophic position. Thus, nitrogen isotopes
provide information on the pathways of nitrogen flow within as well as into a food web.
The purpose of this study was to establish a direct link between carbon and
nitrogen being discharged from the Suwannee River and production of clams and oysters
in the estuary, based on the hypothesis that the clams and oysters are consuming
flocculated organic aggregates of terrestrial origin. Processes that affect the transfer and
fate of DOM in this system are not well understood, in part, because the pathways are
difficult to resolve using only traditional methods (i.e. hydrographic and mass balance
studies) and because of the complexity of the nitrogen cycle and the relatively large
spatial and temporal scales of interest. The stable isotopic signatures of carbon and
nitrogen provide an integrative tool for studying pathways of material transport and
nitrogen flow within coastal food webs.
Methods and Materials
Site Description
The Suwannee River originates in the Okeefenokee Swamp in Georgia, USA, and
is 394 km long with a drainage basin of approximately 25,640 km2 (Nordlie, 1990). The
Suwannee River has the second largest discharge rate in the state of Florida and, on

100
average, is greater than 280 mV. Periods of peak flow occur typically in early spring
and periods of low flow during fall. Flow patterns, however, are significantly altered by
tropical storm activity in the region. Spring and ground-water discharge contribute
significantly to nitrate loading of the river, particularly during periods of low flow
(SRWMD, 2003). The upper part of the estuary, comprising both oligohaline and
mesohaline zones, is bordered by brackish marsh habitat and is dominated by emergent
grasses and rushes. Submerged aquatic vegetation (SAV) is less abundant. The lower
portion of the neashore estuary is a mosaic of saltmarsh, tidal creeks, mudflats, and oyster
habitats. Seagrasses are much less abundant within this estuary when compared to other
areas along Florida’s Big Bend coast due to highly colored surface water and attendant
low light levels (Bledsoe, 1998). The main pathway of nitrogen transfer to higher trophic
levels is likely to occur through the pelagic compartment (i.e. phytoplankton production
in the surface water) (Frazer et al., 1998; Bledsoe and Phlips, 2000).
The Suwannee River estuary and the surrounding Big Bend region is one of the
largest and most productive nursery areas in the Gulf of Mexico (SRWMD, 1979).
Oysters (Crassostrea virginica) are harvested from the Suwannee River estuary
periodically throughout the year (Wolfe and Wolfe, 1985) and the region also supports an
emerging hard clam (Mercenaria mercenaria) aquaculture industry in Florida. The
growth and sustainability of this industry will depend ultimately on the ecological health
of the system.
Sampling
Clams, oysters, and suspended particulate organic matter (SPOM) were sampled at
2 sites (D428 and L512) in the Suwannee River estuary (Figure 4-1). Clam and oyster
seed were provided by a commercial vendor, and then seeded at the lease sites in October

101
2002. Clams, oysters, and SPOM were sampled twice each month, beginning in October
2002. Sampling continued until December 2003. Once collected, samples were placed
immediately on ice and stored in a freezer. Each clam and oyster was measured for body
size (length, width, and thickness) and wet and dry weight. Clams and oysters were
shucked and fresh tissue dried in an oven at 60° C for at least 24 hours. Once dried, the
samples were ground up to a fine powder with a mortar and pestle and stored in a
dessicant cabinet until isotope analyses were completed. Whole water was collected
during each sampling trip. The water was kept in a colored cooler on ice until returned to
the laboratory where it was immediately filtered through precombusted glass fiber filters
(Whatman GF/F, 450°C, 4h) to collect suspended particulate organic matter (SPOM).
Filtered particles were dried at 60°C (>48h) in preparation for isotope analysis.
Stable Isotope Analyses
Clams, oysters, and SPOM were analyzed for stable carbon and nitrogen isotopes.
All isotope samples were analyzed with a Finnigan Delta-C continuous-flow mass
spectrometer. Results are reported in standard 8 notation where:
6'5N (%o) = [((l5N/14N)sample/(l5N/l4N)standard)-1 ] x 1000 (4-la)
and
513C (%o) = [((13C/'2C)sample/(13C/12C)standard)-l] x 1000 (4-lb)
Atmospheric nitrogen and Pee Dee Belemnite served as reference standards. The
reproducibility of both the stable o13C and 8I5N values were within 0.3%o.
Results
The complete sets of 8I3C and 815N values of the suspended particulate organic
matter (SPOM), clams, and oysters are presented in Appendix A. Measures of body size
for clams and oysters are presented in Appendices B and C, respectively. The SI3C

102
Figure 4-1. Map of Sampling Sites for Clams, Oysters, and Suspended Particulate
Organic Matter (SPOM) in the Suwannee River Estuary.

103
values of the SPOM ranged from -17.1 to -25.5%o (average = -20.6%o) and the 8I5N
values of the SPOM ranged from 0.26 to 6.18%o (average = 3.9%o) (Figures 4-2 and 4-3).
The ol3C values of the SPOM were lowest (most negative) in May, 2003. The clams and
oysters collected from the same areas had slightly higher (less negative). 513C values for
clams ranged from -15.9 to -25.0%o (average ol3C = -22.6%o) and -22.4 to -26.5%o for
oysters (average ¿l3C = -23.9%o) (Figures 4-4 and 4-5). The S13C values of the clams did
not change significantly throughout the year (ANOVA, p > 0.05), however the 813C
values of the oysters did change significantly (ANOVA, p < 0.05). From November,
2002 to May, 2003, the 5I3C signatures of the oysters decreased. From May, 2003 to
November, 2003, the ol3C signatures of the oysters increased. The ol5N values of the
clams and oysters were greater than the o15N values of the SPOM. The ol5N of clams
ranged from 5.9 to 9.2%o (average = 6.5%o) and the 815N of oysters ranged from 5.4 to
9.2%o (average = 7.8%o) (Figures 5-6 and 5-7, respectively). On average, the northern
site (D428) had higher stable nitrogen signatures than the southern site (L512) for clams
and oysters.
Discussion
Stable Carbon Isotopes
Most systems have several inputs of organic carbon that serve as potential food
sources, e.g., C3 terrestrial plant material (513C = -23 to -30%o), seagrasses (-3 to -15%o),
macroalgae (-8 to -27%o), C3 marsh plants (-23 to -26%o), C4 marsh plants (-12 to -14%o),
benthic algae (-10 to -20%o), and marine phytoplankton (-18 to -24%o) (Fry and Sherr,
1984; Michener and Schell, 1994). In the Suwannee River estuary system, the 5I3C
values of the suspended particulate organic matter (SPOM) resembled that of marine
phytoplankton. The average á13C signature of the SPOM collected as part of this study

-15
-17
-19
O
<->
le
-21
-23
-25
X
♦ D428 (North Site)
XL512 (South Site)
o
X
♦
♦
-27 H I T T I I
1-Sep-02 21-Oct-02 10-Dec-02 29-Jan-03 20-Mar-03 9-May-03 28-Jun-03 17-Aug-03 6-Oct-03 25-Nov-03 14-Jan-04
Date
Figure 4-2. ó,3C of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River Estuary Sites .

7
6
5
4
3
2
1
O
1-S
4-3.
X
♦ D428 (North Site)
XL512 (South Site)
X
X^
X
♦
o
♦
X
♦
>-02 21-Oct-02 10-Dec-02 29-Jan-03 20-Mar-03 9-May-03 28-Jun-03 17-Aug-03 6-Oct-03 25-Nov-03 14-Jan-04
Date
615N of Suspended Particulate Organic Matter (SPOM) from Two Suwannee River Estuary Sites .

-15
O
T«o
-16
-17
-18
-19
-20
-21
-22
-23
-24
-25
-26
-27
-28
-29
-30
10-Dec-02
I
i
i
I
i
29-Jan-03
20-Mar-03
Date
Figure 4-4. ó13C of Clams from Two Suwannee River Estuary Sites .
♦ D428 (North Site)
XL512 (South Site)
í S j i
o
On
9-May-03
28-Jun-03
17-Aug-03

-22.0
-22.5
-23.0
-25.5
-26.0
-26.5
-27.0
21-Oct-02 10-Dec-02 29-Jan-03 20-Mar-03 9-May-03
Date
Figure 4-5. 5,3C of Oysters from Two Suwannee River Estuary Sites .
o
♦ D428 (North Site)
XL512 (South Site)
28-Jun-03
17-Aug-03
6-Oct-03
25-Nov-03

