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Phosphorus Flux from the Sediments in the Kissimmee Chain of Lakes

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PHOSPHORUS FLUX FROM THE SEDIMENTS IN THE KISSIMMEE CHAIN OF LAKES By CHAKESHA S. MARTIN A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2004

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Copyright 2004 by Chakesha S. Martin

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This thesis is dedicated to my parents and br others. I thank them all for their continued patience, love, and support.

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iv ACKNOWLEDGMENTS I would like to especially thank my comm ittee chair, Dr. John R. White, for giving me the opportunity to study under him and learn so much from his wisdom and guidance. AN additional thanks go to my committee me mbers, Dr. Jana Newman and Dr. K.R. Reddy, for their support and encouragement. I appreciate Matt Fisher’s expertise in th e field and for creating the maps used for this project. I am grateful for Dr. Marco Belmont’s help in the field, as well as Paul Washington. Special thanks go to Ms. Yu Wang for her guidance in the laboratory. I would also like to especially thank Alicia Callery for her invalu able assistance with experiments. This project would not have been possible without funding from the South Florida Water Management District. I really appreciate all the encouragement I have received from my fellow graduate students, professors and friends. Special thanks go to my family for being so instrumental in shaping the person I am toda y. Above all, I would like to thank God, who without, none of this would have been achievable.

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v TABLE OF CONTENTS page ACKNOWLEDGMENTS.................................................................................................iv LIST OF TABLES............................................................................................................vii LIST OF FIGURES..........................................................................................................xii ABSTRACT....................................................................................................................... xv CHAPTER 1 INTRODUCTION........................................................................................................1 Study Rationale.............................................................................................................6 Objectives..................................................................................................................... 8 Site Description............................................................................................................8 2 SEDIMENT CHARACTERIZATION.......................................................................13 Introduction.................................................................................................................13 Hypothesis..................................................................................................................16 Objective.....................................................................................................................1 6 Field Methods.............................................................................................................16 Laboratory Techniques...............................................................................................21 Physical and Chemical........................................................................................21 Inorganic P Fractionation....................................................................................23 Data Analysis..............................................................................................................25 Results........................................................................................................................ .26 Physical and Chemical........................................................................................26 Metals..................................................................................................................27 Inorganic P Fractionation....................................................................................28 Discussion...................................................................................................................33 Physical and Chemical........................................................................................33 Metals..................................................................................................................39 Inorganic P Fractionation....................................................................................45 Conclusion..................................................................................................................49

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vi 3 PHOSPHORUS FLUX OF SEDIMENTS UNDER DIFFERENT SIMULATED LOADING CONDITIONS.........................................................................................51 Introduction.................................................................................................................51 Hypothesis...........................................................................................................54 Objectives............................................................................................................54 Site Selection.......................................................................................................54 Materials and Methods...............................................................................................60 Data Analysis..............................................................................................................61 Results........................................................................................................................ .61 Discussion...................................................................................................................83 Overall Conclusion.....................................................................................................94 APPENDIX A PHOSPHORUS FRACTIONATION DATA.............................................................98 B METALS DATA......................................................................................................101 C NUTRIENTS............................................................................................................103 D AEROBIC WATER COLUMN SRP DATA...........................................................106 E PRELIMINARY SURVEY......................................................................................116 F SEDIMENT TYPE AND COORDINATES............................................................126 LIST OF REFERENCES.................................................................................................129 BIOGRAPHICAL SKETCH...........................................................................................135

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vii LIST OF TABLES Table page 2-1 Average Bulk Density (BD), Loss on Ignition (LOI), Total C, Total N, and Total P for Lakes Tohopekaliga, Cypress, Ha tchineha, Kissimmee, and Istokpoga. n=10 per lake............................................................................................................27 2-2 HCl extractable Ca and Mg concentra tions and oxalae extr actable Fe and Al concentrations for Lakes Tohopekaliga Istokpoga, Cypress, Kissimmee, and Hatchineha. Values are reported as mean and standard deviation (n=10) per lake.28 2-3 Mean and standard deviations for P forms: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P (n=10) for each lake in mg kg-1 for all P forms.........................................................................................................................3 2 2-4 Mean and standard deviations for P fo rms for sand sediments: bulk density (BD), mass loss on ignition (LOI), total car bon (TC), total nitr ogen (TN), total phosphorus (TP) per lake in mg kg-1 for all P forms................................................34 2-5 Mean and standard deviations for P fo rms for mud sediments: bulk density (BD), mass loss on ignition (LOI), total car bon (TC), total nitr ogen (TN), total phosphorus (TP) per lake in mg kg-1 for all P forms................................................35 2-6 Pearson correlations for se lected metals and total P................................................40 2-7 Mean and standard deviations for P fo rms for sand sediments: HCl-Ca and Mg and Oxalate Fe and Al mg kg-1 for all lakes.............................................................41 2-8 Mean and standard deviations for P fo rms for mud sediments: HCl-Ca and Mg and Oxalate Fe and Al mg kg-1 for all lakes.............................................................41 2-9 Mean and standard deviations for P fo rms for sand sediments: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, tota l Po and total P per lake in mg kg-1 for all P forms.....................................................................................................................47 2-10 Mean and standard deviations for P fo rms for mud sediments: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P ............................................47 3-1. X and Y coordinates of each station. All coordinates are Un iversal Mercator, North American Datum 1983, Units meters, UTM Zone 17...................................59

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viii 3-2. Percent change in Water Column SRP (mg L-1) under no P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicates a decrease in SRP concentration while a positive (+) percen t change indicates an increase in SRP concentrations. n=6 for all lakes except Cypress in which n=4.......................63 3-3 Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at no P additions at 2, 7, and 25 days. n=6 for all lakes except Cypress (n=4)............................................................................63 3-4 Sediment characteristics of all stations for each lake for bulk density, mass loss on ignition (LOI), and total C, N, and P (mg kg-1). N=10........................................64 3-5 Sediment characteristics of all stations for each lake for oxalate-Fe and Al and HCl-Ca and Mg. n=10..............................................................................................65 3-6 Correlation between sediment propertie s with the Pearson correlation on top and the P-value on the bottom in parenthese s. All correlations are significant to P<0.05. n=10............................................................................................................67 3-7 Correlation between P flux and EPCw with sediment properties with the Pearson correlation on top and the P-value on the bot tom in parentheses. All correlations are significant to P<0.05. n=10................................................................................68 3-8 Percent change in SRP mg L-1 at 15 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) indicat es a decrease in SRP concentration while a positive (+) percent change indicat es an increase in SRP concentrations. n=6 for all lakes except Cypress in which n=5........................................................70 3-9 Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 15 ug L-1 P additions at 2, 7, and 25 days. n=6 for all lakes except Lake Cypress n=5..............................................................72 3-10 Percent change in SRP mg L-1 at 30 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) ch ange indicate a decrease in SRP concentration while a positive (+) percent change indicate an increase in SRP concentrations. n=6 .................................................................................................74 3-11 Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 30 ug L-1 P additions at 2, 7, and 25 days......................................................................................................................76 3-12 Percent change in SRP mg L-1 at 60 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) ch ange indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP concentrations. n=6..................................................................................................78 3-13 Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 60 ug L-1 P additions at 2, 7, and 25 days..80

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ix 3-14 Percent change in SRP mg L-1 at 120 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) ch ange indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP concentrations. n=6..................................................................................................82 3-15 Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 120 ug L-1 P additions at 2, 7, and 25 days......................................................................................................................83 3-16 Ranges of sediment-water SRP fluxes (mg m-2 d-1).................................................86 3-17 Correlation between Porewater Equilbrato rs (Peepers) and P flux rate with the Pearson correlation on top and the P-valu e on the bottom in parentheses. All correlations are signif icant to P<0.05. n=10............................................................87 3-18 Equilibrium Water Column Phosphorus Concentrations (EPCw) values determined at two stations in each lake Water column concentrations below these concentrations indicate conditions favorable for release of P n=3.................88 A-1 Characterization of inorganic P forms (mg kg-1) in Tohopekaliga, Cypress, and Hatchineha raw data for sand sediments..................................................................98 A-2 Characterization of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga raw data for sand sediments.....................................................................................99 A-3 Characterization of inorganic P (mg kg-1) forms in Tohopekaliga, Cypress and Hatchineha raw data for mud sediments..................................................................99 A-4 Characterization of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga raw data for mud sediments...................................................................................100 B-1 Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha raw data for sand sediments...................................................................................101 B-2 Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for sand sediments........................................................................................................101 B-3 Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha raw data for mud sediments..........................................................................................102 B-4 Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for mud sediments........................................................................................................102 C-1 Characterization of nutrients (mg kg-1) in Tohopekaliga, Cypress, and Hatchineha raw data for sand sediments................................................................103 C-2 Characterization of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data for sand sediments........................................................................................................104

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x C-3 Characterization of nutrients (mg kg-1) in Tohopekaliga, Cypress and Hatchineha raw data for mud sediments................................................................104 C-4 Characterization of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data for mud sediments..................................................................................................105 D-1 Water Column SRP for Lake Tohope kaliga under aerobic conditions for 25 days for station T10 (Coordinate x (4 61809 meters), y (3116800 meters). All coordinates are Universal Mercator, No rth American Datum 1983, Units meters, UTM Zone 17.........................................................................................................106 D-2 Water Column SRP for Lake Tohope kaliga under aerobic conditions for 25 days for station T2. (Coordinate x (460252 meters), y (31258 25 meters). All coordinates are Universal Mercator, No rth American Datum 1983, Units meters, UTM Zone 17.........................................................................................................107 D-3 Water Column SRP for Cypress Lake under aerobic conditions for 25 days for station C16. Coordinate x (46987 5 meters), y (3106370 meters). All coordinates are Universal Mercator, No rth American Datum 1983, Units meters, UTM Zone 17.........................................................................................................108 D-4 Water Column SRP for Cypress Lake under aerobic conditions for 25 days for station C15. Coordinate x (46826 1 meters), y (3105828 meters). All coordinates are Universal Mercator, No rth American Datum 1983, Units meters, UTM Zone 17.........................................................................................................109 D-5 Water Column SRP for Lake Hatchine ha under aerobic conditions for 25 days for station H107. Coordinate x (4613 41 meters), y (3098421 meters). All coordinates are Universal Mercator, No rth American Datum 1983, Units meters, UTM Zone 17.........................................................................................................110 D-6 Water Column SRP for Lake Hatchine ha under aerobic conditions for 25 days for station H103. Coordinate x (4580 82 meters), y (3100650 meters). All coordinates are Universal Mercator North American Datum 1983, Units meters, UTM Zone 17............................................................................................111 D-7 Water Column SRP for Lake Kissimm ee under aerobic conditions for 25 days for station K1004. Coordinate x (47 2394 meters), y (308417 9 meters). All coordinates are Universal Mercator North American Datum 1983, Units meters, UTM Zone 17............................................................................................112 D-8 Water Column SRP for Lake Kissimm ee under aerobic conditions for 25 days for station K1012. Coordinate x (47 3188 meters), y (308842 6 meters). All coordinates are Universal Mercator North American Datum 1983, Units meters, UTM Zone 17............................................................................................113

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xi D-9 Water Column SRP for Lake Istokpoga under aerobic conditions for 25 days for station I10007. Coordinate x (47 2779 meters), y (302691 5 meters). All coordinates are Universal Mercator North American Datum 1983, Units meters, UTM Zone 17............................................................................................114 D-10 Water Column SRP for Lake Istokpoga under aerobic conditions for 25 days for station I10004. Coordinate x (46 9916 meters), y (303075 0 meters). All coordinates are Universal Mercator North American Datum 1983, Units meters, UTM Zone 17............................................................................................115 E-1 Coordinates (x and y), water depth, se diment depth and thickness for Cypress Lake. Units Meters. All coordinates ar e Universal Transverse Mercator, North American Datum 1983, UTM Zone 17..................................................................121 E-2 Coordinates (x and y), water depth, sediment depth and thickness for Lake Hatchineha. Units Meters. All coordina tes are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17........................................................122 E-3 Coordinates (x and y), water depth, sediment depth and thickness for Lake Istopokga. Units Meters. All coordinate s are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17........................................................123 E-4 Coordinates (x and y), water depth, sediment depth and thickness for Lake Kissimmee. Units Meters. All coordina tes are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17........................................................124 E-5 Coordinates (x and y), water depth, sediment depth and thickness for Lake Tohopekaliga. Units Meters. All coor dinates are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17.......................................125 F-1 Coordinates (x and y) and sediment type for stations chosen to sample for Lake Tohopekaliga and Cypress Lake. n=10. All coordinates are Universal Transverse Mercator, North American Datum 1983, units meters, UTM zone 17..................126 F-2 Coordinates (x and y) and sediment type for stations chosen to sample for Lake Hatchineha and Kissimmee Lake. n=10. All coordinates are Universal Transverse Mercator, North Amer ican Datum 1983, units meters, UTM zone 17.........................................................................................................127 F-3 Coordinates (x and y) and sediment type for stations chosen to sample for Lake Istokpoga Lake. n=10. All coordinates ar e Universal Transverse Mercator, North American Datum 1983, units meters, UTM zone........................................128

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xii LIST OF FIGURES Figure page 1-1 Location of Lake Istokpoga and Uppe r Chain of Lakes in relation to Lake Okeechobee................................................................................................................7 1-2 The percent of landuse by county area for Osceola and Highlands for which the lakes are located. The total acres for Osceola and Highlands are 620,016 and 487,207, respectively..................................................................................................9 1-3 Historical TP levels (mg L-1) for Kissimmee upper chain of lakes (personal communication with SFWMD)................................................................................12 2-1 Sampling stations for Lake Tohopekaliga................................................................17 2-2 Sampling stations for Cypress Lake.........................................................................18 2-3 Sampling stations for Lake Hatchineha...................................................................19 2-4 Sampling stations for Lake Kissimmee....................................................................20 2-5 Sampling stations for Lake Istokpoga......................................................................21 2-6 Inorganic P fractionation sc heme after Reddy et al. 1998.......................................25 2-7 Amount of metals, HCl-Mg, HCl-Ca, Oxalate-Fe, and Oxalate Al, in mg kg-1 for all lakes...............................................................................................................29 2-8 Distribution of P forms in La kes Tohopekaliga and Hatchineha.............................31 2-9 Distribution of P forms in Lakes Cypress and Kissimmee......................................32 2-10 Regression between concen trations of total C (g kg-1) to loss on ignition (%). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................35 2-11 Regression between concen trations of total N (g kg-1) to loss on ignition (%). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................36

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xiii 2-12 Regression between concen trations of total P (g kg-1) to loss on ignition (%). The mud sediments values are lo cated at top graph and the sand sediments are located at the bottom graph...................................................................................................37 2-13 Regression between concen trations of total P (mg kg-1)and with total C (g kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................38 2-14 Regression between concen trations of total P (mg kg-1) and with total N (g kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................39 2-15 Regression between concentr ations of oxalate-Al (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................42 2-16 Regression between concentr ations of oxalate-Fe (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................43 2-17 Regression between concen trations of HCl-Ca (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................44 2-18 Regression between concen trations of HCl-Mg (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph......................................................................................45 2-19 The mean percent of mean TP (mg kg-1) of each P fractions (KCl-Pi, NaOH-Pi, HCl-Pi, NaOH-Po, and Residue P) for bot h mud and sand sediments for all the lakes.......................................................................................................................... 48 3-1 Location of sampling stations for Lake Tohopekaliga.............................................55 3-2 Location of sampling st ation for Cypress Lake.......................................................56 3-3 Location of sampling stati ons for Lake Hatchineha.................................................57 3-4 Location of sampling sta tions for Lake Kissimmee.................................................58 3-5 Location of sampling sta tions for Lake Istokpoga...................................................59 3-6 Phosphorus retention by sediments from station T2 of Lake Tohopekaliga at 60 ug L-1 P additions.....................................................................................................77 3-7 Phosphorus retention by sediments from station I10007 of Lake Istokpoga at 120 ug L-1 P additions..............................................................................................81