108
was -20.6%o. The average SI3C signature of the clams was -22.6%o, with almost no
difference between the north and south sites. The 513C values of the oysters differed
significantly throughout the year; however, there was no significant difference between
the north and south sites. During the low flow season, as discussed in Chapter 3 (October
2002 to January 2003 and August 2003 to December 2003), the S13C signature of the
oysters was relatively high (less negative, -22 to -24%o), indicative of a more marine
source of carbon. During the high flow season in February 2003 to July 2003 (Chapter
3), the S13C signatures were, in general, much more negative (-24 to -26.5%o) and
reflective of a more terrestrial source of carbon. The same pattern was seen with the
SPOM (see Figures 4-2 and 4-5). Oysters are filter feeders and depend on water currents
for the delivery of food (Hsieh et al., 2000; Livingston et al., 2000). During the high
flow season, more organic matter is carried to the estuary by the river, whereas during the
low flow season, the oysters’ food source is marine plankton. Damaude et al. (2004)
used stable carbon isotopes to study terrestrial particulate organic material (POM) off the
mouth of the Rhone River Delta in the NW Mediterranean Sea. They determined that
suspension-feeders showed a partial uptake of terrestrial POM depending on its
availability. Flsieh et al. (2000), in studying the SI3C signatures of oysters and POM in a
tropical shallow lagoon in southwestern Taiwan, also found that oysters feed
predominantly on the available water column POM, regardless of its origin.
Clams in this study exhibited a relatively uniform pattern in their S13C signatures
and were generally heavier than oysters, i.e. enriched in 13C. Clams are bottom dwellers,
buried in the sediments, where they feed through a siphon (Ruppert and Bames, 1994).
Oysters, although benthic in nature, occupy a higher position in the water column

10
9
8
6
i
i
O
vo
5
4
10-Dec-02 29-Jan-03 20-Mar-03 9-May-03
Date
Figure 4-6. 615N of Clams from Two Suwannee River Estuary Sites .
♦ D428 (North Site)
XL512 (South Site)
28-Jun-03 17-Aug-03

10
9
8
6
4 J i > .
21 -Oct-02 10-Dec-02 29-Jan-03 20-Mar-03 9-May-03
Date
Figure 4-7. 8I5N of Oysters from Two Suwannee River Estuary Sites .
♦ D428 (North Site)
XL512 (South Site)
28-Jun-03 17-Aug-03 6-Oct-03 25-NOV-03

Ill
(Ruppert and Barnes, 1994). It is possible that stratification of the water column results
in different types of food for these two organisms. Significant amounts of terrestrial
organic matter from the river may not reach the sediment where the clams are located,
possibly due to high flow conditions of the Suwannee River. As a consequence, clams
may be restricted to consuming strictly marine carbon sources during most of the year.
Damaude et al. (2004) studied the impact of terrestrial POM at water depths in the
Rhone River Delta, and found that the contribution of terrestrial POM was the lowest in
deepest areas of the delta. Most of the terrestrial POM had already been consumed or
washed away before many of the benthic species could consume it. Thayer et al. (1983)
studied the influence of terrestrial carbon and phytoplankton on DOC and POM in the
Gulf of Mexico. They found that DOC and particulates had terrestrial 513C values (-
24%o), and that phytoplankton presented more typical marine signatures (-22%o). The
stable carbon isotope signature of the fish and zooplankton (consumers of the particulates
and phytoplankton) indicated a prevalence of marine derived carbon (Thayer et al.,
1983).
It is also important to note the 513C signature of the clams and oysters versus body
weight (Figures 4-8 and 4-9). The 513C signatures of the clams stayed essentially the
same with increasing body weight (Figure 4-8). Therefore, there was no apparent change
in the stable carbon isotope composition of their food over the course of the study. In
contrast, off the coast of Virginia, O’Donnell et al. (2003) found that more enriched
values of 6I3C occurred in adult clams than in juvenile clams. There was, however, a
slight decrease in the oI3C signature of the oysters in the Suwannee River with increasing
body weight. Oysters are capable of selecting particles with high nutritious value

112
(Tamburri and Zimmer-Faust 1996), and therefore may be utilizing some of the
terrestrial-derived organic matter when the marine SPOM, or phytoplankton, is limited.
Stable Nitrogen Isotopes
The slightly increasing trend of 5ISN signatures of the clams and oysters
throughout the sampling year suggests a potential shift in diet (Figures 4-6 and 4-7). On
average, an animal has a 615N signature that is 3 to 5%o higher than that of its food
(Owens, 1987; Peterson and Fry, 1987). In the beginning of the sampling year in the
Suwannee River estuary (November/December 2002) the 6I5N values of the clams were
near 6.5%o, oysters were 6%o, and SPOM were near 4.5%o. Towards the end of the
sampling year (August/October/December 2003) the 61SN values of the clams were near
9%o, oysters were near 8.5%o, and SPOM remained near 4.5%o. There are some possible
reasons for the difference in 615N values between adults and juvenile clams. For
example, smaller clams may have access to different food sources simply because of the
smaller size of their siphons (Rau et al., 1990). There may also be slightly different
isotope fractionations associated with amino acid synthesis at the cellular level based on
different growth strategies and resource allocation needs as the clams mature (O’Donnell
et ah, 2003). O’Donnell et ah (2003) also found that adult clams (Mercenaria spp. from
coastal Virginia) are more enriched in 615N than the juvenile clams. The difference in the
5I5N values of the oysters with body size (this study) was not as evident as with the
clams, and there was high variation in 6ISN values of the smaller oysters as well as of the
larger oysters.
Multiple Stable Isotopes and Food Source
Multiple stable isotopes have historically been used to trace the flow of organic
matter and to determine the trophic structure of estuarine food webs (Peterson et ah,

Dry Body Weight (g)
Figure 4-8. 513C vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary Sites.

-22.0
-27.0 J-
0
0.2
0.4
0.6
0.8
1.2
Dry Body Weight (g)
Figure 4-9. 513C vs. Dry Body Weight (g) of Oysters from Two Suwannee River Estuary Sites .

9.5
5.0 t
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50
Dry Body Weight (g)
Figure 4-10. 615N vs. Dry Body Weight (g) of Clams from Two Suwannee River Estuary Sites .

Dry Body Weight (g)
Figure 4-11. 615N versus Dry Body Weight (g) of Oysters from Two Suwannee River Estuary Sites .

10
8
6
4
2
0
-2
-4
-6 J
-35 -30 -25 -20 -15 -10 -5 0
513C
X
>¿<
X
xxXx
>*< X X*K
X £
x v K
o o
♦ ♦
X
aa
A
X
X
* %
♦ Clams
o Oysters
ASPOM
XFIoc
* X
Xx x x
X
Figure 4-12. The Suwannee River Estuary Food Web Structure Using 613C and 5I5N.

118
1985; O’Donnell et al., 2003). The stable carbon and nitrogen isotope signatures of the
clams, oysters, and SPOM from this study as well as those of the flocculated organic
aggregates from chapter 2 are given in Figure 4-12. The values of the clams and oysters
are very similar. The average S15N values of the clams and oysters are about 3.5%o
heavier than the average values for SPOM and are about 3-8%o heavier than the floes.
These data might lead to the suggestion that bivalves are possibly consuming floes,
however, the 513C values suggests otherwise. The S13C values of the clams and oysters
are similar, and they are approximately the same as the ól3C values of the SPOM. The
S13C values of the floes are about 8%o lighter than the bivalves, indicating that they are
not a significant food source for the bivalves.
Summary
Clams and oysters were planted in the Suwannee River estuary north and south of
the river mouth. Samples of clams, oysters, and suspended particulate organic matter
(SPOM) were collected monthly for approximately one year and subsequently analyzed
for stable carbon and nitrogen isotopes. The results suggest that the clams were
consuming the same food source throughout the year (likely, marine derived organic
matter). The oysters’ isotopic signatures changed consistently with flow patterns in the
river and were more terrestrial in nature during high flow regimes and more marine in
nature during low flow regimes. Neither clams nor oysters appear to consume
flocculated organic aggregates in significant quantity.
Conclusions
The following conclusions may be drawn from the research discussed in this
chapter:

119
• 513C signatures of the suspended particles changed significantly throughout the
sampling year suggesting that marine phytoplankton was likely the dominant
source during low flow periods and that terrestrial-derived organic matter was
relatively more important during high flow periods.
• 81SN signatures of the suspended particles ranged from 0 to 6%o throughout the
sampling year.
• 513C signatures of the clams did not change significantly (average was -22.6%o)
throughout the sampling year indicating that they were consuming a marine-
derived food source.
• S13C signatures of the oysters varied temporally and reflected variation in the 613C
signatures of SPOM, suggesting that river borne organic matter fuels their
production at times.
• Neither clams nor oysters consume flocculated organic aggregates as a dominant
food source.