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xiv 3-8 Water Column SRP (mg L-1) versus spike concentration ug L-1 for each lake at day 2, 7, and 25........................................................................................................84 3-9 Release/retention of P related to water column concentration for Lake Tohopekaliga-stations-T10 (top) and T2 (bottom)...................................................89 3-10 Release/retention of P re lated to water column concentration for Lake Cypressstation C16 (top) and C15 (bottom).........................................................................90 3-11 Release/retention of P related to water column concentration for Lake Hatchineha-station H107 (t op) and H103 (bottom).................................................91 3-12 Release/retention of P related to water column concentration for Lake Kissimmee-stations K1004 (t op) and K1012 (bottom)............................................92 3-13 Release/retention of P re lated to water column conc entration for Lake Istokpogastation 10007 (top) and 10004 (bottom)...................................................................93 E-1 Sediment thickness map for Cypress Lake............................................................116 E-2 Sediment thickness map for Lake Hatchineha.......................................................117 E-3 Sediment thickness map for Lake Istokpoga..........................................................118 E-4 Sediment thickness map for Lake Kissimmee.......................................................119 E-5 Sediment thickness map for Lake Tohopekaliga...................................................120

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xv Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science PHOSPHORUS FLUX FROM THE SEDIMENTS IN THE KISSIMMEE CHAIN OF LAKES By Chakesha S. Martin May 2004 Chair: John R. White Major Department: Soil and Water Science Phosphorus (P) coming from wastewater tr eatment plants and runoff from urban and agricultural areas have impacted water qua lity in many Florida lakes over the last few decades. The continual input of P into la kes can lead to poor water quality, which can result in massive fish kills and harm to humans and animals through drinking water. Bottom sediments also control the trophic status of a lake, even after the external load has been reduced. The P flux study examined the response of lake sediments to changes in water column SRP concentrations in 5 contri butory lakes of Lake Okeechobee in Florida. The objectives of this study were to char acterize the pools of i norganic and organic P, determine the SRP flux rates using intact sediment cores, and determine the equilibrium water column P concentration (EPCw) of the sediment. Sediments were collected from 10 stati ons per lakes for the P characterization study. Sediment samples were collected from the top 10 cm and analyzed for moisture

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xvi content, bulk density, mass loss on ignition (LOI ), HCl extractable Ca and Mg, oxalate Fe and Al, inorganic and organic P fracti ons, as well as total C, N, P. Intact cores were taken from two stations per lake and 15 cores pe r station (total of 150 cores) to determine the SRP flux rate fo r a range of mud and sand sediments and to calculate the EPCw. Five water column concen trations (0, 15. 30, 60, 120 ug L-1) were added once and evaluated in tr iplicate for the SRP flux rate measurements and incubated in the dark under aerobic conditions for 25 days. The sediment P characterization revealed that the mud sediments contained greater amounts of organic matter, total C, N, and P, as well as Ca, Mg, Fe, and Al. Total P concentrations ranged from 38 to 1812 mg kg-1 for the sediments. There was a strong positive correlation found between TP and organic matter (R2=0.94), suggesting that P is a consistent portion in the orga nic fraction. Most of the inor ganic P was associated with the Fe/Al portion. The total organic P frac tion was the greatest ove rall pool, suggesting that the TP coming into the lakes may be associated with organic matter. The aerobic SRP flux rates suggest that P release was highest at ambient water column SRP (6 4 ug L-1) and decreased with an increase in P loading. However, an increase in P loading also maintained high water column SRP concentrations. Flux rates results indicate that sediments in 4 of the 5 lakes are releasing P to the water column at ambient water column SRP concentrations and retaining P at higher concentrations. The EPCw showed that 2 of the 5 lakes have a lo w potential for release of SRP from the sediments as the water column SRP concentratio ns decrease over time. Results from this study will assist water managers in determini ng the internal load of P during efforts to reduce P export to downstream Lake Okeechobee.

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1 CHAPTER 1 INTRODUCTION For years there have been concerns about the impact of excess nutrients (phosphorus (P), nitrogen (N) and carbon (C)) entering lakes from wa stewater treatment plants and runoff from urban and agricultural areas on dete riorations to surface water quality (Carpenter et al. 1998, Sharpley et al. 1999). Phosphorus, N, and C are all macronutrients essential for growth of organi sms but P is often c onsidered one of the most limiting nutrients in freshwater system s (i.e., lakes, and rivers) throughout the world. Phosphorus is documented as a major source influencing phytoplankton mass in freshwater and is generall y derived from controllable point sources (Marsden 1989). However, for N and C there are difficulties in controlling the exchange of N and C between the atmosphere and the water and th e fixation of atmospheric N by some bluegreen algae (Sharpley et al. 1999). Alternativ ely, as salinity increas es, as in estuarine systems, N is sometimes considered the lim iting nutrient controlli ng aquatic productivity (Sharpley et al. 1999). In Florida, there is a particular concern in water quality because of surface water eutrophication from excess P coming from ex ternal sources (i.e., wastewater treatment plants, agriculture, and urban sources). Eutroph ication can be described as an increase in the fertility status of natural waters that cause accelerated growth of algae as well as aquatic weeds (Pierzynski et al. 2000). The growth of undesirable algae and weeds that later die off and decompose cause oxygen deplet ion that can result in massive fish kills and harm to humans and animals through dr inking water (Backer 2002, Carpenter et al.

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2 1998). A few examples of degrading water syst ems due to continual external inputs of P are Loosdrecht lakes (Netherlands); Skaha Lake (British Columb ia), Lake Okeechobee, Florida (USA); and the Everglades (U SA) (Keizer and Sinke 1992, Nordin 1983, Reddy et al 1995, White and Reddy 1999). Phosphorus Forms Phosphorus enters the surface water of lake s in both organic and inorganic forms and can be in either soluble or insoluble form s. Phosphorus can be classified into four forms: i). soluble reactive P (SRP); ii) dissolv ed organic P; iii) particulate inorganic P; and particulate organic P (Re ddy et al. 1999). Soluble reac tive P is the form most available for plants and microbe s. The other three forms must be transformed into the bioavailable form through decomposition pr ocesses regulated by enzymatic hydrolysis. Phosphorus Cycling Inorganic P enters primarily in the form of orthophosphate (PO4 3-) and can enter the water column of a lake by four pathways: i) settling of insoluble (particulate) inorganic and organic P, ii) uptake of soluble reactive P (SRP) by prim ary producers (algae) and its subsequent settling, iii) sorption of soluble inorganic or organi c P onto particles that settle onto the sediments, and iv) sorption of sol uble inorganic and organic P directly onto sediment particles (Reddy et al 1999). Sediments act as a net sink of P; however, when porewater P concentrations exceed the overlyi ng water column concentration, SRP can be released from the sediment to the water (Moor e et al. 1991). The exchange of P between the sedi ment and water column may depend on processes such as i) diffusion and advection (wind/wave action, fl ow, and bioturbation), ii) processes within the water column (bio tic uptake and release, mineralization, and

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3 sorption by particulate matter), iii) diagen etic processes (miner alization, sorption, precipitation, and dissolution) in botto m sediments, iv) redox conditions (oxygen content), v). organic matter content, vi) pH, vii) temperature, and viii) the presence of metals bound to P (Bostrom and Petterss on 1982, Holdren and Armstrong 1980, Moore et al. 1991, Wetzel 2001). Inorganic P is most associated with crystalline or amorphous compounds such as iron (Fe), aluminum (A l), calcium (Ca) and magnesium (Mg). Organic P is mostly associated with und ecomposed residues, microbes, and organic matter (Sharpley et al. 1999). Phosphorus Retention Mechanisms Understanding the forms and properties of P in lake sediments are important to identify factors that control P release from the sediment to the overlying water column. Inorganic P is usually found as i) labile or loosely sorbed P, ii) Al and Fe bound P; and iii) Ca and Mg bound P (Reddy et al. 1995). The mo st available form of P is labile P or exchangeable P, which is essential for plant growth. The slowly av ailable form of P is associated with Fe/Al, Ca/Mg, and labile or ganic compounds. The very slowly available P is associated with discrete mineral form s of Fe, Al, and Ca, and highly decomposed organic matter. Metals (Fe, Al, Ca, and Mg) play a importa nt role in inorganic P retention. The ability of P to be retained by Fe/Al and Ca/Mg compounds depend on pH and/ or redox conditions of the sediments (Patrick and Kh alid 1974). Phosphorus is retained by Fe/Al compounds under acidic conditions and is more stable under low pH conditions. The reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous iron (Fe2+) compound can lead to P released from the sediments (P atrick and Khalid 1974). When there is a

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4 dominance of Ca/Mg P in the sediments, P is more stable under high pH or alkaline conditions (Patrick and Khalid 1974). Or ganic acids from settling or deposited decomposing organic matter can lower pH shor t term and lead to dissolution of Ca bound P (Marsden 1989). Phosphorus External Load Reduction Over the years, improvements in water quality have focused on external phosphorus load reductions. The response of a lake after external load reductions depends on the recycling of phosphorus from the sediment to water column (Marsden 1989). Some studies have shown that reduci ng the external P loading can significantly improve water quality in lakes (Smith and Shapiro 1981). However, other studies have shown that a reduction in external P load does not always result in a decrease in TP in the water column of a lake due to high intern al sediment P load (Marsden 1989, Nordin 1983, Welch and Cooke 1995). The idea of intern al loading is based on the recycling of nutrients from bottom sediment in lakes to th e overlying water column (Carpenter 1983). After load reductions, the intern al load of sediments will dete rmine the trophic status of a lake and the amount of lag time for recovery (Petterson 1998). Many studies have investigated the di ffusive release of phosphorus from the sediments measured from intact sediment cores in the laboratory (Fisher and Reddy 2001, Petterson and Bostrom 1985). Phosphorus re lease rates are stimulated by low redox potential (Istvanovics 1988, Marsden 1989, Mortimer 1941) and high temperature (Holdren and Armstrong 1980, Kamp-Nielsen 1974). In shallow lakes, sediments resuspension can be important for internal loading (Reddy et al 1996, Welch and Cooke 1995). The mobilization of this internal P lo ad in the sediment is determined by the

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5 forms of P in the sediment (Keizer and Si nke 1992). Sediments characterized with a dominance of iron (Fe) associated P can release P under low redox, as well as high pH conditions (Petterson and Bostrom 1985). In other instances, sediments characterized by a dominance of calcium (Ca) may release P under low pH conditions (Marsden 1989). In eutrophic lakes, macrophyt e species with high annual bi omass turnover can be a potential internal source of nut rients to the overlying water column (Carpenter 1983). In oligotrophic lakes biomass turnover and the bi omass of macrophytes are not as large and there may not be a great release of P to the water column from the senescenes of macrophytes. Macrophytes release phosphorus as well as other nutrients from living shoots, but most of the phosphorus released occurs after the shoot dies and decays (Carpenter 1983). The decay of macrophytes at the sediment surface lowers the oxygen concentration and redox potential which can caus e a flux of P from the sediment to water column of a lake (Carpenter 1983). One ma nagement suggestion to reduce the flux of P is to spray with herbicides ; however, this may not be an effective control method (Carpenter 1983). Harvesting macrophytes may be a more effective in removing nutrients and reducing internal nutrient loads because it re moves the nutrients from the system. The equilibrium phosphorus concentration (EPC) can be used to determine the extent to which the internal load will be released during restorat ion of a lake after external load reductions. The EPC is defined as the P in solution that is in equilibrium with the P in the solid phase or the point wher e P is neither being re tained nor released from the sediment to the water column (O lila and Reddy 1993). At water column SRP

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6 concentration above the EPC, P is retained by the sediments, and at concentrations below, the sediments serve as P source. Study Rationale Lake Okeechobee, a large (1800 km2), shallow (mean depth ~2.7 m) eutrophic lake, located in south Florida, has been impact ed by nutrient loads from point and nonpoint sources of pollution for over 30 years (Haven s 1997; Havens and Walker 2002; Reddy et al. 1995). Lake Okeechobee serves as a prim ary source of water for surrounding cities, recharge water for the South Florida aquifer, source of irrigation water for agriculture, source of habitat for wildlife, and as a s ource of recreational a nd commercial fishing (Havens and James 1997). Since the early 1970’s to present, the total phosphorus concentrations in Lake Okeechobee have more than doubled from around 50 ug L-1 to 100 ug L-1 (Havens 1997). Lake Okeechobee, located in south Florida is a large (1800 km2), shallow (mean depth ~ 2.7 m) eutrophic lake Recognizing the need for restoration of water quality in Lake Okeechobee, Florida, the Florida Legislature in 1987 adopted the Surface Water Improvement and Management (SWIM) Act (sections 373.451 to 373.4595 FL statues) that states that the South Florida Water Management District (SFWMD) must create and implement a program to protect the quality of water in Lake Okeechobee (Havens and James 1997). The SWIM Act also mandated a P loading target for Lake Okeechobee. In 1998, the Florida Department of Envi ronmental Protection (FDEP) submitted Lake Okeechobee on a list of impaired wate rs to the United States Environmental Protection Agency (USEPA) (Havens and Walker 2002). In 2000 FDEP began the process of developing a TMDL for Lake Okeechobee. The TMDL goal to Lake

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7 Okeechobee is established at 198 metric tons of TP and the in-lake P concentration is 40 ug L-1 within the pelagic region. Phosphorus load to Lake Okeechobee from water discharging from the Kissimmee upper chain of lakes have increased in phos phorus over the last five years from 23-91 metric tons (personal comm unication with SFWMD). Thus, quantifying P load from these major contributory lakes (Tohopekalig a, Cypress, Hatchineha, Kissimmee, and Istokpoga) is vital for Lake Okeechobee’s rest oration (Figure 1-1). This study fulfills parts of the requirements of the Lake Okeechobee Protection Act (Chapter 373.4595), which required an assessment of P sources from the Kissimmee upper chain of lakes and their contribution to the qua lity of water in Lake Ok eechobee (Walker and Haven 2002). Figure 1-1. Location of Lake Istokpoga and Upper Chain of Lakes in relation to Lake Okeechobee.

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8 In considering factors affecting water qua lity in the upper chain of lakes and P export to downstream Lake Okeechobee, several questions arose, including: i) What are the physical and chemical characteristics of su rface sediments, with particular emphasis on the forms of P and compounds that can affect P sorption or release? ii) What is the current contribution of phosphorus (internal lo ading) from the sediments to the water column of these lakes? iii) What are the Equilibrium Phosphorus Concentrations of the sediments in these lakes? These questions fo cus on whether P is being stored in organic or inorganic forms, the relati ve availability of P forms, and the extent to which the internal load will be released as extern al P loads decline and the water column P concentrations are reduced. Objectives The objectives of this study were to i) characterize and quantify the forms of inorganic P and organic P in the sediment, ii) determine the P flux rate from the sediment to the water column and iii) determine the equilibrium P concentration of the sediment. Site Description Lakes Tohopekaliga (98.4 km2) Cypress (22 km2), Hatchineha (71.6 km2), Kissimmee (179 km2) and Istokpoga (112 km2) are shallow, eutrophic lakes located in the Upper Kissimmee River Basin (Walker and Havens et al. 2002; Williams 2001). The mean depths are 2.6, 1.9, 2.1, 3.4, and 2.7 m respectively for Lakes Tohopekaliga, Cypress, Hatchineha, Kissimmee, and Istokpoga (Havens et al. 2000, Walker and Havens 2002). The surface water pH ranges from 6-8, and secci depth ranges from 0.6-1.2 m for all lakes (Havens et al. 2 000, Walker and Haven 2002). The entire Kissimmee River

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9 Basin (KRB) comprises 3,013 square miles; how ever, the upper basin covers 1600 square miles (USACE 1996) Lake Tohopekaliga is at the headwaters of the KRB, proximal to Walt Disney World, and about 25 km south of the city of Orlando and Kissimmee (James et al. 1992). These hydrological connected lakes in Centra l Florida flow throughout the counties of Osceola and Highlands in a heavily populated and intensively developed part of the watershed (Figure 1-2). The lakes are located in an area that is the hub of the cattle industry in central Florida, St. Cloud, and Haines City (USACE 1996). Citrus farming, tourism and sod farming, as well as the cattle industry are economic bases for the surrounding communities. Citrus industry dom inates north of Lake Cypress and sod farming is prevalent within the Kissimmee Upper Basin. 0 50000 100000 150000 200000 250000 300000A gri c ulture Urban Wetlands Fore st s Rangeland Barren Wate rLanduseAcres Osceola Highlands Figure 1-2. The percent of landuse by county area for Osceola and Highlands for which the lakes are located. The total acre s for Osceola and Highlands are 620,016 and 487,207, respectively. The lakes are used for recreation, irrigati on and flood control. There are less urban and residential development located around La kes Kissimmee, Cypress, and Hatchineha in comparison to Lake Tohopekaliga (Haven s et al. 2000, USACE 1996). Each of the

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10 five lakes receives flow contri butions from other water systems within the KRB: Lake Tohopekaliga (Shingles Creek and East Lake Tohopekaliga), Lake Cypress (Canoe Creek and Dead River), Lake Hatchineha (Reedy and Catfish Creek), Lake Kissimmee (Lake Tiger), and Lake Istokpoga (Josephine Cr eek and Arbuckle Creek) (Walker and Haven 2002, Williams 2001). Under natural conditions, prior to significan t alterations to the watershed, the lake stages fluctuated seasonally from about 0.63.1 m (2-10 ft) and stored water in the wet summer season overflowing into the marshes connected to each lake (USACE 1996). There were no hydrologic connections be tween the lakes during the dry season. Currently, lake levels are regulated a nd maintained by the South Florida Water Management District (SFWMD) through a series of water control structures and canals. Some nuisance or problem vegetation is hydrilla ( Hydrilla verticillate ), water hyacinth ( Pistia stratiotes ), water lettuce ( Eichhornia crassipes ) and the American lotus ( Nelumbo luteal ). The dominant vegetation in the littoral zone of the lakes includes vegetations such as willow ( Salix spp ), buttonbush ( Cephalanthus occidentalis ), topedo grass ( Panicum repens ), maidencane ( Panicum hemitomon ), sawgrass ( Claidium jamaicense ), cattail ( Typha spp .), and pickerel weed ( Pontederia cordata ), (USACE 1996). The lakes are surrounded by pine flat woods, dry and wet praires and cypress domes. The water quality in the lakes have b een affected by Waste Water Treatment Effluent (WWT) coming from four waste treat ment plants via canals and streams into Lake Tohopekaliga, since the late 1950’s (Williams 2001). The water discharged from Lake Tohopekaliga has contributed to the degr adation of water qual ity in the downstream

PAGE 27

11 lakes. The lakes have not only been aff ected by nutrients coming from wastewater treatment plants, but also pollution coming fr om agricultural and ur ban sources. Since the lake 1960’s, a few lake drawdowns, muck removal projects, and control of invasive plants by use of herbicide appl ications have been utilized as a way to restore water quality and habitat for endangered species within the Kissimmee upper chain of lakes (USACE 1996, Williams 2001). In the mid 1980 ’s the nutrients levels coming from wastewater treatment plants to Lake Tohopekaliga were diverted. In general, TP levels in the water co lumn of the Kissimmee upper chain of lakes have declined over time; since 1980’s (Figure 13). In reviewing past water quality data collected by the South Florida Water Manage ment District, since the 1980’s ( no water quality data available prior to 1980), the aver age TP concentrations were greater than 100 ug L-1 in Cypress, Tohopekaliga, and Hatchi neha; however, the concentrations were much lower in Kissimmee and Istokpoga at less than 50 ug L-1. In the 1990’s, the water column TP concentrations decreased to less than about 65 ug L-1 in Tohopekaliga, Cypress, and Hatchineha, but concentr ations nearly double to over 100 ug L-1 for Lake Kissimmee. The water column TP concentration for Istokpoga remained the same as in the 1980’s. Currently, the wate r column TP concentrations have remained relatively the same for most all lakes sin ce the 1990’s, except concentrations have nearly doubled in Istokpoga to 60 ug L-1 and concentrations have declin ed in Kissimmee from over 100 ug L-1 to 60 ug L-1. However, it should be noted that although water column TP concentrations have declined, in general, th e concentrations in the lakes are well above the in-lake P concentration goal of 40 ug L-1 in the pelagic region of Lake Okeechobee.

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12 0 20 40 60 80 100 120 140 160 180 200 80-8990-9900-03 YearsWater Column TP (ug L-1) Cypress Hatchineha Tohopekaliga Kissimmee Istokpoga Figure 1-3. Historical TP levels (mg L-1) for Kissimmee upper chain of lakes (personal communication with SFWMD). In efforts to restore water quality in the Kissimmee upper chain of lakes and reduce P effort to downstream Lake Okeechobee there have been efforts made to control water quality deteriorations co ming from nonpoint and point sources of pollution by implementing Best Management Practices (B MP’s). Some management practices to reduce the external load of P entering a lake include retention or infiltration areas, wet detention ponds, constructed wetlands, sand filt ers, and bio-retention areas. The main BMP’s are usually efficient fertilizers applicat ions (directed in some part to educating citizens), effective stormwater systems, and control of erosion and sediment.

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13 CHAPTER 2 SEDIMENT CHARACTERIZATION Introduction Over the years there have been concerns about the impact of excess P leaving urban and agricultural areas on water quality in many Florida lakes (i.e., Lake Apopka and Lake Okeechobee). Although, P is a limiti ng nutrient essential for plant growth, too much P can lead to eutrophic conditions, resul ting in harm to the quality of water within an aquatic system including declines in fi sh populations, changes in vegetation, and limitations to recreation (Carpenter et al. 1998). Chemical, phys ical, and microbial processes control the exchange of P between the sediment and water column. Thus, for restoration to occur in a lake it is important to understa nd the forms and properties of P in lake sediments to identify the factors that control P release from the sediment to the overlying water column. Phosphorus in soils and sediments exists in both organic and inorganic forms. External inputs of P from such entities as urban and agricultural sources and wastewater treatment plants can be in soluble or insoluble particulate forms. P can be classified into four forms: i) soluble reactive P (SRP) or di ssolved inorganic P; ii) dissolved organic P; (iii) particulate inorganic P; and (iv) particulate organic P (Reddy et al. 1999). Soluble reactive P is the form most available for plan ts and microbes. The other three forms must be transformed into the bioavailable form through decomposition processes regulated by enzymatic hydrolysis.

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14 Inorganic P primarily enters into lakes in the form of orthophosphate and can be transported to the sediments first by upta ke by phytoplankton (bio logical) and through subsequent settling of particulate inorga nic and organic P (Fau lkner and Richardson, 1989, Syers et al. 1973). The forms of inorga nic P which exist in sediments include the ions PO4 3-, HPO4 2and H2PO4 with the dominant form dependent on pH. Sediment in lake systems in Florida typically range from 6-8, with the HPO4 2and H2PO4 forms most dominant. Inorganic phosphorus is usually found as (i) labile or loosely absorbed P; ii) Al and Fe bound P; and (iii) Ca and Mg bound P (Reddy et al. 1995). The most available form of P is the labile P or exchangeable P. The slowly available P is associated with Fe/Al, Ca/Mg and labile organic compounds. Th e very slowly available P is associated with discrete mineral forms of Fe, Al, a nd Ca. and highly decomposed organic matter. Factors that regulate inorganic P rete ntion are pH, redox (Eh), organic matter content, calcium carbonate content, temperature, and am ounts of Fe, Al, Ca and Mg compounds. The ability of P to be retain ed by Fe/Al and Ca/Mg depends on the pH and/or redox conditions of the sediments (Patrick and Khalid 1974). Phosphorus is retained by Fe/Al compounds under acidic condi tions and is more stable under low pH conditions. The reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous iron (Fe2+) compound can lead to P released from th e sediment (Patrick and Khalid 1974). When there is a dominance of Ca/Mg P in the sediments, P is more stable under high pH or alkaline conditions (Patrick and Khalid 1974). Organic acids from settling or deposited decomposing organic matter can lower the pH short term and lead to dissolution of Ca bound P (Marsden 1989).

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15 Organic P is contained in undecomposed residues, microbes and organic matter (Sharpley 1999). The most common form of organic P is inositol phosphates, which are found as hexaphosphates (Ivanoff et al. 1998). Inositols are high molecular weight phosphates (up to 60% of total Po) that are the most stable or resistant to degradability; thus microbes do not readily have access to inositols (Anderson 1976, Ivanoff et al. 1998). Other forms of organic P compounds ar e phospholipids, nucleic acids, glucose-1phosphate, glycerophosphate, and phosphoprotei ns, which make up only 2% of total organic P (Ivanoff et al. 1998). Phospholipid s are commonly found in plant material and animal waste, or found through the process of microbial synthesis (Ivanoff et al. 1998). Since much of organic P is contained in sedime nt particles and organisms, it is not readily available to microbes and plants. Therefore, organic P must be transformed into the bioavailable form of pho sphorus (Wetzel 1999). Chemical fractionation schemes have been used to distinguish and quantify the various forms of P in sediments (Graetz and Nair 1999). There are several methods that have been developed to quantify the various forms of P; but, there is not a widely accepted method to measure organic P conten t (Change and Jackson 1957, Hieltjes and Lijklema 1980, Ruttenberg 1992). Organic P can be measured indirectly through inorganic P fractionation schemes. There have been criticisms of the se quential fractionation schemes. It is important to keep in mind that various chemical reagents only extrac t a pool of P related to a given chemical group. Therefore, it is critical that adequate tests of sequential extraction methods be calibrated (Ruttenberg 1992). Phosphorus extraction methods are often considered operationally defined and th erefore subject to broad interpretations

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16 (Graetz and Nair 1999). It can be difficult to compare data between researchers who use vastly different P fractionation methods thus complicating data in terpretation obtained among literary sources (Graetz and Nair 1999). Nevertheless, sequential fractionation schemes do provide a method of determining va rious pools of P in lake sediments. Hypothesis Recently accreted mud sediments will contain significantly higher P than the natural sand sediment bottom. Objective The objective of this study was to charac terize and quantify the forms of P in the sediments. Field Methods We performed a preliminary sediment survey of the lakes (August/2002) that provided information for selection of each samp ling station. A jet probe rod was used to determine where soft sediments were locat ed and how thick (Appendix E). During the initial survey, coordinates, water depth, se diment depth, and thickness were recorded (Appendix E). In addition, sediment type was recorded in which there were clean sand to organic muds for all lakes. After reviewing the preliminary sediment survey observations and measurements, 10 stations per lake were chosen to be sampled and were representative of the major sediment types in each lake (Figure 2-1 to Figure 2-5). Using GPS equipment, each station was located within +/5 m of the true coordinates and sediment type was reco rded (Appendix F). Dissolved oxygen and temperature measurements were taken at th ree depths: 30cm below the water surface, mid-depth, and 30 cm from the bottom using a YSI hand-held DO meter. In general, the dissolved oxygen levels were greater than 5 (mg L-1) in the top 30 cm and decrease with

PAGE 33

17 an increase in depth. The temperature measur e was relatively the same at all depth a mean of 29.9 1.21 for all lakes. Sediment samples (0-10cm) were collected from each site for analysis of various forms of P and a number of physical and chemi cal properties. Samples were extruded in the field using plexiglas t ubes and immediately sectione d immediately into 10 cm intervals. Immediately following sectioning, th e sediment samples were transferred to air tight pre-weighted glass jars, purged with nitrogen gas to maintain anaerobic conditions, and placed on ice. Samples were stored at 4C upon return to the laboratory until analysis. # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y1 2 3 4 5 6 7 8 9 10 N 02468Kilometers L. Tohopekaliga Figure 2-1. Sampling stations for Lake Tohopekaliga

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18 # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y11 12 13 14 15 16 17 18 19 20 N 01234Kilometers Cypress Lake Figure 2-2. Sampling sta tions for Cypress Lake.

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19 # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y101 102 103 104 105 106 107 108 109 110 N 01234Kilometers L. Hatchineha Figure 2-3. Sampling stati ons for Lake Hatchineha.

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20 # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y1001 1002 1003 1004 1005 1006 1009 1010 1011 1012 N 01234Kilometers L. Kissimmee Figure 2-4. Sampling sta tions for Lake Kissimmee

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21 # Y # Y # Y # Y # Y # Y # Y # Y # Y # Y10001 10002 10003 10004 10005 10006 10007 10008 10009 10010 01234Kilometers NL. Istokpoga Figure 2-5. Sampling stations for Lake Istokpoga. Laboratory Techniques Physical and Chemical All sediment sub-samples were measured for a number of physical and chemical properties: water content, bulk density, mass loss on ignition (LOI), and total C, N, and P. Percent moisture was determined after drying a known amount of moist sediment at 70C to a constant dry weight. Total C and N were determined on dried, ground sub-

PAGE 38

22 samples and analyzed on the Carlo-Er ba NA-1500 C-N-S Analyzer (Haak-Buchler Instruments, Saddlebrook, NJ) (White and Reddy 2000). For the measurement of sediment total P, 0.5 g dried ground sub-samples were weighed and placed in a muff le furnace initially at 250 C and increased to 550 C for 4 hours. The remaining ash was treated with 20 mL of 6 M HCl and placed on a hot plate at approximately 120 C (Anderson 1976). The samples were cooled and filtered through Whatman #41 filter paper. The total P concentrations were determined using an automated ascorbic acid colorimetric technique (Method 365.4, USEPA, 1993). The organic matter content was determined by LOI. Oven dried sub-samples were weighed out to approximately 0.5 g for analyses of total inorganic P using 25 mL of a 1 M HCl extraction on oven dried sediment (Reddy et al. 1998). The samples were shaken on a mechanical shaker for 3 hours and the supernatant was filtered with 0.45 um filter paper. Total inor ganic P concentrations were analyzed using an automated ascorbic acid colorimetric method (Method 365.4, USEPA, 1993). The same 1 M HCl extraction was analyzed for metals, which were Ca and Mg (Reddy et al. 1998). Sub-samples of approxi mately 0.25 g of dry ground sediment were weighed and treated with 20 mL of oxalate reagent. Samples were shaken in the dark for about 4 hours, centrifuged for 10 minutes, and filter through with 0.45 um filter paper. The oxalate extraction was used to determ ine the Fe and Al bound P, which is the reactive fraction of amorphous Fe-Al oxides. Metal analyses were determined by inductively coupled argon plasma sp ectrometry (model Spectro Ciros CCD, manufactured by Spectro AI, Inc, Fitch burg, MA). Analyses were determined using a

PAGE 39

23 modified version of EPA Method 200.7 (EPA 1983). Total organic P was calculated as the difference between total P and total inorganic P. Inorganic P Fractionation The fractions of inorganic P were dete rmined based on a scheme by Change and Jacksons 1957 in which acid and alkaline reagents were used to extract various pools of P in the soil. In this study, a modified vers ion of Change and Jacksons’ scheme by Reddy et al. 1998 was used to determine the various inorganic P fractions (F igure 2-6). It is important to keep in mind that various chemical reagents only extrac t a pool of P related to a given chemical group. The chem icals used in this study were 1.0 M potassium chloride (KCL), 0.1 M sodium hydroxide (NaOH), and 0.5 M 6.0 M hydrochloric acid (HCL) in which, (i) bioavailab le or loosely adsorbed Pi; ii) Pi associated with Fe and Al; and iii) Pi associated with Ca and Mg were ex tracted, respectively. The remaining sediment P was considered to be th e residual, recalcitrant organic P. For the KCl-Pi extraction, samples we re weighed out to a 0.5 g dry weight equivalent and placed in centrifugation tube s in an oxygen-free gloved box to maintain anaerobic conditions. Dissolved oxyge n readings were less than 0.10 mg L-1. Samples were placed in centrifuge tube s with caps outfitted with r ubber septa. Using a syringe needle, 25 mL of 1 M KCl were added. The samples we re placed on a mechanical shaker for 2 hours, followed by centrifugation at 6000 (reps per minute) rpm for 10 minutes. The supernantant of the solutions were f iltered through with 0.45 um Whatman filter paper under anaerobic conditions. Extracts were analyzed for soluble reactive phosphorus (SRP), using a Shimadzu UV160 visible spectrophotometer (Method 365.1, USEPA 1993).