CHAPTER 5
SUMMARY, CONCLUSIONS, AND RECOMMENDATIONS
Summary
The overall goal of this research was to study the transformation and fate of DOM
originating in the Suwannee River using stable carbon and nitrogen isotopes. This
included three main objectives: (1) determining if flocculated organic aggregates could
be produced in the laboratory and if they maintained a terrestrial isotopic signature, (2)
characterizing the spatial pattern of stable isotope structure in particulate organic matter
in the Suwannee River and its estuary during two different flow regimes, and (3) using
stable isotope ratios to investigate aspects of the food web in the Suwannee River estuary.
The findings from the laboratory study indicate that the SI3C signatures of flocculated
organic matter might be used to quantify its role as a food source for estuarine fauna.
The findings from the initial field study indicated that stable nitrogen isotopes serve as in
situ tracers of the processing of nitrogen as it moves through an estuarine system, and that
stable carbon isotopes might serve as in situ tracers of the source of organic matter within
these systems. Distinct spatial gradients in the stable nitrogen isotope composition of the
suspended particles were evident and consistent with expected patterns with the
exception of the December 2003 sampling event. The results of the food web
investigations indicate that the clams were likely consuming the same source of organic
material throughout the year (marine-derived organic matter), and suggested that the
oysters’ food source changed with flow patterns in the river (e.g., more terrestrial isotope
signatures were observed during high flow regimes and more characteristically marine
120

121
signatures during low flow regimes). Neither clams nor oysters were consuming
flocculated organic aggregates as a dominant food source.
Conclusions
The following conclusions are drawn as they relate to the research performed to
meet this study’s objectives:
• Formation of organic aggregates, i.e. floes, can be induced by mixing salts with
Suwannee River water rich in dissolved organic material.
• 51SN signatures of aggregates increased significantly with salinity, but exhibited
pronounced variability.
• S13C signatures did not change significantly with increasing salinity indicating that
stable carbon isotope ratios might be used as a tracer of terrestrial derived dissolved
organic matter in estuarine and coastal food webs.
• The C:N ratios increased significantly with increasing salinity, but did not exceed
values of 17 indicating that salinity induced aggregates are a potentially high
quality food source for suspension feeding organisms in the Suwannee River
estuary and associated nearshore coastal waters.
• Nitrate concentrations in the river were greatest during the low flow periods.
• Most chemical parameters decreased with distance offshore indicating mixing.
• 615N of the suspended particles exhibited distinct spatial gradients with distance
offshore consistent with a theoretical model incorporating fractionation effects.
• SI5N signatures of dissolved inorganic nitrogen, however did not exhibit spatial
patterns consistent with the theory.
• 5i3C signatures of the suspended particles did not change significantly with
distance offshore indicating that stable carbon isotope ratios might be used as a
tracer of terrestrial derived dissolved organic matter in estuarine and coastal food
webs.
• Stable carbon and nitrogen isotope signatures of the oysters, zooplankton, and
suspended particles provide some food web insights and suggest that oysters and
calanoid copepods consume SPOM
• SI3C signatures of the suspended particles changed significantly throughout the
sampling year suggesting that marine phytoplankton was likely the dominant

122
source during low flow periods and that terrestrial-derived organic matter was
relatively more important during high flow periods.
• S15N signatures of the suspended particles ranged from 0 to 6%o throughout the
sampling year.
• 513C signatures of the clams did not change significantly (average was -22.6%o)
throughout the sampling year indicating that they were consuming a marine-
derived food source.
• S13C signatures of the oysters varied temporally and reflected variation in the o13C
signatures of SPOM, suggesting that river borne organic matter fuels their
production at times.
• Neither clams nor oysters consume flocculated organic aggregates as a dominant
food source.
Recommendations for Further Research
The following recommendations are made to further the extent of knowledge
relating to flocculation, isotope biogeochemistry, and foodweb studies:
• An analysis of bacteria should be performed on flocculated organic aggregates to
determine their importance in the flocculation process.
• The specific contents of the flocculated organic aggregates should be analyzed.
• Sulfur isotopes should be considered when using isotope chemistry to determine
food source.
• Additional fauna, such as mussels or pelagic fish, should be analyzed for isotope
analyses to more fully characterize the foodweb structure of the Suwannee River
estuary.

APPENDIX A
SUPPLEMENTAL STABLE CARBON AND NITROGEN ISOTOPE DATA
Table A-l. Stable Carbon and Nitrogen Isotopes ofClams, Oysters, and Suspended
Particulate Organic Matter (SPOM).
Site
Collection
Date
Label
815N
513C
umol N
umol C
C:N
CLAMS |
D428
14-Jan-03
ME691
6.79
-21.50
6.76
33.76
5.00
D428
14-Jan-03
ME692
6.47
-21.51
ND
27.58
4.87
D428
14-Jan-03
ME693
7.32
-18.65
2.91
12.86
4.42
D428
14-Jan-03
ME694
6.64
-21.55
4.20
21.52
5.13
D428
14-Jan-03
ME695
6.72
-21.38
4.79
23.48
4.90
D428
14-Jan-03
ME696
6.98
-21.09
5.06
24.70
4.88
D428
14-Jan-03
ME697
6.56
-21.16
5.58
26.77
4.80
D428
14-Jan-03
ME698
7.03
-21.54
4.15
20.18
4.86
D428
14-Jan-03
ME699
6.92
-21.87
3.74
18.88
5.05
D428
14-Jan-03
ME700
6.90
-21.25
3.98
19.53
4.90
D428
14-Jan-03
ME701
6.50
-20.88
3.65
17.69
4.85
D428
14-Jan-03
ME702
6.66
-20.99
2.63
12.95
4.92
D428
14-Jan-03
ME703
7.02
-21.31
3.20
16.06
5.02
D428
14-Jan-03
ME704
6.62
-21.42
5.05
25.64
5.07
D428
14-Jan-03
ME705
6.72
-21.32
5.00
25.88
5.18
D428
14-Jan-03
ME706
6.76
-21.66
4.61
23.06
5.00
D428
14-Jan-03
ME707
7.01
-21.04
2.83
13.99
4.94
D428
14-Jan-03
ME708
6.87
-21.01
2.42
12.02
4.96
D428
14-Jan-03
ME709
6.26
-21.37
2.55
13.10
5.14
D428
14-Jan-03
ME710
6.57
-21.67
2.92
14.54
4.97
D428
14-Jan-03
ME711
6.67
-21.39
5.32
24.94
4.69
D428
14-Jan-03
ME712
6.82
-21.57
6.87
31.69
4.62
D428
14-Jan-03
ME713
6.55
-21.26
3.33
16.42
4.93
D428
14-Jan-03
ME714
6.75
-21.73
2.80
13.98
4.99
D428
14-Jan-03
ME715
6.79
-15.94
5.27
2.75
0.52
D428
14-Jan-03
ME716
7.08
-21.35
6.25
28.93
4.63
D428
14-Jan-03
ME717
6.53
-21.35
4.10
18.56
4.52
D428
14-Jan-03
ME718
6.79
-21.46
4.32
20.34
4.70
D428
14-Jan-03
ME719
6.44
-21.27
5.80
27.73
4.78
D428
14-Jan-03
ME720
6.54
-21.40
3.95
18.51
4.69
123

124
Site
Collection
Date
Label
615N
513C
umol N
umol C
C:N
L512
2-Feb-03
ME721
7.19
-22.65
6.31
32.68
5.18
L512
2-Feb-03
ME722
7.06
-22.40
3.45
17.76
5.14
L512
2-Feb-03
ME723
7.05
-22.25
4.33
23.19
5.36
L512
2-Feb-03
ME724
6.68
-21.86
4.46
22.99
5.15
L512
2-Feb-03
ME725
7.00
-22.76
5.54
29.31
5.30
L512
2-Feb-03
ME726
7.22
-22.72
5.99
30.52
5.09
L512
2-Feb-03
ME727
7.20
-22.33
5.75
31.26
5.44
L512
2-Feb-03
ME728
7.27
-22.39
4.97
27.18
5.47
L512
2-Feb-03
ME729
7.33
-22.50
3.32
19.20
5.78
L512
2-Feb-03
ME730
7.26
-22.36
3.40
18.63
5.48
L512
2-Feb-03
ME731
7.54
-22.25
3.76
20.30
5.40
L512
2-Feb-03
ME732
7.62
-22.08
5.11
25.47
4.98
L513
2-Feb-03
ME733
7.41
-22.26
4.88
27.97
5.74
L514
2-Feb-03
ME734
7.84
-21.98
2.84
15.70
5.53
L515
2-Feb-03
ME735
7.34
-21.74
5.05
27.01
5.35
L516
2-Feb-03
ME736
8.15
-22.51
3.20
17.63
5.50
L512
2-Feb-03
ME737
7.67
-22.81
5.39
29.89
5.55
L512
2-Feb-03
ME738
7.67
-22.41
4.17
22.03
5.28
L512
2-Feb-03
ME739
7.29
-22.19
3.68
18.88
5.13
L512
2-Feb-03
ME740
7.19
-22.55
4.91
26.49
5.40
L512
2-Feb-03
ME741
7.57
-22.28
3.80
21.95
5.78
L512
2-Feb-03
ME742
7.48
-22.50
3.80
20.70
5.44
L512
2-Feb-03
ME743
7.32
-22.33
3.91
20.63
5.28
L512
2-Feb-03
ME744
6.95
-22.39
4.21
23.24
5.52
L512
2-Feb-03
ME745
7.14
-21.98
6.11
36.67
6.00
L512
2-Feb-03
ME746
7.26
-22.63
3.19
17.71
5.54
L512
2-Feb-03
ME747
7.60
-22.52
2.39
14.10
5.90
L512
2-Feb-03
ME748
7.70
-22.62
3.84
21.65
5.63
L512
2-Feb-03
ME749
7.67
-21.96
4.52
24.47
5.41
L512
2-Feb-03
ME750
8.95
-22.21
3.34
19.41
5.81
L512
20-Feb-03
ME451
6.89
-14.96
6.66
38.59
5.80
L512
20-Feb-03
ME452
7.15
-17.28
5.02
30.11
6.00
L512
20-Feb-03
ME453
7.07
-24.22
3.25
19.58
6.02
L512
20-Feb-03
ME454
7.67
-22.69
3.49
21.66
6.22
L512
20-Feb-03
ME455
7.83
-18.90
6.01
36.79
6.12
L512
20-Feb-03
ME456
7.15
-22.49
2.73
15.34
5.63
L512
20-Feb-03
ME457
6.62
-22.60
3.50
21.64
6.19
L512
20-Feb-03
ME458
7.55
-20.36
4.34
26.07
6.01
L512
20-Feb-03
ME459
7.15
-21.34
3.87
22.75
5.89
L512
20-Feb-03
ME460
7.34
-22.80
2.71
16.65
6.15
L512
20-Feb-03
ME461
7.54
-18.22
5.10
28.70
5.62
L512
20-Feb-03
ME462
7.36
-20.29
3.75
22.32
5.95
L512
20-Feb-03
ME463
7.65
-17.50
3.80
23.61
6.22
L512
20-Feb-03
ME464
7.43
-19.40
5.14
31.24
6.08
L512
20-Feb-03
ME465
7.01
-23.10
3.90
23.08
5.91
L512
20-Feb-03
ME466
7.08
-23.24
3.57
21.30
5.97
L512
20-Feb-03
ME467
7.15
-21.76
2.97
18.31
6.16

125
Site
Collection
Date
Label
815N
513C
umol N
umol C
C:N
L512
20-Feb-03
ME468
7.73
-19.33
4.51
26.74
5.93
L512
20-Feb-03
ME469
7.24
-19.30
4.37
26.39
6.04
L512
20-Feb-03
ME470
7.49
-15.79
6.14
37.23
6.06
L512
20-Feb-03
ME471
7.52
-20.38
3.16
18.90
5.99
L512
20-Feb-03
ME472
7.16
-18.00
5.33
32.01
6.01
L512
20-Feb-03
ME473
6.21
-15.98
3.97
22.77
5.74
L512
20-Feb-03
ME474
7.42
-17.18
4.42
25.46
5.75
L512
20-Feb-03
ME475
7.19
-24.97
3.87
22.33
5.78
L512
20-Feb-03
ME476
7.43
-20.02
3.78
23.85
6.31
L512
20-Feb-03
ME477
7.68
-18.41
4.85
27.33
5.64
L512
20-Feb-03
ME478
7.64
-21.13
3.15
20.38
6.46
L512
20-Feb-03
ME479
7.20
-18.44
4.43
27.41
6.19
L512
20-Feb-03
ME480
7.47
-20.81
3.33
21.57
6.47
D428
10-Mar-03
ME863
6.28
-23.04
5.32
25.46
4.79
D428
10-Mar-03
ME864
6.60
-22.54
4.23
23.23
5.49
D428
10-Mar-03
ME865
7.15
-22.46
5.84
29.69
5.08
D428
10-Mar-03
ME866
5.64
-23.37
3.84
19.10
4.98
D428
10-Mar-03
ME867
6.50
-22.48
4.98
25.00
5.02
D428
10-Mar-03
ME868
6.54
-22.75
4.05
20.84
5.15
D428
10-Mar-03
ME869
7.04
-22.80
5.61
29.91
5.33
D428
10-Mar-03
ME870
6.18
-22.84
3.77
18.96
5.03
D428
10-Mar-03
ME871
5.99
-22.83
5.27
26.76
5.07
D428
10-Mar-03
ME872
6.28
-22.59
3.44
17.64
5.13
D428
10-Mar-03
ME873
7.21
-22.81
4.59
24.17
5.26
D428
10-Mar-03
ME874
6.89
-22.69
6.03
30.16
5.00
D428
10-Mar-03
ME875
7.13
-22.85
5.29
25.81
4.88
D428
10-Mar-03
ME876
6.83
-22.51
4.65
22.58
4.85
D428
10-Mar-03
ME877
5.91
-22.73
4.32
22.19
5.13
D428
10-Mar-03
ME878
6.27
-23.39
4.55
24.09
5.29
D428
10-Mar-03
ME879
6.46
-22.43
4.32
21.81
5.05
D428
10-Mar-03
ME880
5.94
-22.66
3.67
18.97
5.17
D428
10-Mar-03
ME881
6.61
-22.02
6.06
31.66
5.22
D428
10-Mar-03
ME882
6.50
-22.47
4.34
22.34
5.14
D428
10-Mar-03
ME883
7.43
-22.48
3.16
16.16
5.12
D428
10-Mar-03
ME884
7.04
-22.32
4.41
20.53
4.66
D428
10-Mar-03
ME885
6.51
-22.74
4.68
23.84
5.09
D428
10-Mar-03
ME886
6.34
-22.65
5.09
24.25
4.77
D428
10-Mar-03
ME887
6.38
-22.76
4.75
24.02
5.06
D428
10-Mar-03
ME888
5.98
-22.47
3.91
19.73
5.04
D428
10-Mar-03
ME889
6.16
-22.19
2.78
13.79
4.96
D428
10-Mar-03
ME890
6.74
-22.57
4.82
24.71
5.13
D428
10-Mar-03
ME891
6.59
-22.44
4.50
23.03
5.11
D428
10-Mar-03
ME892
6.65
-21.68
6.07
29.22
4.81
L512
25-Mar-03
ME541
7.77
-17.12
5.39
25.59
4.75
L512
25-Mar-03
ME542
8.03
-22.46
2.82
13.33
4.73
L512
25-Mar-03
ME543
7.77
-19.53
4.89
23.42
4.79

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bsbjsipio^ubw
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roioeoiouioroeoro
osw^sos-^co
en oí en a
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eo lo to io
(jioosmcocoseos
sso)0)0)C3cntno)en
roAAio^cobiobw
COOCO-t^O—*C0OOM
L514 15-Dec-02 CV133 7.42 -24.20 2.99 16.94 5.67
L515 15-Dec-02 CV134 7.57 -24.26 4.71 26.47 5.61
L516 15-Dec-02 CV135 7.54 -25.57 5.65 32.83 5.81
en en
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oooooooooo
- ‘ * - 4». ^ ^ ^ ^ -t».
01(71010)010)01010303
6666666666
CDCDCDCD(D(DCD(D(D(D
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ppiuipiuipipipienp
bénabico^u^iou
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biosuA^biAÍnk)
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co m n co
co co oj
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co ro co co
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CO S O) O LO ^ O)
LO LO LO LO CO LO LO
Ti- o CO O) O Tí- co
r; CO N W (O O S
o lo Tt ai ai co co
cn co co co t* lo co tj- co
CO N CO (O O) co co
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t-COCNCNCOCNCNCOt-
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CNlOTtTtCOlOCOTfCO
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coo>iqcpinsr-0)g-
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coidcococococbcor^-io
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CNCNCN-»— CNCOt— T— CNt-
LOOJOTfiOT— OIOCNCN
Or-OCqqr;T-(\jSCO
lOTfidcoTfidcdcoTtcN
NqconTfinc\jT-c\jcq
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_ - — _ . . . . Tt LO
g-g-g-Tíioioioioioio
CNCNCNCNCNCNCNCNCNCN
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CNCNCNCNCNCNCNCNCNCN
TÍ-N-Tí-rt'N-TtTfTtTí-'N-
OOQOOQQQOO