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24 The residual sediment sample was treated with 25 mL of 0.1 M NaOH. Sediment suspensions were agitated on a mechanic al shaker, followed by centrifugation for 10 minutes. The supernatant solution were filt ered through with 0.45 um filter paper. For analysis of SRP (NaOH-Pi), concentrated sulfuric acid (H2SO4) was added to each solution. This portion is represented as th e Fe-Al bound P. The solutions were also analyzed for total phosphorus (NaOH-TP) by digestion with 11 N sulfuric acid (H2SO4) and potassium persulfate (K2S2O8) at 380 C. Extraction with 0.1 M NaOH also removed the P associated with humic and fulvic ac ids. The difference between NaOH-TP and NaOH-Pi is alkali extractable organic P ( NaOH-Po) associated with both fulvic and humic acids. The residual soils from the NaOH extr action were treated with 25 mL of 0.5 M HCl. Sediment solutions were shaken con tinuously for 24 hrs, followed by centrifugation for 10 minutes. The supernatants were filt ered through 0.45um filters Filtered solutions were analyzed for HCL-Ca-Mg bound P fraction. The residue from the 0.5 M HCL extraction was combusted at 550 C for 4 hours. Samples were filtered with Whatman #41 f ilter paper and the ash was dissolved in 6 M HCl. All supernatants, except the KCl extrac tions, were analyzed by using the automated ascorbic acid colorimetric method (EPA 365.1, 1993).

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25 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual Po[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP] Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual P[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent [SRP]NaOH-Po 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual Po[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP] Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual P[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent [SRP]NaOH-Po 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual Po[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent 0.5 M HCl[24 hrs] 1 M KCl[2 hrs] 0.1 M NaOH[17 hrs] Soil Residue Residue Residue Readily available Pi[SRP] [TP] Ca-Mg bound Pi[SRP] Fe-Al bound Pi [SRP] (acidified) Residual P[TP] Ashed@ 550C 6 M HCldigestion Wet samples weighed out to a 0.5 g dry weight equivalent [SRP]NaOH-Po Figure 2-6. Inorganic P fractiona tion scheme after Reddy et al. 1998. Data Analysis A variance check was conducted to test for normality. The data was not normal, so we transformed the data using two transforma tions (log and square root). However, the transformations were found not to be nor mal. A Wilcoxon/Kruskal-Wallis test was performed to compare the medians instead of the means using JMP Statistics, Version 4 (SAS Institute). Microsoft excel (Microsoft 2000) was used to performed any regression analyses and correlations.

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26 Results Physical and Chemical Several physical and chemical sediment properties were measured for each sample station including bulk density and or ganic matter. Bulk density ranged from 0.06-1.18 g cm-3, for all the lakes, with sediment texture varying from organic mud to sand. Lake Tohopekaliga had the highest average bulk density (0.83 0.31g cm-3) and Lake Kissimmee had the lowest (0.42 0.47 g cm-3) of all the lakes (Table 2-1). The loss on ignition (LOI), which estimates orga nic matter content, ranged from 0-55%. The higher percent values represent the greatest c ontent of organic matter in the sediment. Lake Kissimmee had the highest average LOI value (26.3 25.1%) and Lake Tohopekaliga had the lowest ( 3.2 3.6%). There were no significant differences found between the lakes for bulk density and LOI due to high standard deviations, an artifact of the different sediment types. Total analyses of macroelements were conducted for the sediments of each lake (Table 2-1). Total carbon values fo r the sediments ranged from 4-293 g kg-1 for all lakes, with an overall mean of 70.6 85.9g kg-1. The mean total C values were higher in Lake Kissimmee (124 121 g kg-1) and lowest in Lake Tohopekaliga (16.3 18.8 g kg-1). Total nitrogen values ranged from 0.32-26.5 g kg-1 with an overall mean of 6.4 7.98 g kg-1. The highest value of total N was in Lake Kissimmee (11.7 11.3 g kg-1) and the lowest was Lake Tohopekaliga (1.37 1.38 g kg-1). The total P values ranged from 38.1-1811 mg kg-1 with an overall mean of 468 557 mg kg-1. The highest total P levels were found in Lake Kissimmee (703 685 mg kg-1) and lowest levels were found in Lake Tohopekaliga (138 127 mg kg-1). There

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27 were no significant differences found between th e lakes for total C, N, and P due to high standard deviations, an artifact of the different sediment types. Table 2-1. Average Bulk Density (BD), Loss on Ignition (LOI), Total C, Total N, and Total P for Lakes Tohopekaliga, Cypr ess, Hatchineha, Kissimmee, and Istokpoga. n=10 per lake. Lake BD LOI Total C Total N Total P g cm-3 % g kg-1 g kg-1 mg kg-1 Tohopekaliga 0.83 0.31 3.2 3.6 16.3 18.8 1.37 1.38 138 127 Cypress 0.47 0.43 17.8 17.8 79.8 85.5 7.36 7.87 642 700 Hatchineha 0.51 0.47 17.8 18.6 51.8 83.7 7.8 8.1 581 594 Kissimmee 0.42 0.47 26.3 25.1 124 121 11.7 11.3 703 685 Istokpoga 0.63 0.44 10.7 12.6 51.8 61.9 3.88 4.63 276 297 Metals Sediments were analyzed fo r select metals using a 1 M HCl extraction to determine Calcium (Ca) and Magnesium (Mg) and an oxalate extraction was used to determine the iron (Fe) and aluminum (A l) concentrations (amorphous & poorlycrystalline). The range of Ca values was from 11585-12367 mg kg-1 with an overall mean of 3290 3601 mg kg-1 (Table 2-2). Lake Hatchine ha had the higher average Ca value (5090 5123 mg kg-1) while Lake Tohopekaliga had the lowest (912 918 mg kg1). There was no significant difference in Ca among the lakes, due to the high standard deviation, an artifact of different sediment types. The mean value of Mg was 549 731 and ranged from 0-2756 mg kg-1. Lake Hatchineha had the higher amount (936 1077 mg kg-1) and Lake Tohopekaliga was found to have the least amount of Mg (102 79 mg kg-1). There was no significant difference in Mg between the lakes. The mean Fe amount was 6409 8082 mg kg-1 ranging from 383-26473 mg kg-1. Lake Kissimmee had the highest mean value of Fe (11736 11003 mg kg-1) and Lake Tohopekaliga had the lowest (1515 1333 mg kg-1).

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28 The Fe concentration in Lake Tohopekalig a was significantly lower than in Lake Kissimmee ( P < .05). Aluminum ranged from 517-36135 mg kg-1 with a mean value of 8180 10541 mg kg-1. Lake Hatchineha had the highest amount of Al (12733 14068) mg kg-1) and Lake Tohopekaliga had the lowest (2578 3166 mg kg-1). There was no significant difference found for Al between the la kes. Overall, Al wa s higher in all lakes (8180 10541 mg kg-1) while Mg had the lowest c oncentration (549 731 mg kg-1) (Figure 2-7). Table 2-2. HCl extractable Ca and Mg concen trations and oxalae ex tractable Fe and Al concentrations for Lakes Tohopekaliga Istokpoga, Cypress, Kissimmee, and Hatchineha. Values are reported as m ean and standard deviation (n=10) per lake. Lake Ca Mg Fe Al mg kg-1 mg kg-1 mg kg-1 mg kg-1 Tohopekaliga 912 918 102 79 1515 1333 2578 3166 Cypress 3515 3283 676 779 8423 9174 11943 13224 Hatchineha 5090 5123 936 1077 7458 7803 12733 14068 Kissimmee 4159 3970 639 645 11736 11003 10194 10204 Istokpoga 2775 2432 390 502 2913 3208 3457 3895 Inorganic P Fractionation Inorganic P extracted with 1 M KCl is identified as the labile Pi portion that is most bioavailable and readily releas ed to the overlying water colu mn of a lake (Reddy et al. 1998). The proportions of the P fractions were relatively similar across all five lakes (Figure 2-8 and Figure 2-9). Th e KCl-Pi represented <1% of total P in all 5 lakes. The NaOH-Pi fraction, considered to represent Fe and Al bound P, ranged from 21 to 37% of total P with a mean of 29%. The greatest concentration of Fe and Al bound P was found in Lake Cypress (221 250 mg kg-1) while the lowest concentration was found in Lake Tohopekaliga (39.6 43.3 mg kg-1) (Table 2-3).

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29 0 4000 8000 12000 16000 HCl-MgHCl-CaOxa-FeOxa-Almg kg-1 Tohopekaliga Cypress Hatchinea Kissimmee Istokpoga 0 4000 8000 12000 16000 HCl-MgHCl-CaOxa-FeOxa-Almg kg-1mg kg-1 Tohopekaliga Cypress Hatchinea Kissimmee Istokpoga Figure 2-7. Amount of metals, HCl-Mg, HClCa, Oxalate-Fe, and Oxalate Al, in mg kg-1 for all lakes. The HCl-Pi fraction which represents the Ca and Mg bound P ranged from 4 to 8% of total P with a mean of 5%. Calcium and Mg bound P were found to be the highest in Lake Hatchineha (39.5 37.1 mg kg-1) and the lowest in Lake Tohopekaliga (11.6 11.7 mg kg-1). Total inorganic phosphorus (TPi) was calculated by summing the KCl, NaOH, and HCl extract values, and represented betw een 26-39% of total P. Lake Cypress was found to have the highest amount of total inorganic P (246 265 mg kg-1) while Lake Tohopekaliga had the least amount (52.3 54.9). Some organic P fractions such as NaOH P o, which is associated with humic and fulvic acids were identified. The distribution of NaOH Po ranged from 17 to 34% of total P with a mean of 26%. Lake Kissimmee had the highest amount (214 238 mg kg-1) of humic and fulvic acids while Lake Tohope kaliga had the least amount (40.9 46.8 mg kg-1). The residual organic P, which is cons idered the most recalcitrant fraction ranged, from 28-43% of total P with a mean of 40% with Lake Kissimmee having the higher

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30 amount (291 296 mg kg-1) while Lake Tohopekaliga had the least of amount (51.0 59.9 mg kg-1) of residual organic P. Total orga nic P, calculated by summing NaOH-Po and residual organic P, represented between 59-74% of total P. The highest amount of total organic P was found in Lake Kissimmee (506 508 mg kg-1) and the least amount was found in Lake Tohopekaliga (91.9 106 mg kg-1). The percent of total organic P was much higher than total inorgani c P at 65 and 35%, respectively. Sediment total P values for the lakes were 144, 274, 511, 660, and 680 mg kg-1 for lakes Tohopekaliga, Istokpoga, Hatchineha, Cypress, and Kissimmee, respectively. There was no significant difference found between each lake for each P forms determined, which may be due to the high stan dard deviations, an artifact of different sediment types.

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31 Lake Hatchineha29% 8% 25% 38% 0.23% KCl-Pi NaOH-Pi HCl-Pi NaOH-Po Residue-P TP=510 mg kg-1 Lake Tohopekaliga27% 8% 28% 36% 0.76% KCl-Pi NaOH-Pi HCl-Pi NaOH-Po Residue-P TP=144 mg kg-1 Lake Cypress37% 4% 17% 42% 0.18% KCl-Pi NaOH-Pi HCl-Pi NaOH-Po Residue-P TP=600 mg kg-1 Figure 2-8. Distribution of P forms in Lakes Tohopekaliga and Hatchineha.

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32 Lake Kissimmee21% 4% 32% 43% 0.16% KCl-Pi NaOH-Pi HCl-Pi NaOH-Po Residue-P Lake Istokpoga32% 6% 33% 28% 0.58% KCl-Pi NaOH-Pi HCl-Pi NaOH-Po Residue-P TP=274 mg kg-1 Figure 2-9. Distribution of P forms in Lakes Cypress and Kissimmee. Table 2-3. Mean and standard deviations fo r P forms: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P (n=10) for each lake in mg kg-1 for all P forms. TohopekaligaCypress Hatchineha Kissimmee Istokpoga P forms KCl-Pi 1.1 0.8 1.1 0.4 1.2 0.7 1.1 0.6 1.6 1.0 NaOH-Pi 39.6 43.3 221 250 150 162 145 174 87.2 93.4 HCl-Pi 11.6 11.7 23.9 22.1 39.5 37.1 27.7 48.3 17.6 17.1 TPi 52.3 54.9 246 265 191 190 173 174 106 110 NaOH-Po 40.9 46.8 103 97.4 125 127 214 238 92.0 114 Residue P 51.0 59.9 251 272 193 225 291 296 75.8 84.1 Total Po 91.9 106 354 366 319 322 506 508 167 196 Total P 144 160 600 629 510 510 680 660 274 298 TP=680 mg kg-1

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33 Discussion Physical and Chemical The lakes characterized as mud had less than 62 u m of clay and silt in the sediments of the lakes and all othe r lakes were defined as sand (>63 u m) (Oui and McComb 2000). The lakes, such as Cypre ss, Kissimmee, and Hatchineha, with a high mean total P contained primarily mud se diments with low bulk density and high concentrations of total C, N and organic matte r. Lake sediments with low total P, high bulk density, and low total C, N and organi c matter, such as Istokpoga and Tohopekaliga were dominantly sand sediments. These re sults are comparable to the mud and sand sediments of Lake Okeechobee, Florid a (McArthur 1991, Olila and Reddy 1993). Typically, nutrient content tends to increase with an increase in organic matter (Farnham and Finney 1965). The sample data was divided into sand and mud sediment type to compare the distribution of bulk density, LO I, and total P, N, and C be tween the two major types. There were 26 sand stations and 24 mud stati ons for all lakes combined (Table 2-4 and Table 2-5). When looking at th e individual stations and thei r respective sediment type, the muds had bulk densities ranging from 0.04 to 0.50 g cm-3 while the sands had bulk densities ranging from 0.56 to 1.18 g cm-3. The muds had higher organic matter content and nutrients compared the sands. There were no differences found between the sand stations of each lake. However, Tohopekaliga’s mud stations were significantly higher in bulk density compared to the mud sediments of Hatchineha; and Kissimmee ( P <0.007). Lake Kissimmee’s mud stations were significantly hi gher in LOI, total C and N compared to the mud sediments of Tohopekaliga ( P <0.05). The mud stations (n=24) were