131
Site
Collection
Date
Label
81!N
S13C
umol N
umol C
C:N
D428
15-Sep-03
CV 257
8.39
-23.57
5.42
26.16
4.82
D428
15-Sep-03
CV 258
7.76
-23.59
3.69
18.80
5.10
D428
15-Sep-03
CV 259
9.17
-23.44
6.34
30.98
4.89
D428
15-Sep-03
CV 260
8.36
-23.68
4.27
22.58
5.29
D428
15-Sep-03
CV 261
8.60
-24.28
4.96
26.25
5.30
D428
15-Sep-03
CV 262
8.50
-24.00
3.10
15.19
4.89
D428
15-Sep-03
CV 263
8.39
-23.28
4.21
21.21
5.04
D428
15-Sep-03
CV 264
8.46
-23.59
3.76
19.54
5.20
D428
15-Sep-03
CV 265
8.74
-23.86
3.01
14.78
4.92
D428
11-Aug-03
CV 266
8.28
-23.91
4.58
23.76
5.19
D428
11-Aug-03
CV 267
7.82
-24.11
5.22
25.43
4.87
D428
11-Aug-03
CV 268
8.00
-24.30
3.85
21.19
5.51
D428
11-Aug-03
CV 269
8.38
-24.31
3.40
18.91
5.55
D428
11-Aug-03
CV 270
8.75
-24.14
5.67
32.16
5.67
D428
11-Aug-03
CV 271
8.22
-24.62
5.47
31.78
5.81
D428
11-Aug-03
CV 272
8.53
-24.14
5.53
30.28
5.48
D428
11-Aug-03
CV 273
8.12
-24.51
4.12
25.06
6.09
D428
11-Aug-03
CV 274
8.18
-23.68
4.62
24.60
5.33
D428
11-Aug-03
CV 275
8.50
-24.35
6.02
35.57
5.91
D428
22-Oct-03
CV 276
8.85
-22.95
2.59
13.85
5.35
D428
22-Oct-03
CV 277
8.79
-23.26
3.95
22.84
5.78
D428
22-Oct-03
CV 278
8.48
-23.31
4.24
22.05
5.20
D428
22-Oct-03
CV 279
8.34
-22.84
5.89
28.41
4.83
D428
22-Oct-03
CV 280
8.13
-22.80
6.49
30.94
4.77
D428
22-Oct-03
CV 281
8.62
-22.76
3.35
16.47
4.91
D428
22-Oct-03
CV 282
8.12
-23.10
3.74
20.86
5.58
D428
22-Oct-03
CV 283
7.95
-22.85
4.72
26.09
5.53
D428
22-Oct-03
CV 284
8.27
-22.86
5.45
26.94
4.94
D428
22-Oct-03
CV 285
8.09
-23.22
3.69
19.30
5.23
Site
Collection
Date
Label
8,5N
8”C
umol N
umol C
C:N
I SPOM
D428
3-Dec-02
SPOM 21
3.88
-21.34
2.38
23.80
10.01
D428
3-Dec-02
SPOM 22
3.16
-19.45
2.16
23.23
10.76
D428
16-Dec-02
SPOM 23
2.64
-17.87
1.96
19.76
10.10
D428
16-Dec-02
SPOM 24
3.44
-17.80
1.60
17.00
10.62
D428
14-Jan-03
SPOM 25
2.39
-19.33
1.69
15.68
9.27
D428
14-Jan-03
SPOM 26
2.34
-19.65
1.59
14.53
9.16
D428
26-Jan-03
SPOM 27
2.75
-18.84
1.24
12.31
9.94
D428
26-Jan-03
SPOM 28
2.86
-19.43
1.20
11.56
9.65
D428
10-Mar-03
SPOM 29
0.58
-22.93
1.32
13.55
10.24

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csjcvjCNjT-T-CNjoooT-^ooo^CTíoDaiCTjaicrjcxj^^Z
I C\| 05 CM CO CO
LO CO C\Í CD
T- CM (N T-
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cococococococooococococococo
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OCOCDO)lOTtCDCOT-05lOOOCOLOh-C»CMCOCDCOCOCD05
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CMlOTfT-CDCO-»-05(DCMCOT-COCONCMO)r^O)h>-COCOCOCM
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cocdcdoidodoi^^cvicNico^dódddoiódscD
YYYT^CMCMeMTj-CNjCMCMCMCMCMCgCjJCMCMCMTj-CMCMY-pj-
CMO-«tCON-T-lOlOO>-»-COCOCOOOCMTj-COlOO>COCMCMT-
TtCOOJr^OJCOCOCMCDpCDpCMTj-CDCMCqpiqCMCMOOlO
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L512 14-Oct-03 SP0M71 4.55 -18.06 2.34 26.14 11.17
L512 14-Oct-03 SPOM72 3.37 -18.11 1.91 21.24 11.12
L512 21-NOV-03 SPOM73 3.41 -20.85 1.38 14.60 10.55
L512 21-NOV-03 SPOM74 5.88 -21.55 1.53 15.29 10.02

APPENDIX B
SUPPLEMENTAL SIZE AND WEIGHT DATA OF CLAMS
Table B-l. Size (mm) and Weight (g) Data of Clams.
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(9)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
D428
14-Jan-03
ME691
21.3
19.8
11.00
13.54
0.44
0.06
D428
14-Jan-03
ME692
15.9
15.3
7.6
13.42
0.2
0.03
D428
14-Jan-03
ME693
14.5
13.2
6.8
13.17
0.06
0.01
D428
14-Jan-03
ME694
13.5
12.5
6.5
13.32
0.12
0.02
D428
14-Jan-03
ME695
18.2
16.5
8.8
13.37
0.28
0.03
D428
14-Jan-03
ME696
15.9
14.6
7.9
13.4
0.17
0.02
D428
14-Jan-03
ME697
17.7
16.1
9.2
13.55
0.29
0.03
D428
14-Jan-03
ME698
13.7
12.2
7.4
13.36
0.12
0.01
D428
14-Jan-03
ME699
21.1
19.5
10.6
13.56
0.44
0.06
D428
14-Jan-03
ME700
15.1
14.1
8.3
13.33
0.14
0.02
D428
14-Jan-03
ME701
16.4
15.8
8.9
13.45
0.21
0.03
D428
14-Jan-03
ME702
17.3
16.1
8.7
13.38
0.25
0.03
D428
14-Jan-03
ME703
13.2
12.2
6.3
13.33
0.07
0.01
D428
14-Jan-03
ME704
21.4
19.2
11
13.56
0.51
0.07
D428
14-Jan-03
ME705
19.2
16.8
9.5
13.57
0.34
0.05
D428
14-Jan-03
ME706
16.1
15.5
8.7
13.26
0.15
0.02
D428
14-Jan-03
ME707
19.1
16.5
8.9
13.5
0.28
0.04
D428
14-Jan-03
ME708
13.4
12.2
6.7
13.16
0.1
0.01
D428
14-Jan-03
ME709
14
12.5
7.1
13.17
0.1
0.01
D428
14-Jan-03
ME710
23.3
21.6
12
14.07
0.79
0.11
D428
14-Jan-03
ME711
17.5
15.7
8.8
13.5
0.25
0.03
D428
14-Jan-03
ME712
19.2
17.3
9.7
13.43
0.34
0.05
D428
14-Jan-03
ME713
16.4
14.8
8
13.32
0.25
0.04
D428
14-Jan-03
ME714
13.7
12.9
7.5
13.36
0.13
0.02
D428
14-Jan-03
ME715
14.6
13.6
7.8
13.18
0.14
0.02
D428
14-Jan-03
ME716
16.9
15.3
8.4
13.38
0.21
0.02
D428
14-Jan-03
ME717
13.9
12.6
7
13.35
0.12
0.01
D428
14-Jan-03
ME718
14.5
13.7
7.4
13.36
0.15
0.02
D428
14-Jan-03
ME719
19.4
17.2
9.5
13.47
0.26
0.04
D428
14-Jan-03
ME720
13.4
12.1
6.9
13.3
0.1
0.02
L512
2-Feb-03
ME721
18.7
17.2
10.1
13.59
0.33
0.04
133

134
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(a)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
L512
2-Feb-03
ME722
16.1
14.3
9.4
13.47
0.25
0.03
L512
2-Feb-03
ME725
21
18.9
10.6
13.48
0.42
0.07
L512
2-Feb-03
ME726
19.9
17.2
9.9
13.52
0.3
0.04
L512
2-Feb-03
ME727
21.6
19.7
11.5
13.86
0.61
0.09
L512
2-Feb-03
ME728
15.1
13.9
7.8
13.19
0.17
0.03
L512
2-Feb-03
ME729
21.1
19.1
11
13.68
0.45
0.07
L512
2-Feb-03
ME730
17.1
15.7
8.6
13.37
0.28
0.04
L512
2-Feb-03
ME731
28.5
25.4
14.3
14.21
1.24
0.19
L512
2-Feb-03
ME732
26.5
24.2
13.8
13.9
1
0.15
L512
2-Feb-03
ME733
20.3
18
10.1
13.46
0.53
0.09
L512
2-Feb-03
ME734
16.7
13.7
7.9
13.15
0.19
0.03
L512
2-Feb-03
ME735
29.2
24.4
13.9
13.93
0.99
0.14
L512
2-Feb-03
ME736
15.7
14.4
7.7
13.16
0.18
0.02
L512
2-Feb-03
ME737
20.3
18.3
10.1
13.45
0.46
0.07
L512
2-Feb-03
ME738
23.1
20
11.7
13.53
0.56
0.08
L512
2-Feb-03
ME739
17.7
16.3
9.2
13.25
0.31
0.04
L512
2-Feb-03
ME740
22.5
20.4
11.1
13.46
0.51
0.08
L512
2-Feb-03
ME741
19.7
18.1
10
13.39
0.48
0.08
L512
2-Feb-03
ME742
24.3
21
12.1
13.63
0.68
0.11
L512
2-Feb-03
ME743
22.5
20.1
10.8
13.53
0.58
0.08
L512
2-Feb-03
ME744
15.9
14.1
8
13.15
0.2
0.03
L512
2-Feb-03
ME745
18.5
16.8
9.2
13.29
0.34
0.06
L512
2-Feb-03
ME746
23.8
21.9
12
13.73
0.81
0.12
L512
2-Feb-03
ME747
13.8
12.5
7
13.07
0.16
0.03
L512
2-Feb-03
ME748
19.8
17
10.1
13.46
0.45
0.06
L512
2-Feb-03
ME749
26.2
23.5
13.7
13.84
0.84
0.13
L512
2-Feb-03
ME750
15.2
13.5
8
13.22
0.19
0.03
L512
20-Feb-03
ME451
23.8
22
ND
13.99
0.9
0.15
L512
20-Feb-03
ME452
21.5
19.2
ND
13.96
0.72
0.12
L512
20-Feb-03
ME453
20.3
18.3
ND
13.72
0.56
0.1
L512
20-Feb-03
ME454
21
18.3
ND
13.85
0.62
0.1
L512
20-Feb-03
ME455
17
15.4
ND
13.41
0.3
0.06
L512
20-Feb-03
ME456
14.4
13.7
ND
13.24
0.21
0.03
L512
20-Feb-03
ME457
19.9
17.8
ND
13.73
0.53
0.1
L512
20-Feb-03
ME458
24.5
21.5
ND
14.07
0.99
0.17
L512
20-Feb-03
ME459
17.6
16.5
ND
13.7
0.49
0.08
L512
20-Feb-03
ME460
16.8
16
ND
13.51
0.45
0.09
L512
20-Feb-03
ME461
22.1
20
ND
14.01
0.8
0.14
L512
20-Feb-03
ME462
17.7
16.1
ND
13.6
0.39
0.07
L512
20-Feb-03
ME463
18.9
16.7
ND
13.68
0.46
0.08
L512
20-Feb-03
ME464
15.1
13.7
ND
13.39
0.29
0.04
L512
20-Feb-03
ME465
22.8
20.8
ND
13.9
0.85
0.14
L512
20-Feb-03
ME466
15.6
14.1
ND
13.48
0.28
0.05
L512
20-Feb-03
ME467
18
15.7
ND
13.5
0.42
0.07
L512
20-Feb-03
ME468
17.2
16.2
ND
13.51
0.45
0.08