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34 significantly higher in bulk density, LOI, and total C, N, and P compared the sand stations (n=26) for all lakes combined ( P <0.05). Total P, C, and N were highl y correlated to LOI with R2 = 0.87, 0.99, and 0.98 respectively for the mud sediments (Figure 2-10 to Figure 2-12). However, total P, C, N were not highly correlated with LOI for the sand sediments with R2=0.24, 0.57 and 0.48 respectively. A strong positive correlation between sediment total P and LOI suggests that organics are important as a P reser voir (Oui and McComb 2000). Total N and C were well correlated to P with R2= 0.84 and 0.87, respectively, indicating that the P source in these mud sediments may be relate d to organic matter (Figure 2-13 and Figure 2-14). However, there was not a strong re lationship found between total C and N to P with R2=0.54 and 0.55, respectively. The strong correlation of nutri ent content with organic matter demonstrates the importance of organic matter in nutrient cycling in lake sediments. Table 2-4. Mean and standard deviations for P forms for sand sediments: bulk density (BD), mass loss on ignition (L OI), total carbon (TC), total nitrogen (TN), total phosphorus (TP) per lake in mg kg-1 for all P forms. Tohopekaliga Cypress HatchinehaKissimmee Istokpoga n=7 n=4 n=5 n=4 n=6 Sand BD 1.0 0.1 0.9 0.3 0.9 0.2 0.9 0.02 1.0 0.2 LOI 1.2 0.4 2.9 1.9 1.7 0.7 1.7 1.7 2.4 1.0 TC 5.8 1.2 9.8 7.6 9.0 4.0 6.5 1.0 9.9 5.1 TN 0.6 0.2 0.9 0.7 0.8 0.3 0.7 0.2 0.7 0.4 TP 66 16 81 49 69 29 48 10 68 30

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35 Table 2-5. Mean and standard deviations for P forms for mud sediments: bulk density (BD), mass loss on ignition (L OI), total carbon (TC), total nitrogen (TN), total phosphorus (TP) per lake in mg kg-1 for all P forms. Tohopekaliga Cypress HatchinehaKissimmee Istokpoga n=3 n=6 n=5 n=6 n=4 mud BD 0.4 0.1 0.2 0.2 0.1 0.05 0.1 0.1 0.2 0.1 LOI 7.8 3.4 27 17 34 11 42.7 18 23 12 TC 41 18 127 81 153 52 203 88 115 52 TN 3.2 1.3 12 8.0 15 5.0 19 8.0 9.0 4.0 TP 307 104 1016 679 1092 371 1139 523 587 217 y = 4.70x + 0.03 R2 = 0.99 0 100 200 300 400 010203040506070 Loss on Ignition (%)Total C (g kg-1) y = 2.65x + 3.00 R2 = 0.57 0 5 10 15 20 25 0123456 Loss on Ignition (%)Total C (g kg-1) Figure 2-10. Regression between co ncentrations of total C (g kg-1) to loss on ignition (%). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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36 y = 0.44x 0.63 R2 = 0.98 0 5 10 15 20 25 30 010203040506070 Loss on Ignition (%)Total N (g kg-1) y = 0.21x + 0.34 R2 = 0.48 0 1 2 3 0123456 Loss on Ignition (%)Total N (g kg-1) Figure 2-11. Regression between co ncentrations of total N (g kg-1) to loss on ignition (%). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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37 y = 28.8x + 52.7 R2 = 0.87 0 400 800 1200 1600 2000 010203040506070 Loss on Ignition (%)Total P (mg kg-1) y = 11.2x + 44.7 R2 = 0.24 0 50 100 150 200 0246 Loss on Ignition (%)Total P (mg kg-1) Figure 2-12. Regression between concentrations of total P (g kg-1) to loss on ignition (%). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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38 y = 4.83x + 27.28 R2 = 0.54 0 100 200 300 400 0510152025 Total C (g kg-1)Total P ( mg kg-1) y = 6.02x + 69.1 R2 = 0.84 0 400 800 1200 1600 2000 050100150200250300350Total C (g kg-1)Total P (mg kg-1) Figure 2-13. Regression between co ncentrations of total P (mg kg-1)and with total C (g kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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39 y = 64.0x + 98.2 R2 = 0.87 0 400 800 1200 1600 2000 051015202530 Total N (g kg -1)Total P (mg kg -1) y = 55.9x + 24.3 R2 = 0.55 0 50 100 150 200 0123 Total N (g kg -1)Total P (mg kg -1) Figure 2-14. Regression between co ncentrations of total P (mg kg-1) and with total N (g kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph. Metals Metals may increase the capacity of sediments to retain P under certain conditions. The ability of P to be retained by Fe/Al and Ca/Mg depends on the pH and/or redox conditions of the sediments. Phos phorus is retained by Fe/Al compounds under acidic conditions and therefore is more st able under low pH conditions. Depending on redox conditions, the reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous iron (Fe2+) compound can lead to P released from the sediment. When there is a dominance of Ca/Mg P in the sediments, P is more stable under high pH or alkaline

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40 conditions. Organic acids from settling or deposited decomposing organic matter can lower the pH short term and lead to dissolution of Ca. The sandier lakes, such as Lake T ohopekaliga and Istokpoga had lower amounts of Ca, Mg, Fe, and Al, compared to the m uddier sediments of Cypress, Kissimmee, and Hatchineha ( refer to Figure 2-10). Phosphorus accre tion in these lakes is significantly associated with Ca, Mg, Fe, and Al; thus th e presences of these metals play a very important role in inorganic P retent ion in lake sediments (Table 2-6). Table 2-6. Pearson correlations fo r selected metals and total P Total P Ca Mg Fe Ca 0.924 (<0.001) Mg 0.924 0.962 (<0.001) (<0.001) Fe 0.969 0.887 0.879 (<0.001) (<0.001) (<0.001) Al 0.943 0.929 0.970 0.908 (<0.001) (<0.001) (<0.001) (<0.001) Samples were again divided into muds a nd sands to look at the difference in the relationship between metals w ith total P amongst the mud an d sand sediments (Table 2-7 and Table 2-8). The mud sediments in each of the five lakes contain greater amounts of Ca, Mg, Fe and Al compared to the sand se diments. Total phosphorus concentrations were regressed against Ca, Mg, Fe and Al fo r the mud sediments Both Ca, Mg, and Al were significantly correlated with phosphorus with a R2=0.72, 0.68 and 0.77 respectively ( P <0.001) (Figure 2-18 to Figure 2-21). Oxal ate-Fe was highly correlated with phosphorus with R2=0.88, which suggest that Fe play s a greater role in inorganic P stability. Calcium, Mg, Fe and Al were also regressed against total P for the sand

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41 sediments and did not correlate well with phosphorus with a R2=0.01, 0.68, 0.58 and 0.39 respectively (Figure 2-15 to Figure 2-18). There were no significant di fferences in metals found between the sand stations of each lake. However, there was a difference found in the mud stations in Mg between Tohopekaliga and Hatchineha (P<.05). There was also a significant difference found in the mud stations in Fe content between Lake Kissimmee and Tohopekaliga (P<0.03). There were also significan t differences found between the mud and sand sediments within each lake for all meta ls (Ca, Mg, Fe, Al) (P<0.05). Table 2-7. Mean and standard deviations for P forms for sand sediments: HCl-Ca and Mg and Oxalate Fe and Al mg kg-1 for all lakes Tohopekaliga Cypress HatchinehaKissimmee Istokpoga n=7 n=4 n=5 n=4 n=6 Sand Ca 470 375 1041 846 669 164 237 42.8 1403 1080 Mg 14.9 17.7 42.2 53.4 46.7 30.2 2.7 3.5 49.7 39.4 Fe 800 114 1070 579 971 458 1182 195 727 324.2 Al 1060 616 1343 824 1131 376 632 122 851 404 Table 2-8. Mean and standard deviations for P forms for mud sediments: HCl-Ca and Mg and Oxalate Fe and Al mg kg-1 for all lakes Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga n=3 n=6 n=5 n=6 n=4 mud Ca 1946 1042 5165 3288 9511 3186 6774 2802 4834 2527 Mg 304 234 1098 745 1825 7795 1063 456 902 416 Fe 3185 1409 13325 8899 13947 5617 18772 8328 6193 2609 Al 61117 4137 19010 12828 24335 10423 16569 8093 7366 3360

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42 y = 17.8x 140 R2 = 0.77 0 8000 16000 24000 32000 40000 0500100015002000 Total P (mg kg-1)oxalate-Al (mg kg-1) y = 14.6x + 33.6 R2 = 0.58 0 1000 2000 3000 050100150200 Total P (mg kg-1)oxalate-Al (mg kg-1) Figure 2-15. Regression between co ncentrations of oxalate-Al (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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43 y = 14.6x 835 R2 = 0.88 0 6000 12000 18000 24000 30000 0500100015002000 Total P (mg kg-1)oxalateFe (mg kg-1) y = 8.1832x + 373.97 R2 = 0.3928 0 1000 2000 3000 050100150200 Total P (mg kg-1)oxalateFe (mg kg-1) Figure 2-16. Regression between co ncentrations of oxalate-Fe (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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44 y = 5.58x + 968 R2 = 0.72 0 4000 8000 12000 16000 0500100015002000 Total P (mg kg-1)HCl-Ca (mg kg-1) y = 2.78x + 590 R2 = 0.01 0 1000 2000 3000 4000 050100150200 Total P (mg kg-1)HCl-Ca (mg kg-1) Figure 2-17. Regression between concentrations of HCl-Ca (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph.

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45 y = 1.11x + 105 R2 = 0.68 0 500 1000 1500 2000 2500 3000 0500100015002000 Total P (mg kg-1)HCl-Mg (mg kg-1) y = 1.05x 38.1 R2 = 0.68 0 40 80 120 160 050100150200 Total P (mg kg-1)HCl-Mg (mg kg-1) Figure 2-18. Regression between concentrations of HCl-Mg (mg kg-1) with total P (mg kg-1). The mud sediments values are located at top graph and the sand sediments are located at the bottom graph. Inorganic P Fractionation The sandier lakes, such as Tohopekali ga and Istokpoga had less inorganic and organic P compared to the lakes characteri zed as muds (Kissimmee, Hatchineha, and Istokpoga). There were no differences found be tween these any of these lakes due to a high standard deviation, an arti fact of different sediment types. The sample data was divided into sand and mud sediment type to compare the distribution of P between the two types (Table 2-9 and Table 2-10). The proportions of P fractions were relatively the same for both sediment type (Figure 2-19). However, the mean total P concentrations for the sand sediments were

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46 much less than for the mud sediment 61 30 and 855 459 mg kg-1, respectively. Although, the sand sediments had the greater per centage of available P (KCl-Pi) than was found in the mud sediments, the muddier sedi ments may release more P, due to their greater amount of total P. These results ar e similar to those found in Lake Okeechobee for these major sediment types, in which gr eater concentrations of total P was found in the muds compared to the sands (Olila and Reddy 1993). Sand sediment had a slightly greater pe rcent of NaOH-Pi (Fe and Al-P) fraction (31%) than the mud sediments (29%). A similar trend was found for HCl-Pi (Ca and Mg-P) and NaOH-Po (humic and fulvic acid s ) fractions. Residue P distribution was greater in the mud sediments th an in the sand sediments. There were no significant di fferences found between the sand stations of each lake for each P fractions. For the mud sediments of Lake Istokpoga, concentration of KCl-Pi (labile P) fraction was significantly higher than Tohopekaliga and Kissimmee (P<0.05). Total organic P was found to be signifi cant higher in Kissimmee compared to Tohopekaliga for the muds ( P <0.05). There were also si gnificant differences found between the mud and sand sediments with in each lake for all parameters ( P <0.05).

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47 Table 2-9. Mean and standard deviations fo r P forms for sand sediments: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, to tal Po and total P per lake in mg kg-1 for all P forms. TohopekaligaCypress HatchinehaKissimmee Istokpoga Sand n=7 n=4 n=5 n=4 n=6 P forms KCl-Pi 1.2 0.9 0.7 0.3 0.6 0.1 0.6 0.04 1.3 0.8 NaOH-Pi 17.7 5.6 24.9 21.2 15.5 4.5 11.4 3.4 26.1 19.1 HCl-Pi 6.3 2.4 8.7 5.8 9.2 5.0 3.3 1.2 5.9 3.9 TPi 25.2 8.0 34.3 25.3 25.3 7.1 15.2 4.5 33.2 21.0 NaOH-Po 14.6 4.6 17.6 14.5 21.9 7.3 9.3 3.4 14 13.8 Residue P 19.7 5.5 28.3 18.2 12.8 6.1 13.2 3.1 18.9 14.3 Total Po 34.4 7.2 45.8 32.1 34.7 9.3 22.5 5.9 32.9 22.4 Total P 59.6 3.3 80.2 56.8 60.0 12.2 37.8 10.4 66.1 40.4 Table 2-10. Mean and standard deviations for P forms for mud sediments: KClPi, NaOH Pi, HCl-Pi, TPi, NaOH Pi, resi due P, total Po and total P TohopekaligaCypress Hatchineha Kissimmee Istokpoga mud n=3 n=6 n=5 n=6 n=4 P forms KCl-Pi 1.5 0.4 1.4 0.3 1.8 0.3 1.5 0.4 2.1 0.8 NaOH-Pi 234 175 352 248 285 119 234 175 179 82.9 HCl-Pi 43.9 58.3 34 23.6 69.7 27.9 43.9 58.3 35.2 12.9 TPi 279 145 384 263 356 112 280 145 216 95.1 NaOH-Po 351 214 163 80.0 230 97.1 352 214 209 94.0 Residue P 478 235 418 234 375 181 478 235 161 68.4 Total Po 191 145 553 350 605 175 829 392 370 155 Total P 1109 483 948 591 962 281 1109 483 586 220

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48 Mud Sediment29% 5% 26% 40% 0.2% KCL-Pi NaOH-Pi HCL-Pi NaOH-Po Residue P TP = 855 459 mg kg-1 Sand Sediments1% 33% 11% 25% 30% KCL-Pi NaOH-Pi HCL-Pi NaOH-Po Residue P TP = 61 30 mg kg-1 Figure 2-19. The mean pe rcent of mean TP (mg kg-1) of each P fractions (KCl-Pi, NaOH-Pi, HCl-Pi, NaOH-Po, and Re sidue P) for both mud and sand sediments for all the lakes

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49 Conclusion Lake sediments can function as a sour ce or sink for dissolved P coming from nonpoint and point sources. Chemical, physi cal, and microbial processes control the exchange of P between the sediment and wate r column. For any planned restoration to occur in these lakes, it is im portant to understand the forms and properties of P in lake sediments to identify the fact ors that control P release from the sediment to the overlying water column. The sediments of each of the five lakes were characterized for bulk density, mass loss on ignition (LOI), total C, N, and P, as we ll as selected metals (Ca, Mg, Fe and Al). The bulk density ranged from 0.06-1.18 g cm-3 with sediment texture varying from organic mud to sand. The LOI values range d from 0-55% with the highest values representing the greatest conten t of organic matter. The sand stations tended to have low organic matter and high bulk density and the mud stations typically had greater organic matter and low bulk density. The lakes char acterized as sandy la kes (Tohopekaliga and Istokpoga) exhibit the ch aracteristics of low organic ma tter and high bulk density while the muddier lakes had the greater amount of organic matter and low bulk density The lakes characterized as muds, primarily ha d high nutrient levels (total P, total N, and total C) and organic matter content. Th e sandy lakes typically had less nutrients (total P, total N and total C) and organic ma tter. There were str ong correlations of total P, N, C and bulk density to LOI for the mud st ation within each lake. Total C and total N are generally found to be related to organi c matter in sediments. A strong positive correlation between total P and LOI were found, which suggest the importance of organics as a P reservoir.

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50 The muddier lakes also cont ained greater amounts of Ca, Mg, Al, and Fe than the sandier lakes and are well correlated with to tal P. The mud stations of each lake contained the greatest amount of iron compared to the sand stations and is significantly and positively correlated with total P, which indicates that Fe plays a greater role in inorganic P stability. The sand stations were not well correlat ed with any of the metals, suggesting these selected metals may not pl ay a great role in inorganic P stability. The inorganic P results suggest that the gr eatest portion of inorganic P was in the form most associated with Fe and Al (NaOH-Pi). The total organic P was proportionally greater in each lake than total inorganic P. The mud stations contained the greatest amount of TP and P associated with organics and also had greater amounts of available or easily exchangeable P than the sands. The sand and mud stations were not at all different in their distribution of P; however, the muds contained greater amounts of total P, so this sediment type may contribute more to P rel ease to the overlying wate r column of a lake.