135
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(g)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
L512
20-Feb-03
ME470
23.2
21.9
ND
14.01
0.79
0.14
L512
20-Feb-03
ME471
12.1
10.8
ND
13.22
0.13
0.03
L512
20-Feb-03
ME472
17
16.2
ND
13.63
0.38
0.08
L512
20-Feb-03
ME473
17.2
16.4
ND
13.49
0.39
0.07
L512
20-Feb-03
ME474
20.1
17.5
ND
13.64
0.55
0.09
L512
20-Feb-03
ME475
19.1
17
ND
13.54
0.45
0.08
L512
20-Feb-03
ME476
16
14.1
ND
13.55
0.3
0.06
L512
20-Feb-03
ME477
19
17.5
ND
13.6
0.44
0.07
L512
20-Feb-03
ME478
13.7
12.9
ND
13.42
0.19
0.03
L512
20-Feb-03
ME479
17.2
15.6
ND
13.39
0.3
0.04
L512
20-Feb-03
ME480
15.9
14.3
ND
13.45
0.25
0.04
D428
10-Mar-03
ME863
25.8
23.3
12.8
13.64
0.71
0.09
D428
10-Mar-03
ME864
19.5
17.2
9.4
13.26
0.3
0.05
D428
10-Mar-03
ME865
28.6
25.5
15.3
13.96
1.04
0.15
D428
10-Mar-03
ME866
18.3
17.1
9.2
13.25
0.3
0.04
D428
10-Mar-03
ME867
24.9
21.8
12
13.7
0.68
0.09
D428
10-Mar-03
ME868
32.2
29.2
16.4
14.31
1.32
0.17
D428
10-Mar-03
ME869
23.2
21
11.6
13.62
0.66
0.1
D428
10-Mar-03
ME870
18.2
16.3
8.8
13.18
0.26
0.04
D428
10-Mar-03
ME871
15.8
14.8
8.4
13.15
0.2
0.02
D428
10-Mar-03
ME872
23.8
21.2
10.9
13.59
0.6
0.08
D428
10-Mar-03
ME873
21.2
18.6
10.3
13.34
0.36
0.05
D428
10-Mar-03
ME874
27.9
24.8
14
13.99
0.95
0.13
D428
10-Mar-03
ME875
25.7
23.2
12.2
13.59
0.64
0.09
D428
10-Mar-03
ME876
19.3
17.6
9.6
13.25
0.31
0.05
D428
10-Mar-03
ME877
20.1
18.3
9.7
13.28
0.37
0.05
D428
10-Mar-03
ME878
18.9
17.4
9.7
13.12
0.26
0.03
D428
10-Mar-03
ME879
27.8
24.9
13.7
13.86
0.9
0.12
D428
10-Mar-03
ME880
19.2
18.1
10.2
13.17
0.32
0.04
D428
10-Mar-03
ME881
27.6
25.1
15
13.66
0.8
0.12
D428
10-Mar-03
ME882
24.8
21.9
12
13.58
0.63
0.08
D428
10-Mar-03
ME883
16.8
16
8.4
13.19
0.21
0.03
D428
10-Mar-03
ME884
21.9
19.9
11.3
13.37
0.39
0.06
D428
10-Mar-03
ME885
24.7
22.1
11.8
13.51
0.6
0.08
D428
10-Mar-03
ME886
18.6
17.7
9.3
13.28
0.34
0.04
D428
10-Mar-03
ME887
21.5
18.7
10.6
13.23
0.4
0.05
D428
10-Mar-03
ME888
17.6
15.9
9.3
13.21
0.22
0.03
D428
10-Mar-03
ME889
25.5
22.4
12.6
13.66
0.7
0.1
D428
10-Mar-03
ME890
17.8
16.1
8.4
13.24
0.21
0.03
D428
10-Mar-03
ME891
18.9
17
8.9
13.28
0.28
0.04
D428
10-Mar-03
ME892
13.3
11.5
7.1
13.07
0.09
0.01
L512
25-Mar-03
ME541
29.3
24.5
14.4
14.36
1.29
0.16
L512
25-Mar-03
ME542
25.8
23.4
12.4
14.05
0.82
0.09
L512
25-Mar-03
ME543
27.1
24.5
15.4
14.21
0.99
0.14

136
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT.w/
VIAL
(9)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(g)
L512
25-Mar-03
ME545
25.2
22.4
13.5
13.7
0.67
0.09
L512
25-Mar-03
ME546
31.3
28.2
16.2
14.85
1.65
0.24
L512
25-Mar-03
ME547
19.8
17.1
9.7
13.47
0.32
0.04
L512
25-Mar-03
ME548
28.2
24.9
14.2
14.3
1.11
0.16
L512
25-Mar-03
ME549
25.4
22.8
12.7
13.91
0.81
0.1
L512
25-Mar-03
ME550
22.4
20
11.7
13.53
0.48
0.07
L512
25-Mar-03
ME551
22.7
20
11.7
13.68
0.48
0.08
L512
25-Mar-03
ME552
26
22.9
12.1
13.96
0.86
0.11
L512
25-Mar-03
ME553
28.7
25.4
14.3
14.35
1.15
0.16
L512
25-Mar-03
ME554
27.5
24
12.6
14.02
0.95
0.13
L512
25-Mar-03
ME555
26.7
23.4
13.6
13.89
0.81
0.11
L512
25-Mar-03
ME556
21.2
19.2
11
13.55
0.43
0.06
L512
25-Mar-03
ME557
32.3
27.4
16.1
14.77
1.6
0.23
L512
25-Mar-03
ME558
20
17.9
10.6
13.54
0.41
0.05
L512
25-Mar-03
ME559
25.7
23
13.7
14.11
0.89
0.14
L512
25-Mar-03
ME560
22.5
21.4
11.7
13.67
0.45
0.06
L512
25-Mar-03
ME561
27.5
24.6
13.7
14.16
0.98
0.13
L512
25-Mar-03
ME562
21
18.6
10.7
13.5
0.42
0.05
L512
25-Mar-03
ME563
23.9
21.6
12.9
13.82
0.59
0.07
L512
25-Mar-03
ME564
27.9
25.2
14.5
14.14
0.94
0.11
L512
25-Mar-03
ME565
28
24.5
15
14.24
1.1
0.15
L512
25-Mar-03
ME566
28.6
25.6
14.1
14.12
1.02
0.14
L512
25-Mar-03
ME567
19.8
17.9
10.5
13.46
0.35
0.05
L512
25-Mar-03
ME568
20.7
18.6
10.1
13.5
0.34
0.06
L512
25-Mar-03
ME569
25.1
22.5
12.1
13.78
0.71
0.09
L512
25-Mar-03
ME570
22.3
20.5
10.8
13.66
0.46
0.07
L512
6-May-03
ME835
19.1
17.7
10.5
13.25
0.36
0.07
L512
6-May-03
ME836
23.5
21.5
12.7
13.58
0.66
0.11
L512
6-May-03
ME837
16.1
14.8
7.9
13.28
0.26
0.05
L512
6-May-03
ME838
30
27.5
15.9
14.27
1.28
0.22
L512
6-May-03
ME839
32.6
28.8
16.3
14.48
1.54
0.25
L512
6-May-03
ME840
32.1
29
16.3
14.5
1.51
0.22
L512
6-May-03
ME841
31.3
27.2
15.6
14.53
1.59
0.23
L512
6-May-03
ME842
27.9
25.4
14.6
14.08
1.1
0.18
L512
6-May-03
ME843
26.9
24
13.9
13.8
0.88
0.14
L512
6-May-03
ME844
28.4
25.9
14.3
14.05
1.06
0.16
L512
6-May-03
ME845
20.9
19.4
11
13.32
0.39
0.05
L512
6-May-03
ME846
29
26
14.5
14.08
1.15
0.18
L512
6-May-03
ME847
21.3
20
11.1
13.34
0.37
0.07
L512
6-May-03
ME848
30
27.2
16.1
14.34
1.38
0.21
L512
6-May-03
ME849
32.2
28.4
16.2
14.51
1.6
0.25
L512
6-May-03
ME850
23.5
21.5
12.5
13.58
0.65
0.1
L512
6-May-03
ME851
27.2
23.8
13.9
13.83
0.92
0.15
L512
6-May-03
ME852
31.4
27.5
16.5
14.36
1.44
0.24
L512
6-May-03
ME853
23.5
21.1
12.1
13.5
0.59
0.09