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51 CHAPTER 3 PHOSPHORUS FLUX OF SEDIMENTS UNDER DIFFERENT SIMULATED LOADING CONDITIONS Introduction Phosphorus is essential for plant growt h, but excessive amounts entering lakes can lead to eutrophic conditions re sulting in harm to the quality of water in many freshwater systems such as Lake Okeechobee and Lake Apopka. Harm to fisheries, changes in vegetation, and recreation can be some of the results of exce ssive quantities of P entering into lakes. Phosphorus enters the surface wa ter of freshwater lakes primarily by way of nonpoint and point source pollutions from entities such as wastewater treatment plants and from surface runoff from agricultural and urban areas. Reducing nutrient inputs fr om nonpoint and point sources of pollution are essential to restoring lake water quality. However, even after external P load to lakes have been curtailed, internal P flux from the sediment to the water column can occur, contributing heavily to the degrada tion of water quality in lakes (Welch and Cooke 1995). The idea of internal loading is based on th e recycling of nutrients from bottom sediments in lakes to the overlying water column (Carpenter 1983). After load reduction, the internal load of sediments will determine the trophic status of a lake and the amount of lag time for recovery (Petterson 1998). The equilibrium phosphorus concentrati on (EPC) can be used to determine the extent of which the internal load will be released during restorat ion of a lake after external load reductions. The EPC is defined as the P in solution th at is in equilibrium

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52 with P in the solid phase or the point where P is neither being retained nor released from the sediment to the water column (Olila and Reddy 1993). At water column SRP concentrations above the EPC, P is retain ed by the sediments and at concentrations below, the sediments serve as a P source. The EPC can be a useful tool for water managers to determine the water column SR P concentration for which sediments may act as a potential source of P to the overlying water column of a lake. Water managers can manage for the internal sediment P load by de termining the EPC of aquatic systems. For example, water managers may consider dredgi ng a lake as a component of a restoration plan; however dredging is very cost and labor intensive. Therefore, it is important to look at the EPC of a lake to determine if this lake should be dredged or if focus should be aimed at other activit ies during restoration. There are four pathways for the exchange of P from the sediment to water column of a lake: i) settling of in soluble (particulate) inorganic and organic P, ii) uptake of soluble reactive P (SRP) by primary producer s (algae) and its subsequent settling, iii) sorption of soluble inorganic or organic P onto particles that settle onto the sediments, and iv) sorption of soluble inorganic or organi c P directly onto sedi ment particles (Reddy et al. 1999). Sediments act as a net sink of P; however, when porewater P concentration exceed the overlying water column concentration, SRP can be released from the sediment (Moore et al. 1991). The flux of P from the sediment to the water column can depend on processes such as: i) diffusion and advection ( wind/wave action, flow, and biotur bation), ii) processes within the water column (b iotic uptake and release, mi neralization, and sorption by particulate matter), iii) diagenetic processe s (mineralization, so rption, precipitation, and

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53 dissolution) in bottom sediments, and iv) redox conditions (oxygen content), organic matter content, pH, temperature and the pr esence of metal bound to P (Fe, Al, Ca, and Mg) (Bostrom and Pettersson 1982, Holdren and Armstrong 1980, Moore et al 1991, Wetzel 2001). Wind/wave action can induce sediment resu spension and cause event driven large P release from the sediment to the water co lumn and thereby available for uptake by primary producers (Pettersson and Bostrom 19 85). Bioturbation can also increase the release of P. However, P release may not occur over the entire la ke sediment surface, thus bioturbation may not be sufficient to pe rpeturate eutrophic c onditions (Holdren and Armstrong 1980). Diagenetic processes such as sorption (P release from soil mineral surfaces or retention of P onto soil minera l surfaces), precipit ation (formation of amorphous precipitates), disso lution (solubilization of the precipitates), and mineralization (breakdown of organic matter) ca n also mediate the release of P from the sediments. A decrease in dissolved oxygen of the water co lumn can result in an increase in P release from the sediments in freshwater la kes. However, oxygenation of the sediments can result in a decrease in P release to the water column (Holdren and Armstrong 1980, Patrick and Khalid 1974). It is important to note that for shallow and eutrophic lakes that are well mixed, anaerobic conditions rarely persist for any extended periods of time (Welch and Cooke 1995). However, these ep hemeral anaerobic events can significantly after water quality. The release of P may result from the reduction of ferric iron (Fe3+) to ferrous iron (Fe2+) in sediments or from the decomposition of organic matter (Holdren and Armstrong

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54 1980). The ability of P to be retained by Fe/Al and Ca/Mg depends on pH. Phosphorus is retained by Fe/Al compounds under low pH or acidic conditions (Patrick and Khalid 1974). When there is a dominance of Ca/Mg P in sediments, P is more stable under high pH or alkaline conditions (Patrick and Kha lid 1974). Organic acids from settling or deposited decomposing organic matter can lowe r pH short term and l ead to dissolution of Ca bound P (Marsden 1989). Studies have al so shown that temperature plays an important role in P release from sediments, in which P release increased with increases in temperature due in part to increased mine ralization rates (Holdren and Armstrong 1980). Hypothesis The equilibrium P concentration will be higher in sediments with higher TP and therefore provide a greater inte rnal release of P during lake restoration as water quality continues to improve. Objectives The objectives of this study were to: i) determine the release rate of P from the sediments to the water column and ii) determ ine the equilibrium P concentration of the sediments. Site Selection Data collected from the P characteri zation study provided the information for selection of each site for the phosphorus flux st udy. Two stations per lake were chosen from the P characterization study based on a range of sediment TP concentrations and organic matter content (Figure 3-1 to Figur e 3-5). Geographical Positioning Satellite (GPS) equipment was used to locate each site within +/-5m of the true coordinates for the stations chosen. The sampling location and latitude/longitude were documented at each station (Table 3-1).

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55 # Y # Y2 10 N 02468Kilometers L. Tohopekaliga Figure 3-1. Location of sampling st ations for Lake Tohopekaliga.

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56 # Y # Y15 16 N 01234Kilometers Cypress Lake Figure 3-2. Location of sampli ng station for Cypress Lake.

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57 # Y # Y103 107 N 01234Kilometers L. Hatchineha Figure 3-3. Location of sampling st ations for Lake Hatchineha.

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58 # Y # Y1012 1004 N 01234Kilometers L. Kissimmee Figure 3-4. Location of sampling stations for Lake Kissimmee.

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59 # Y # Y 10007 10004 01234Kilometers NL. Istokpoga Figure 3-5. Location of sampling stations for Lake Istokpoga. Table 3-1. X and Y coordinates of each stati on. All coordinates ar e Universal Mercator, North American Datum 1983, Units meters, UTM Zone 17. LakeStationx_coordy_coord Toho24602523125825 Toho104618093116800 Cypress154682613105828 Cypress164698753106370 Hatch1034580823100650 Hatch1074613413098421 Kissimmee10044723943084179 Kissimmee10124731883088426 Istokpoga100044699163030750 Istokpoga100074727793026915

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60 Materials and Methods Intact sediment cores were taken from two stations per lake (10 station total) by a SCUBA diver using 7.5 cm wide plexiglas tube to collect 15 cores per site (~30 cores per lake; ~150 cores total). The cores were care fully driven approximately 30 cm into the sediment with minimal impact to the sediment -water interface. St oppers were inserted into both ends of the cores and secured with tape for tr ansport back to Gainesville, Florida. Surface water from each lake was co llected in 30 L containers for purposes of re-flooding each core with lake water. Upon arrival to the laboratory, the surface water was filtered with 0.45 u m Whatman filter paper to remove any particul ates. The water column of each core was slowly drained and replaced with 1 L of f iltered lake surface water for a 30 cm water column. The SRP concentration of the surface water was determined during analysis using the Murphy and Riley Method (1962). A ll cores were spiked with SRP to yield concentrations of 0, 15, 30, 60, 120 ug L-1 at the beginning of the experiment. Three replicates per loading concentration fo r each site and flux measurements were determined. Water columns in each core were constantly aerated with room air using aquarium pumps to maintain dissolved oxygen levels close to 5 mg L-1 for 25 days. Aluminum shrouds were placed over the cores so that light could not penetrate and the cores were incubated in a water bath to mainta in a constant temperature (22 0.34 C). Water was periodically removed for analysis with a 10 mL plastic syringe fitted with tubing to withdraw samples from the middle of the water column, in which, 10 ml were taken and filtered with a 0.45 um syri nge filter and analyzed for SRP using a

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61 segmented flow colorimetric analyzer (U SEPA 1993, Method 365.4). The water column levels (1 L or 30 cm) were maintained afte r sampling by adding 10 ml of lake water back into each core. Background water column SR P concentrations were an average of 6 4 ug L-1. Filtered water samples were imme diately frozen until analysis. Data Analysis Data were analyzed using a one way anal ysis of variance (ANOVA) with a p value of 0.05. The Tukey-Kramer test was used to evaluate differences between means. Data were analyzed using JMP statistics version 4. Microsoft excel (Microsoft 2000) was used to perform regression analyses and correlations. Results No P Addition Water column SRP concentrations In general, water column SRP concentrations (filtered water with no P addition) tended to increase over time, suggesting P flux from the sediment. The initial site water was 0.002, 0.003, 0.005, 0.009 and 0.011 for Lakes Kissimmee, Istokpoga, Tohopekaliga, Cypress and Hatchineha, respectively. Water column SRP concentrations increased over the first 2 da ys in all lakes, except Lake Hatchineha, in which concentratio ns declined slightly at a rate of -36.4% (Table 3-2). Concentrations increased in all the other lakes between 22% in Lake Cypress to 400% in Lake Kissimmee. The mean water column SRP concentrations at day 2 ranged from a low in Lake Hatchineha (0.007 0.002 mg L-1) to a high in Lake Istokpoga (0.014 0.003 mg L-1) at day 2. Mean water column SRP concentrations ranged from a low of 0.013 0.006 mg L-1 in Cypress Lake to higher concentrati ons in Lake Istokpoga at 0.022 0.007 mg L-1 at

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62 day 7 (Table 3-2). Between day 2 and 7 wate r column SRP concentrations increased for all lakes, however, Lake Cypr ess and Hatchineha values were close to their initial water column SRP concentration at day 7. The ch ange in water column SRP concentrations ranged from a high of 650%in Lake Ki ssimmee to 27% in Lake Hatchineha. After 7 days, the SRP concentrations, for the most part, increased over the course of the experiment (Table 3-2). Water column SRP concentrations ranged from a high in Lake Tohopekaliga (0.045 0.059 mg L-1) to 0.015 0.003 mg L-1 in Lake Kissimmee by the end of the study (~25 days). The ch ange in concentrati on increased between 1233% from the initial concentration in La ke Istokpoga to 100% in Cypress Lake. P flux rates. The SRP flux rate was determined based on the slope of the curve of water column SRP concentration over time. At 2 days, the mean P flux ranged from a rate of -1.668 0.885 (mg m-2 d-1) in Lake Hatchineha to a positive rate of 0.784 0.458( mg m-2 d-1) in Lake Istokpoga (Table 3-3). The positive P flux rates of Lakes Tohopekaliga, Kissimmee and Istokpoga suggest that the lakes are releasing phosphorus to the water column, while the negative fl ux rates of Lake Cypress and Hatchineha suggest P retention by sediments. There wa s a difference in P fl ux rates at day 2, in which, rates were lower in Lake Hatchine ha compared to the other lakes (Istokopoga, Tohopekaliga, Kissimmee and Cypress P<0.0001). This difference may be due to differences in the sediment characteristics of the lakes (sediment t ype) or past nutrient loading (Table 3-4 and Table 3-5). The mean 7 day P flux rate for th e lakes ranged from -0.036 0.168 mg m-2 d-1 in Lake Hatchineha to a high of 0.439 0.296 mg m-2 d-1 in Lake Istokpoga (Table 3-3).

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63Table 3-2. Percent change in Water Column SRP (mg L-1) under no P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicates a decrease in SRP concentration wh ile a positive (+) percent change indicates an increase in SRP concentrations. n=6 for all lakes except Cypress in which n=4. --------------------SRP (mg L-1)-------------------------------Percent Ch ange (%)----------Lake Initial SRP (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d Tohopekaliga 0.005 0.008 0.002 0.017 0.012 0.045 0.059 60 240 800 Cypress 0.009 0.011 0.003 0.013 0.006 0.018 0.015 22 44 100 Hatchineha 0.011 0.007 0.002 0.014 0.007 0.033 0.033 -36 27 200 Kissimmee 0.002 0.010 0.001 0.015 0.002 0.015 0.003 400 650 650 Istokpoga 0.003 0.014 0.003 0.022 0.007 0.040 0.036 367 633 1233 Table 3-3. Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpog a, Cypress, and Hatchineha at no P additions at 2, 7, and 25 days. n=6 fo r all lakes except Cypress (n=4). ----------------------P flux mg m-2 d1---------------------Lakes 2 day 7 day 25 day Tohopekaliga 0.103 0.430 0.311 0.255 0.418 0.734 Cypress -0.003 0.520 0.085 0.180 0.070 0.142 Hatchineha -1.67 0.885 -0.036 0.168 0.298 0.412 Kissimmee 0.192 0.271 0.249 0.255 0.065 0.019 Istokpoga 0.784 0.458 0.439 0.296 0.295 0.403

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64Table 3-4. Sediment characteristics of all stations for each la ke for bulk density, mass loss on ignition (LOI), and total C, N and P (mg kg-1). N=10 Sediment Bulk DensityLOI TC TN TP Lake Station Type G cm-3 % g kg-1 g kg-1 mg kg-1 Tohopekaliga T2 organic mud 0.25 11.2 57.9 4.54 423 Tohopekaliga T10 sand 1.06 1.4 5.41 0.57 61.8 Cypress C15 organic mud 0.08 32.6 140 12.4 1036 Cypress C16 organic mud 0.06 42.7 201 19.4 1694 Hatchineha H103 organic mud 0.17 15.0 72.8 6.81 494 Hatchineha H107 organic mud 0.06 38.8 180 17.8 1126 Kissimmee K1004 sand 0.57 1.94 7.59 1.09 60.6 Kissimmee K1012 organic mud 0.05 51.9 245 22.1 1333 Istokpoga I10004 organic mud 0.13 25.8 127 8.51 721 Istokpoga I10007 organic mud 0.13 19.7 95.7 7.68 555

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65Table 3-5. Sediment characteristics of all stations for each lake for oxalate-Fe and Al and HCl-Ca and Mg. n=10 Lake Station Fe Al Ca Mg Tohopekaliga T2 4800 10529 3088 563 Tohopekaliga T10 760.3 721.3 288.4 0.0 Cypress C15 17844 23532 6686 1360 Cypress C16 19970 28238 8221 1649 Hatchineha H103 5510 8813 4214 680 Hatchineha H107 13641 21335 9619 1636 Kissimmee K1004 1403 801 274 7 Kissimmee K1012 24150 20218 7303 1252 Istokpoga I10004 8238 10925 6257 1152 Istokpoga I10007 5653 6189 3977 796

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66 The positive P flux values of Lakes Istokpoga, Kissimmee, Tohopekaliga and Cypress suggest P release to the overlying water column, while the negative P flux rates of Lake Hatchineha suggest retention by the sediments. The P flux rates were significantly lower in Lake Hatchineha co mpared to Lake Istokpoga (P<0.05). This dissimilarity may be due to differences in sediment characteristics. Lake Istokpoga sediments are characterized mostly by sand co mpared to the muddier sediments of Lake Hatchineha, with greater pot ential binding sites. There were no significant co rrelations between P flux and any of the sediment characteristics, however, TP was significantl y and negatively correlated to bulk density and significantly and positively correlated to Ca, Mg, Fe, and Al (Table 3-6 and Table 37). At day 25, the mean P flux ranged from a low rate of 0.065 0.019 mg m-2 d-1 in Lake Kissimmee to a high of 0.418 0.734 mg m-2 d-1 in Lake Tohopekaliga (Table 3-3). The positive P flux rates of all these lakes s uggest P release from the sediments. There were no significant differences in P flux rates at day 25 at no P additions.

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67Table 3-6. Correlation between sediment pr operties with the Pearson co rrelation on top and the P-value on the bottom in parent heses. All correlations are significant to P<0.05. n=10 Bulk Density LOI total C total N total P Fe Al Ca Mg LOI -0.76 (<0.05) total C -0.77 1.00 (<0.05) (<0.001) total N -0.73 0.99 0.99 (<0.05) (<0.001) (<0.001) total P -0.74 0.95 0.95 0.96 (<0.05) (<0.001) (<0.001)(<0.001) Fe -0.67 0.96 0.95 0.95 0.94 (<0.05) (<0.001) (<0.001)(<0.001) (<0.001) Al -0.72 0.89 0.88 0.90 0.96 0.92 (<0.05) (<0.001) (<0.001)(<0.001) (<0.001)(<0.001) Ca -0.82 0.92 0.92 0.91 0.91 0.83 0.90 (<0.001) (<0.001) (<0.001)(<0.001) (<0.001)(<0.001)(<0.001) Mg -0.83 0.92 0.91 0.90 0.93 0.84 0.93 0.99 (<0.001) (<0.001) (<0.001)(<0.001) (<0.001)(<0.001)(<0.001)(<0.001)

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68Table 3-7. Correlation between P flux and EPCw with sediment properties with the Pearson correlation on top and the P-value on the bottom in parentheses. All corr elations are significant to P<0.05. n=10 Bulk Density LOI total C total N total P EPCw Fe Al Ca Mg P Flux No P 0.184 -0.307 -0.274 -0.329 -0.314 0.488 -0.357 0.465 -0.437 -0.385 (0.611) (0.388) (0.444) (0.353) (0.377) (0.153) (0.312) (0.176) (0.207) (0.272) 15 -0.014 0.046 0.081 -0.006 -0.079 0.423 -0.136 -0.291 -0.003 -0.010 (0.968) (0.899) (0.823) (0.987) (0.828) (0.223) (0.707) (0.415) (0.994) (0.977) 30 0.568 -0.426 -0.422 -0.439 -0.464 0.105 -0.480 -0.559 -0.425 -0.435 (0.087) (0.220) (0.225) (0.204) (0.176) (0.773) (0.161) (0.093) (0.220) (0.208) 60 0.221 -0.360 -0.358 -0.390 -0.247 0.208 -0.396 -0.261 -0.256 -0.168 (0.540) (0.306) (0.309) (0.266) (0.491) (0.563) (0.258) (0.467) (0.475) (0.643) 120 -0.010 -0.041 -0.064 0.023 0.155 -0.410 -0.008 0.252 0.128 0.174 (0.979) (0.910) (0.861) (0.949) (0.668) (0.239) (0.982) (0.483) (0.726) (0.631)

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69 Phosphorus Addition (15 ug L-1) Water column SRP concentrations. The initial SRP concentrations ranged from 0.017 mg L-1 in Lake Kissimmee to a high of 0.026 mg L-1 in Lake Hatchineha (Table 38). The mean water column SRP concentratio ns at day 2 ranged from a low in Lake Kissimmee (0.0100.001 mg L-1) to a high in Cypress Lake (0.0230.003 mg L-1). Concentrations decreased in all lakes, except, Lake Tohopekaliga, in which concentrations increased at a ra te of 8% and declined in all other lakes at a rate between 6% in Cypress Lake to 41% in Lake Kissi mmee. These results suggest P retention by sediments in all lakes, except Lake Tohopekaliga The mean SRP concentration ranged from a high in Lake Istokpoga (0.024 0.008 mg L-1) to a low concentration in Lake Kissimmee (0.015 0.002 mg L-1) at day 7 (Table 3-8). Water column SRP concentrations in creased in Lake Tohopekaliga and Istokpoga over a 7 day period, even after the initial spike, suggesting P release from the sediments at a rate of 5 and 33%, respectively. In Lake Kissimmee, Cypress Lake and Lake Hatchineha water column SRP concentrati ons decreased at a rate less than 45%, suggesting P retention by the sediments. After 7 days, the water column SRP concen trations continued to increase over the course of the experiment for all lakes at a rate between 0% in Lake Kissimmee to 75% in Lake Tohopekaliga. The mean water column SRP concentrations at day 25 ranged from a low in Lake Kissimmee (0.0170.002 mg L-1) to a high in Lake Tohopekaliga (0.0350.019 mg L-1) (Table 3-8). These results suggest that all the lakes all releasing P from the sediments at this P addition (15 ug L-1).

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70 Table 3-8. Percent change in SRP mg L-1 at 15 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) indicates a decrease in SRP concentrati on while a positive (+) percen t change indicates an increase in SRP concentrations. n=6 for all lakes except Cypress in which n=5. ----------------SRP (mg L-1)--------------------Percent Change (%)---Lake Initial Conc. (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d Tohopekaliga 0.020 0.022 0.002 0.0210.0100.0350.0198 5 75 Cypress 0.024 0.0230.003 0.0180.0050.0320.020-6 -25 33 Hatchineha 0.026 0.0220.002 0.0180.0040.0300.026-15 -31 15 Kissimmee 0.017 0.0100.001 0.0150.0020.0170.002-41 -12 0 Istokpoga 0.018 0.0130.003 0.0240.0080.0290.016-28 33 61

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71 P Flux rates. At 2 days, the mean SRP flux ranged from a rate of -0.64 1.094 (mg m-2 d-1) in Lake Tohopekaliga to a rate of -2.32 0.237 (mg m-2 d-1) in Lake Istokpoga (Table 3-9). The negative P flux rates of all the lakes suggest that the sediments are retaining phosphorus. Phosphorus flux rates were significantly higher for Lake Kissimmee with Lake Tohopekaliga and Cypress at day 2 (P<0.001). The dissimilarities may be due to differences in sediment type and physical and chemical properties of the sediment. For example, La ke Tohopekaliga is a sandier lake with lower total C, N, and P (16.3 18.8, 1.37 1.38, and 138 127 mg kg-1 compared to Lake Kissimmee C, N, P (124 121, 11.7 11.3, and 703 685 mg kg-1 ( see chapter 2, Table 2-1). The mean 7 day SRP flux rates ranged from -0.061 0.270 mg m-2 d-1 in Lake Kissimmee to 0.367 0.228 mg m-2 d-1 in Lake Istokpoga. The positive P flux rates of Lake Istokpoga suggest P releas e from the sediments, while th e negative P flux rate of all the other lakes indicate P retention by the se diments. This data suggests that Lake Istokpoga may be the only lake functioning as a source of P to the overlying water column at this water column P level (15 ug L-1). Phosphorus flux rates were significantly lower for Lake Istokpoga compared with Kissimmee, Tohopekaliga, Cypress, and Hatchineha (P<0.05). Phosphorus flux was not significantly correlate d with any of the sediments characteristic, however, TP was significantly and positively correlated with LOI, Ca, Mg, Fe, and Al. At 25 days, the mean P flux range d from a rate of 0.137 0.146 mg m-2 d-1in Lake Istokpoga to a rate of 0.027 0.232 mg m-2 d-1 in Lake Hatchineha. The positive P flux

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72 rates of all the lakes suggest that the lakes are releasing phos phorus to the water column. There were no significant diffe rences in P flux rates at day 25 at this P addition. Table 3-9. Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 15 ug L-1 P additions at 2, 7, and 25 days. n=6 for all lakes except Lake Cypress n=5 -------------------------P flux mg m-2 d-1--------------------------Lakes 2 day 7 day 25 day Tohopekaliga -0.64 1.094 -0.081 0.0.285 0.112 0.208 Cypress -0.96 0.621 -0.235 0.164 0.024 0.139 Hatchineha -1.17 0.687 -0.237 0.160 0.027 0.232 Kissimmee -2.32 0.237 -0.061 0.270 0.028 0.030 Istokpoga -0.61 0.421 0.367 0.228 0.137 0.146 Phosphorus additions (30 ug L-1) Water column SRP concentrations. The site water ranged from 0.002-0.011 mg L-1 plus the P addition which increased the concentration to 32, 33, 35, 39 and 41 ug L-1 for Lake Kissimmee, Istokpoga, Tohopekaliga, Cypress, and Hatchineha, respectively. The mean water column SRP concentrations at day 2 ranged from a low in Lake Kissimmee (0.0210.002 mg L-1) to a high in Cypress Lake (0.0360.003 mg L-1) and Lake Tohopekaliga (0.0360.005 mg L-1) (Table 3-10). Lake Tohopekaliga water column SRP concentrations increased at a rate of 2% while all other lakes concentrations declined in rates ranging from 8% in Cypre ss Lake to 30% in La ke Kissimmee at day 2. The mean water column SRP concentr ations ranged from (0.039 0.005 mg L-1) in Lake Tohopekaliga to (0.017 0.003 mg L-1) Lake Kissimmee on day 7. Water column SRP concentrations decreased in Lakes C ypress, Hatchineha, Kissimmee and Istokpoga at day 7 at a rate between 15% in Lake Hatchineha and Istokpoga to 47% in Lake Kissimmee, which suggests P retention by th e sediments in these lakes. Lake

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73 Tohopekaliga was the only lake to increase in water column SRP concentration at a rate of 11%, which suggests P release from the sediments at day 7. The mean water column SRP concentr ations ranged from (0.0520.031 mg L-1) in Lake Tohopekaliga to (0.0140.003 mg L-1) Lake Kissimmee on day 25. The SRP concentrations increased in Lake Tohopekalig a, Cypress, Hatchine ha, and Istokpoga over the course of the experiment for all lakes at day 25 at a rate be tween 13% in Cypress Lake to 63% in Lake Hatchineha. Water co lumn SRP concentrations on day 25 for Lake Tohopekaliga were much higher in one core at 0.106 mg L-1. This may be due to heterogeneity of the sediment in the lake or bi ological release from organisms in the core. Water column concentrations decreased in La ke Kissimmee at a rate of 56%, respectively at this P addition (30 ug L-1).

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74 Table 3-10. Percent change in SRP mg L-1 at 30 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicate a decrease in SRP concentration while a positive (+) percent change indicate an increase in SRP concentrations. n=6 -----------------SRP (mg L-1)-------------------Percent Change (%)--Lake Initial Conc. (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d Tohopekaliga 0.035 0.0360.0050.0390.0230.0520.031 2 11 49 Cypress 0.039 0.0360.0030.0290.0070.0440.0027-7 -26 13 Hatchineha 0.041 0.0340.0030.0350.0130.0670.060 -17 -15 63 Kissimmee 0.032 0.0210.0020.0170.0030.0140.003 -34 -47 -56 Istokpoga 0.033 0.0240.0030.0280.0110.0400.027 -27 -15 21

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75 P flux rates. At 2 days, the mean P flux ranged from a rate of -0.339 0.977 (mg m-2 d-1) in Lake Tohopekaliga to a rate of -3.12 0.425 (mg m-2 d-1) in Lake Kissimmee (Table 3-11). The negative P flux rates of all the lakes suggest that the sediments are retaining phosphorus at day 2. Phosphorus fl ux rates were significantly higher in Lake Hatchineha than Tohopekaliga. Flux rates were significantly highe r in Lake Kissimmee compare to Lakes Tohopekaliga, Cypress a nd Istokpoga (P<0.001). The differences may be related to the different physical an d chemical properties of the sediment. The average P flux rate ranged from a negative rate of -0.381 0.174 (mg m-2 d-) in Cypress Lake to a positive rate of 0.007 0.839 (mg m-2 d-1) in Lake Tohopekaliga at day 7. The positive P flux values for Lake Tohopekaliga and Lake Istokpoga suggest that the lakes are functioning as a P source to wa ter column while the negative P flux rate of the other lakes suggest P retention. There we re no significant differe nces in P flux rates between the lakes at day 7. This variability in P flux rates may be due to wide sediment variability within the lakes, due to the presence of both sands and muds. The mean P flux rate ranged from a negative rate of -0.117 0.202 mg m-2 d-1 in Lake Istokpoga to a positiv e rate of 0.295 0.554 mg m-2 d-1 in Lake Hatchineha at day 25. The positive P flux values for Lake Hatchineha Tohopekaliga and Cypress suggest that the lakes are functioning as a P sour ce to water column while Lake Istokpoga and Kissimmee negative P flux rates suggest P rete ntion by the sediments. There were no significant differences in P flux rates between lakes.

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76 Table 3-11. Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 30 ug L-1 P additions at 2, 7, and 25 days. -----------------------P flux mg m-2 d1------------------------Lakes 2 day 7 day 25 day Tohopekaliga -0.339 0.977 0.007 0.839 0.207 0.326 Cypress -1.04 0.920 -0.381 0.174 0.045 0.251 Hatchineha -1.80 1.064 -0.117 0.453 0.295 0.554 Kissimmee -3.12 0.425 -0.373 0.132 -0.109 0.041 Istokpoga -1.23 0.681 0.073 0.365 -0.117 0.202 Phosphorus additions (60 ug L-1) Water column SRP concentrations. Water column SRP concentrations tended to decrease in all the lakes over the course of the study, leading to P retention by the sediments (Figure 3-6). At 2 days, the m ean water column SRP concentrations ranged from a low of 0.045 0.002 (mg L-1) in Lake Kissimmee to a high of 0.061 0.005 (mg L-1) in Cypress Lake and 0.061 0.002 (mg L-1) Lake Tohopkeliga, respectively (Table 3-12). Concentrations declined at a rate be tween 6 % in Lake T ohopekaliga to 38% in Lake Kissimmee. At day 7, the mean water column SRP concentration ranged between (0.046 0.007 mg L-1) in Lake Tohopekaliga to (0.018 0.007 mg L-1) in Lake Kissimmee. The SRP concentrations in the water column d eclined at a rate between 29% in Lake Tohopekaliga to 75% in Lake Kisimmee. The mean water column SRP concentrations at day 25 ranged from a low in Lake Kissimmee (0.011 0.004 mg L-1) to a high in Lake Hatchineha (0.065 0.050 mg L-1). The concentrations in the water column declined at a rate of 8% in Lake Hatchineha to a rate of 85% in Lake Kissimmee at day 25.

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77 0.00 0.02 0.04 0.06 0.08 0510152025Time (days)SRP (mg/l) Figure 3-6. Phosphorus retenti on by sediments from station T2 of Lake Tohopekaliga at 60 ug L-1 P additions.