137
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(g)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
L512
6-May-03
ME855
24
21.5
12.8
13.58
0.67
0.11
L512
6-May-03
ME856
31.4
28.2
16
14.33
1.4
0.24
L512
6-May-03
ME857
23
21
12
13.48
0.56
0.1
L512
6-May-03
ME858
19.3
17.8
9.7
13.29
0.28
0.05
L512
6-May-03
ME859
19.2
18.2
10.6
13.31
0.38
0.06
L512
6-May-03
ME860
23.7
21.4
13.1
13.69
0.67
0.11
L512
6-May-03
ME861
19.8
18.4
11.1
13.29
0.33
0.06
L512
6-May-03
ME862
16.1
14.6
9.4
13.22
0.23
0.04
L512
9-Jun-03
ME751
31.9
27.8
16.7
14.89
1.73
0.25
L512
9-Jun-03
ME752
24.5
22
12.6
13.95
0.73
0.14
L512
9-Jun-03
ME753
28.2
25.5
15.1
14.39
1.24
0.18
L512
9-Jun-03
ME754
30.4
27.8
16.4
14.65
1.52
0.22
L512
9-Jun-03
ME755
22.6
20.3
12.5
13.78
0.64
0.09
L512
9-Jun-03
ME756
34.2
29
17.3
15.3
2.06
0.28
L512
9-Jun-03
ME757
31.8
28.2
17.1
14.6
1.42
0.22
L512
9-Jun-03
ME758
22
20.3
12
13.74
0.61
0.1
L512
9-Jun-03
ME759
35.7
31.9
18.5
15.71
2.56
0.38
L512
9-Jun-03
ME760
24.5
22.1
13.1
13.87
0.65
0.09
L512
9-Jun-03
ME761
38
34.7
19.6
16.12
2.9
0.4
L512
9-Jun-03
ME762
26.9
24.2
14.4
14.07
0.92
0.13
L512
9-Jun-03
ME763
31.5
27.4
16.5
14.63
1.4
0.2
L512
9-Jun-03
ME764
32.3
28.2
16.9
14.77
1.61
0.24
L512
9-Jun-03
ME765
28.7
25.9
16.1
14.53
1.35
0.2
L512
9-Jun-03
ME766
26.1
24
14
14.02
0.84
0.12
L512
9-Jun-03
ME767
28.9
25.9
15.2
14.53
1.32
0.2
L512
9-Jun-03
ME768
30.5
27.5
15.9
14.66
1.49
0.24
L512
9-Jun-03
ME769
25.6
23.5
14.3
13.99
0.86
0.13
L512
9-Jun-03
ME770
24.7
22.7
13.5
13.95
0.76
0.11
L512
9-Jun-03
ME771
25
23.7
14.1
14.07
0.85
0.12
L512
9-Jun-03
ME772
27.3
23.9
15
14.14
0.99
0.15
L512
9-Jun-03
ME773
25.6
23.1
13.6
13.94
0.77
0.12
L512
9-Jun-03
ME774
35.9
31.6
18.4
15.39
2.23
0.34
L512
9-Jun-03
ME775
20.4
19.4
11.8
13.61
0.41
0.07
L512
9-Jun-03
ME776
28.5
25.2
15.2
14.26
1.06
0.17
L512
9-Jun-03
ME777
24.6
21.9
12.6
13.91
0.71
0.11
L512
9-Jun-03
ME778
21.6
20.3
11.6
13.86
0.63
0.09
L512
9-Jun-03
ME779
24.9
22.8
13.7
13.93
0.81
0.12
L512
9-Jun-03
ME780
24.9
22.4
12.9
13.95
0.79
0.12
L512
7-Jul-03
ME806
41.6
35.4
22.4
16.96
3.76
0.44
L512
7-Jul-03
ME807
24
21.5
12.7
13.87
0.63
0.09
L512
7-Jul-03
ME808
24.6
22.7
13.8
13.77
0.84
0.12
L512
7-Jul-03
ME809
29.3
25.4
15.5
14.08
1.09
0.14
L512
7-Jul-03
ME810
26.8
24.1
14.5
13.74
0.82
0.13
L512
7-Jul-03
ME811
29.1
25.9
15
14.12
1.22
0.16

138
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(9)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
L512
7-Jul-03
ME813
26.1
23.4
14
13.74
0.79
0.12
L512
7-Jul-03
ME814
24.6
21.9
13.3
13.55
0.62
0.09
L512
7-Jul-03
ME815
41.1
34.9
19.9
15.72
2.81
0.33
L512
7-Jul-03
ME816
37.7
33.7
21
15.72
2.81
0.38
L512
7-Jul-03
ME817
31.4
30
17.2
14.63
1.67
0.23
L512
7-Jul-03
ME818
34
30.8
17.6
14.65
1.7
0.22
L512
7-Jul-03
ME819
25.7
23.7
14.1
13.73
0.78
0.12
L512
7-Jul-03
ME820
36.1
33.3
20.8
15.45
2.52
0.32
L512
7-Jul-03
ME821
34.9
30.4
18.2
15.12
2.18
0.26
L512
7-Jul-03
ME822
38.4
33.8
19.3
15.62
2.61
0.32
L512
7-Jul-03
ME823
26.2
23.7
14.3
13.81
0.89
0.12
L512
7-Jul-03
ME824
28.9
26
15.9
14.1
1.14
0.15
L512
7-Jul-03
ME825
30.3
27.5
16.9
14.35
1.36
0.2
L512
7-Jul-03
ME826
23.1
21.2
12.6
13.43
0.48
0.07
L512
7-Jul-03
ME827
26.8
23.8
15
13.76
0.85
0.15
L512
7-Jul-03
ME828
24.9
23.1
13.7
13.81
0.83
0.12
L512
7-Jul-03
ME829
33.6
29.9
16.6
14.81
1.88
0.24
L512
7-Jul-03
ME830
35.8
32
18.6
14.92
1.9
0.26
L512
7-Jul-03
ME831
27
25.4
14.8
13.97
0.97
0.16
L512
7-Jul-03
ME832
25.1
22.2
14.4
13.78
0.86
0.13
L512
7-Jul-03
ME833
24.3
21.9
13.1
13.65
0.67
0.1
L512
7-Jul-03
ME834
24.8
22.4
13.2
13.73
0.76
0.1
L512
5-Aug-03
ME781
35.1
31.1
18.2
15.24
2.07
0.3
L512
5-Aug-03
ME782
29.8
26.5
15.8
14.29
1.13
0.14
L512
5-Aug-03
ME783
27.1
24
14.1
14.11
0.92
0.15
L512
5-Aug-03
ME784
37.1
33
19.5
15.38
2.19
0.32
L512
5-Aug-03
ME785
27.1
24.1
14.4
14
0.8
0.12
L512
5-Aug-03
ME786
30.2
27.5
15.9
14.49
1.24
0.17
L512
5-Aug-03
ME787
28
25.9
15.2
14.17
1.03
0.16
L512
5-Aug-03
ME788
29
25.9
14.1
14.15
0.98
0.12
L512
5-Aug-03
ME789
29.9
27.2
17.1
14.47
1.36
0.2
L512
5-Aug-03
ME790
34.6
30.9
18.5
15.2
1.94
0.27
L512
5-Aug-03
ME791
39.5
33.1
19.8
15.83
2.65
0.33
L512
5-Aug-03
ME792
22.8
21
12.8
13.81
0.63
0.12
L512
5-Aug-03
ME793
36.5
31.6
19.2
15.22
1.98
0.28
L512
5-Aug-03
ME794
38.8
33.8
19.9
15.79
2.62
0.34
L512
5-Aug-03
ME795
28.6
25.5
15.3
14.15
1.04
0.18
L512
5-Aug-03
ME796
36.8
31.6
19.3
15.32
2.15
0.35
L512
5-Aug-03
ME797
36
31
18.8
15.15
2
0.32
L512
5-Aug-03
ME798
32.8
29.6
18.4
15.03
1.88
0.27
L512
5-Aug-03
ME799
23.9
22.8
12.8
13.81
0.68
0.1
L512
5-Aug-03
ME800
18.4
16.4
9
13.45
0.27
0.04
L512
5-Aug-03
ME801
27.6
25.2
15.5
14.26
1.09
0.17
L512
5-Aug-03
ME802
37.5
33.3
20
15.32
2.17
0.28
L512
5-Aug-03
ME803
28.1
25.9
14.3
14.1
0.96
0.1

139
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. w/
VIAL
(g)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
L512
5-Aug-03
ME805
29.2
26.1
16.2
14.27
1.1
0.16
Note: ND = Not Determined

APPENDIX C
SUPPLEMENTAL SIZE AND WEIGHT DATA OF OYSTERS
Table C-l. Size (mm) and Weight (g) of Oysters.
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
D428
3-Dec-02
CV246
38.3
47.8
13.4
0.88
0.14
D428
3-Dec-02
CV247
25
35.3
12.6
0.51
0.1
D428
3-Dec-02
CV248
41
44
13.3
1.06
0.15
D428
3-Dec-02
CV249
30.2
38.4
17.5
0.76
0.11
D428
3-Dec-02
CV250
31.6
35.6
14.1
0.45
0.06
D428
3-Dec-02
CV251
38.3
52.7
19.2
1.41
0.22
D428
3-Dec-02
CV252
38.6
56.3
16
1.46
0.22
D428
3-Dec-02
CV253
46.2
63.6
20.6
2.43
0.3
D428
3-Dec-02
CV254
38.8
60.7
17.3
1.58
0.23
D428
3-Dec-02
CV255
33.7
64.4
18.3
1.93
0.27
L512
15-Dec-02
CV131
30
36.5
ND
0.8658
ND
L512
15-Dec-02
CV132
34.8
38.2
ND
1.543
ND
L512
15-Dec-02
CV133
37.1
47.9
ND
2.4126
ND
L512
15-Dec-02
CV134
39.5
49
ND
2.7801
ND
L512
15-Dec-02
CV135
33.1
52.2
ND
2.2793
ND
D428
16-Dec-02
CV071
29.1
36.4
11.5
0.9717
ND
D428
16-Dec-02
CV072
28.7
39.6
13.5
1.3554
ND
D428
16-Dec-02
CV073
30.9
41.8
16.3
2.1324
ND
D428
16-Dec-02
CV074
33.7
47.1
12
2.0085
ND
D428
16-Dec-02
CV075
34
51.1
14.4
2.5504
ND
D428
16-Dec-02
CV076
33.9
52.3
15
2.936
ND
D428
16-Dec-02
CV077
28.8
63.6
19.3
3.7176
ND
D428
16-Dec-02
CV078
41.2
61.8
17.6
4.0128
ND
D428
16-Dec-02
CV079
48.4
59.3
19.7
4.2879
ND
D428
16-Dec-02
CV080
41
53.8
16.1
4.2461
ND
L512
8-Jan-03
CV146
38.9
40.6
13.6
1.48
ND
L512
8-Jan-03
CV147
45.3
51.8
19.1
4.64
ND
D428
26-Jan-03
CV217
36.4
73.4
15.6
1.57
0.23
140

141
SITE
DATE
INDIVIDUAL
NO.
SHELL
LENGTH
(mm)
SHELL
HEIGHT
(mm)
SHELL
WIDTH
(mm)
SOFT
BODY
WT. (g)
DRY
BODY
WT.
(9)
D428
26-Jan-03
CV218
55.6
76.5
21.8
4.01
0.57
D428
26-Jan-03
CV220
40.5
55.9
16.1
1.2
0.15
D428
26-Jan-03
CV221
49
68.5
18.5
2.06
0.24
D428
26-Jan-03
CV222
39.2
61.5
16.3
1.2
0.17
D428
26-Jan-03
CV223
37
40.5
13.2
0.75
0.1
D428
26-Jan-03
CV224
37.1
44.2
12.2
0.42
0.05
D428
26-Jan-03
CV225
38.6
46
15.9
0.75
0.12
D428
26-Jan-03
CV226
41.4
48.7
17
1.31
0.21
L512
2-Feb-03
CV158
40.7
46.2
15.4
1.98
ND
L512
2-Feb-03
CV159
37
45.8
17.2
3.2
ND
L512
2-Feb-03
CV160
48.5
51.6
15.4
3.7
ND
L512
2-Feb-03
CV161
50.6
52.8
16.2
4.32
ND
L512
2-Feb-03
CV162
44.3
59.4
22
5.78
ND
L512
2-Feb-03
CV163
47.7
63.7
21.1
5.4
ND
L512
2-Feb-03
CV164
49.1
66
21.2
6.82
ND
L512
2-Feb-03
CV165
51
71.1
21.1
8.18
ND
L512
2-Feb-03
CV166
53.9
66.6
21.4
6.71
ND
L512
2-Feb-03
CV167
44.5
66.5
23.3
6.71
ND
L512
20-Feb-03
CV198
56.8
64.8
21
3.86
0.63
L512
20-Feb-03
CV199
61.4
73.5
20.6
4.87
0.94
L512
20-Feb-03
CV200
69.5
59.9
21.7
3.98
0.89
L512
20-Feb-03
CV201
56.6
59.1
17.5
2.76
0.63
L512
20-Feb-03
CV202
57.8
64.3
25.5
5.38
1.09
L512
20-Feb-03
CV203
37.7
45.4
12.5
1.06
0.18
L512
20-Feb-03
CV204
47.9
57.9
18.4
2.83
0.6
L512
20-Feb-03
CV205
58.7
62
23.8
3.76
0.69
L512
20-Feb-03
CV206
43.7
62.9
19.7
3.39
0.69
L512
25-Mar-03
CV207
38.1
56.3
16.6
3.33
0.44
L512
25-Mar-03
CV208
59.6
66.3
19.5
4.14
0.6
L512
25-Mar-03
CV209
53.8
60.2
20.4
3.32
0.57
L512
25-Mar-03
CV210
34.5
42.4
16.7
0.79
0.1
L512
25-Mar-03
CV211
53.7
70.7
20.9
4.52
0.51
L512
25-Mar-03
CV212
58.8
67.1
24.4
5.09
0.76
L512
25-Mar-03
CV213
61.9
61.7
26.1
4.4
0.68
L512
25-Mar-03
CV214
52.1
60.8
22.4
3.1
0.48
L512
25-Mar-03
CV215
43.2
51.4
18
1.76
0.24
L512
25-Mar-03
CV216
59.1
76.3
26.2
5.03
0.89
D428
10-Mar-03
CV236
36.8
56
15.63
1.25
0.17
D428
10-Mar-03
CV237
43
47.2
18.7
0.68
0.09
D428
10-Mar-03
CV238
39.6
51.5
19
1.21
0.15
D428
10-Mar-03
CV239
27.8
39.6
10.4
0.16
0.02
D428
10-Mar-03
CV240
43.6
55.4
16.4
1.15
0.16

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BIOGRAPHICAL SKETCH
Emily Rubé Hall was bom in Cooperstown, New York, in 1976. She was raised in
Sarasota, Florida, since the age of five. In 1995, she graduated from high school and
started her college career at Mercer University in Macon, Georgia, where she was a
member of the women’s varsity soccer team and a member of Chi Omega sorority. She
graduated cum laude in 1999 earning a Bachelor of Science in environmental science and
a Bachelor of Arts in Spanish.
Emily is a 2001 graduate of the University of Florida, Department of
Environmental Engineering Sciences, where she received a Master of Science. In 2001
she began her career as a doctoral student at the same university. Her degree includes a
wetlands certificate and a hydrological sciences certificate. She received the Outstanding
Graduate Student Award from the American Chemical Society in 2004 and she received
a Women’s Club fellowship in 2004.
158

I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a
dissertation for the degree of Doctor of Philosophy
Jpáéph J. Demho, Chairma
Professor of Environmental Engineering
Sciences
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a
dissertation for the degree of Doctor of Philosophy.
Thomas K. Frazer,
Associate Professor of Fisheries and Aquatic
Sciences
, Cochair
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a
dissertation for the degree of Doctor of Philosophy.
Jean-Claude Bonzongo /
Assistant Professor of Environmental
Engineering Sciences
I certify that I have read this study and that in my opinion it conforms to acceptable
standards of scholarly presentation and is fully adequate, in scope and quality, as a
dissertation for the degree of Doctor of Philosophy.
Mark Brenner
Associate Professor of Geological Sciences

This dissertation was submitted to the Graduate Faculty of the College of
Engineering and to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
December 2004 1 AAvw^ nir*-.
Pramod P. Khargonekar
Dean, College of Engineering
Kenneth Gerhardt
Interim Dean, Graduate School

UNIVERSITY OF FLORIDA
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3 1262 08556 6254