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78 78Table 3-12. Percent change in SRP mg L-1 at 60 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicates a decrease in SRP concentration while a pos itive (+) percent change indicates an increase in SRP concentrations. n=6. ----------------SRP (mg L-1)--------------------Percent Change %-----Lake Initial Conc. (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d Tohopekaliga 0.065 0.0610.0020.0460.0070.0300.020-6 -29 -54 Cypress 0.069 0.0610.0050.0450.0120.0610.033-12 -35 -12 Hatchineha 0.071 0.0570.0040.0370.0110.0650.050-19 -48 -8 Kissimmee 0.072 0.0450.0020.0180.0070.0110.004-38 -75 -85 Istokpoga 0.073 0.0470.0080.0370.0130.0370.022-36 -49 -49

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79 P flux rates. At 2 days, the mean P flux ranged from a rate low of -0.937 0.923 (mg m-2 d-1) in Lake Tohopekaliga to hi gh rate of -3.615 0.518 (mg m-2 d-1) in Lake Kissimmee (Table 3-13). The negative P fl ux rates of all the lakes suggest that the sediments are retaining phosphorus at day 2 at P additions of 60 ug L-1. Phosphorus flux rates were significantly higher in Lake Kissimmee compare to Lake Tohopekaliga (P<0.05) at day 2. The average P flux rate at day 7 ra nged from a low of -0.543 0.420 (mg m-2 d-1) in Lake Istokpoga to a high of -1.31 0.227 (mg m-2 d-1) in Lake Kissimmee. These negative P flux rates suggest P retention by sedi ments for all five lakes. Phosphorus flux rates were significantly higher in Lake Kissimmee with Lakes Tohopekaliga and Istokpoga at day 7. At day 25, the mean P flux ranged fro m a rate low of -0.081 0.471 (mg m-2 d-1) in Lake Istokpoga to high ra te of -0.399 0.269 (mg m-2 d-1) in Lake Tohopekaliga. The negative P flux rates of all th e lakes suggest that the sedi ments are retaining phosphorus at day 25. There were no significant differe nces in P flux rates at day 25 at this P addition. Phosphorus additions (120 ug L-1) Water column SRP concentration. Water column SRP concentrations decreased in all the lakes over the c ourse of the study, suggesting P retention by the sediments (Figure 3-7). At 2 days, the mean water co lumn SRP concentration ranged from a low of 0.0880.001 (mg L-1) in Lake Kissimmee to a high of 0.1230.023 (mg L-1) in Lake Hatchineha (Table 3-14). Concentrations declined at a rate between 7% in Lake Hatchineha to 89% in Lake Kissimmee at day 2.

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80 Table 3-13. Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 60 ug L-1 P additions at 2, 7, and 25 days. ------------------------P flux mg m-2 d-1-----------------------Lakes 2 day 7 day 25 day Tohopekaliga -0.937 0.923 -0.675 0.281 -0.399 0.269 Cypress -1.969 1.429 -0.771 0.371 -0.354 0.048 Hatchineha -2.669 0.749 -1.00 0.384 -0.346 0.286 Kissimmee -3.615 0.518 -1.31 0.227 -0.116 0.220 Istokpoga -2.648 1.854 -0.543 0.420 -0.081 0.471 At day 7, the mean water column SRP concentration ranged between (0.0130.014 mg L-1) in Lake Kissimmee to (0.120 0.040 mg L-1) in Lake Hatchineha. The SRP concentrations in the water column declined at a rate between 8% in Lake Hatchineha to 94% in Lake Kissimmee at day 7. The mean water column SRP concentrations at day 25 ranged from a low in Lake Kissimmee (0.0070.010 mg L-1) to a high in Lake Hatchineha (0.1290.065 mg L-1). The concentrations in the water column declined at a rate of 2% in Lake Hatchineha to a rate of 94% in Lake Kissimmee at day 25. Phosphorus additions (120 ug L-1) P flux rates. At 2 days, the mean P flux ranged from a rate low of -2.443 1.149 (mg m-2 d-1) in Cypress Lake to high rate of -6.821 1.032 (mg m-2 d-1) in Lake Kissimmee (Table 3-15). The negative P fl ux rates of all the lakes suggest that the sediments are retaining phosphorus at day 2. The P flux rate for Cypress Lake was significantly lower than La kes Istokpoga and Kissimmee (P<0.001). Phosphorus flux rates were also significantly higher in Lakes Kissimmee co mpared to Lake Hatchineha and Lake Tohopekaliga (P<0.001) at day 2.

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81 0.00 0.03 0.06 0.09 0.12 06121824Time (days)SRP (mg L-1) Figure 3-7. Phosphorus reten tion by sediments from stati on I10007 of Lake Istokpoga at 120 ug L-1 P additions. The mean P flux rate at day 7 ranged from -0.87 0.419 (mg m-2 d-1) in Lake Cypress to -2.91 0.494 (mg m-2 d-1) in Lake Kissimmee (Table 3-13). All lakes appear to be retaining P (negative flux ra tes) at this P addition (120 ug L-1). These results imply that none of the sediments in th e lakes are net re leasers of P to the water column at this P addition. However, even though sediments are taking up P, they still may not be taking out enough P to lower the P concentrations in the water column. Flux rates were significantly lower in Cypre ss Lake compared to Lakes Istokpoga (P<0.05). Lake Kissimmee P flux rates were significantly highe r than Cypress Lake, Lake Hatchineha, and Lake Tohopekaliga (p<0.05). At day 25, the mean P flux ranged fro m a rate low of -0.006 0.656 (mg m-2 d-1) in Lake Hatchineha to high rate of -0.808 0.069 (mg m-2 d-1) in Lake Istokpoga (Table 311). The negative P flux rates of all the la kes suggest that the sediments are retaining

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82 82Table 3-14. Percent change in SRP mg L-1 at 120 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP concentrations. n=6. -----------------SRP (mg L-1)-----------------------Percent Change %----Lake Initial Conc. (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d Tohopekaliga 0.125 0.113 0.002 0.081 0.015 0.062 0.014 -9.3 -35.2 -50.4 Cypress 0.129 0.115 0.006 0.097 0.012 0.097 0.074 -11.0 -24.8 -24.8 Hatchineha 0.131 0.123 0.023 0.120 0.040 0.129 0.065 -6.5 -8.4 -1.5 Kissimmee 0.122 0.088 0.001 0.013 0.014 0.007 0.010 -27.9 -89.3 -94.3 Istokpoga 0.123 0.090 0.005 0.043 0.026 0.028 0.033 -26.8 -65.0 -77.2

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83 phosphorus at day 25. Phosphorus flux rates were significantly lower in Lake Hatchineha compared to Lakes Istokpoga, Tohopekaliga, and Kissimmee (P<0.01). Table 3-15. Mean phosphorus flux rate (mg m-2 d-1) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at 120 ug L-1 P additions at 2, 7, and 25 days. ---------------------P flux mg m-2 d1---------------------Lakes 2 day 7 day 25 day Tohopekaliga -3.364 2.145 -1.54 0.499 -0.700 0.207 Cypress -2.443 1.149 -0.87 0.419 -0.527 0.262 Hatchineha -2.896 0.257 -1.05 1.07 -0.006 0.656 Kissimmee -6.821 1.032 -2.91 0.494 -0.817 0.077 Istokpoga -5.055 1.380 -2.20 0.884 -0.808 0.069 Discussion In general, the water column SRP con centration increased over time at no P additions, showing P release from the sediment and decreased at hi gh P additions (60 and 120 ug L-1), showing P retention by the sediment fo r all the lakes. Despite, retention by the sediments at high P additions, water column SRP levels remained high (Figure 3-9). This trend was observed for all lakes at day 2, 7, and 25, except on day 7 and 25 for Kissimmee. For Lake Kissimmee, the water column SRP concentration was much lower at high P additions (120 ug L-1) than at no P additions, which may be due to the trapping of P at the aerobic sediment surface to which P adsorption by iron occurs under oxidized conditions (Gachter and Meyer 1993, Keizer and Sinke 1992, Patrick and Khalid 1974). For example, Lake Kissimmee has a great con centration of Fe and Al in the sediment compared to any other metals (refer to chapte r 2; Table 2-2). This is important because Fe can either trap P at the aerobic sediment surface, preventing diffusive P release or bind P at the anaerobic sediment surface, resulting in P release from the sediments. In Lake

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84 Kissimmee, at P additions of 120 ug L-1, the mean water column SRP concentrations was lower at 0.013 0.014 (mg L-1) compared to 0.015 0.002 mg L-1 at no P additions at day 7. Day 70 0.04 0.08 0.12 0.16 060120 Spike ( ug L-1)WC SRP (mg L-1) Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga Day 20 0.06 0.12 0.18 060120Spike (ug L-1)WC SRP (mg L-1) Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga Day 250 0.04 0.08 0.12 0.16 060120Spike (ug L-1)WC SRP (mg L-1) Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga Figure 3-8. Water Column SRP (mg L-1) versus spike concentration ug L-1 for each lake. at day 2, 7, and 25.

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85 Although these lake sediments may have some capacity to retain P at high P loads (120 ug L-1), the lakes may still be a signifi cant source of P to downstream Lake Okeechobee due to high water column SRP con centrations. Studies have shown that despite sediment P retention by lakes unde r high P loads, a high water column SRP concentration was maintained ( Reddy et al. 2002 ) In efforts to restore water quality in the Upper Chain of Lakes and reduce P e xport to downstream Lake Okeechobee, the concentration of P in the water column should be taken into consideration. The sediment P flux rates showed that as the P load increased, there was a decrease in sediment P release. The minimum averag e P flux rate were (0.011) to a maximum of (-1.714) for the range of P additions. These P flux rates are comparab le to other P flux studies found in aquatic systems throughout the world for both sand and mud sediment types (Holdren and Armstrong 1980, Lofgren and Bostrom, 1989, Moore et al. 1998) (Table 3-16). The sands P flux rate had a minimum average P retention of -0.073 0.173 and a maximum flux rate of -2.00 1.06 mg m-2 d-1 for stations T10 and K1004; however, P release ranged between 0.091 0.701 to 0.269 0.021 mg m-2 d-1. All other station were mud and had a minimum av erage P flux of 0.005 0.293 and a maximum flux of -1.643 0.929 mg m-2 d-1. The stations characteri zed as mud had less than 62 u m of clay and silt in the sediments of the lake s and all other lakes were defined as sand (>63 u m) (Oui and McComb 2000). From the results, we found some differences in P flux rates between each lake; however, no significant correlations between P flux and any of the sediment P characteristics were found (i.e., nutrients, organic matter, bulk density, metals, EPCw). So, porewater equilibration data, not previous ly mentioned, was collected and regressed

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86 against the P flux rate at all P additions to see if a relationship could be found between P flux and porewater to maybe explain some of the differences found between each lake. There was a significant and negative relationship found between P flux and porewater SRP at no P and 15 ug L-1 additions (Table 3-17). Some studies have shown that lakes dominated by Fe, as in the Upper Chain of Lakes, may not show a relationship Table 3-16. Ranges of sedime nt-water SRP fluxes (mg m-2 d-1) Study Area Sediment Type Min Max Author Kissimmee River sand -0.26 3.35 Moore et al.1998 Taylor Creek sand -0.08 1.86 Moore et al.1998 Lake Vallentunasjon -1.80 22.5 Lofgren and Bostrom 1989 Lake Ontario 0.03 0.8 Holdren and Armstrong 1980 Lake Ontario 0.03 0.8 Holdren and Armstrong 1980 Lake Balaton 0.20 10.0 Lijklema et al. 1983 Lake Okeechobee mud -0.37 0.40 Moore et al.1998 Lake Okeechobee sand -0.02 0.11 Moore et al.1998 between porewater SRP gradient and P flux into aerobic water column (Premazzi and Provini 1985). At high P additions (120 ug L-1) there were a significant and negative relationship found at depth from 1-6, which suggest that ad sorption and precipitation in the oxidized zone, rather than diffusion from the reduced zone, was the process governing P exchange between the sediment and water column (Moore et al. 1998). The equilibrium water column phosphorus concentration (EPCw) can be used to determine the extent of which the internal lo ad will be released during restoration of a lake after external load reductions. The EPCw can be a useful tool for water managers to determine the water column SRP concentration for which sediments may act as a potential source of P to the overlying water column of a lake. The EPCw can predict P movement between the sediment and the in terstitial water (O lila and Reddy 1993).

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87 Table 3-17.Correlation between Porewater Equilb rators (Peepers) and P flux rate with the Pearson correlation on top and the P-valu e on the bottom in parentheses. All correlations are signif icant to P<0.05. n=10 Spike Levels No P added15 ug L-130 ug L-160 ug L-1120 ug L-1 Peeper (1-3 cm depth) 0.284 0.502 0.393 -0.184 -0.747 (0.427) (0.140) (0.261) (0.611) (0.013) Peeper (4-6 cm depth) 0.484 0.004 -0.170 -0.196 -0.643 (.157) (0.991) (0.639) (0.587) (<0.05) Peeper (7-10 cm depth) -0.719 -0.631 -0.186 -0.540 0.063 (0.01) (0.05) (0.606) (0.107) (0.863) Equilibrium Phosphorus Concentration Water managers can manage for the internal sediment P load by determining the EPCw of aquatic systems. For example, water managers may consider dredging a lake as a component of a restoration plan; however dr edging can be cost and labor intensive. Therefore, the EPCw can be used to determine which of these lakes should be dredged or if focus should be aimed at othe r activities during restoration. The SRP flux rates gave an idea of wh ich lake sediments were releasing or retaining P under the five water column concentrations added (0, 15, 30, 60, 120 ug L-1). The EPCw was calculated by plotting the SRP flux rate (mg m-2 d-1) against the initial water column SRP concentration (mg L-1) and taking the regression of those data points. The EPCw is the point that intercepts th e x-axis, where x = 0. The EPCw is defined as the P in solution that is in equilibrium with P in the solid phase (Olila and Reddy 1993). Sediments function as a net source of P at water column concentrations less than the EPCw and as a sink of P to the overlying water column at values gr eater than the EPCw.

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88 Phosphorus fluxed from the sediment to the water column in Lake Tohopekaliga for the sand station (T10) a nd mud station (T2) at EPCw less than 0.037 and 0.013 mg L-1, respectively (Table 3-18). This data suggest that the sandier station (T10) will release P first at an EPCw less than 0.037 mg L-1 compared to the muddier station (T2) at 0.013 mg L-1 (Figures 3-9). A study done on Lake Okeechobee found similar results in that the sand station had a higher EPCw than the mud station (Olila and Reddy 1993). There were no significant differences found between th ese two stations, maybe due to a small sample size. However, the sand station had less amounts of metals (Ca, Mg, Fe, and Al), total C, N, and P, as well as organic matter compared to the muds of Lake Tohopekaliga There were no signi ficant correlations found between EPCw with P flux or any sediment characteristic ( see Table 3-6 and Table 3-7). Table 3-18. Equilibrium Water Column Phosphorus Concentrations (EPCw) values determined at two stations in each lake Water column concentrations below these concentrations indicate conditi ons favorable for release of P n=3. Lake Station EPCw (mg L-1) Tohopekaliga T10 0.030 Tohopekaliga T2 0.013 Kissimmee K1004 0.013 Kissimmee K1012 0.015 Istokpoga I10007 0.044 Istokpoga I10004 0.024 Cypress C16 ~0 Cypress C15 0.007 Hatchineha H107 0.003 Hatchineha H103 0.004 The EPCw for the mud stations of Cypress Lake were ~0 and 0.007 (mg L-1) for stations C16 and C15, respectively (Figure 3-10 ). The mud stations of C15 will release P first at an EPCw less than 0.007 (mg L-1); while station C16 appear s to be retaining P at

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89 almost all water column SRP concentrations. There were not any si gnificant differences found in EPCw between the stations of Cypress Lake, maybe due to small sample size. y = -12.884x + 0.3765 R2 = 0.9685 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.000.020.040.060.080.100.120.14Water column SRP (mg L-1)Phosphorus flux (mg m-2d-1) EPCw=0.030 mg L-1 y = -16.925x + 0.2277 R2 = 0.9602 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw=0.013 (mg/L) Figure 3-9. Release/retention of P related to water column concentration for Lake Tohopekaliga-stations-T10 (top) and T2 (bottom). The EPCw for Lake Hatchineha were 0.003 and 0.004 (mg L-1) for stations H107 and H103, respectively (Figure 3-11). The mud station of H103, EPCw is slightly higher than the mud station of H103 and will release P first at an EPCw less than 0.004(mg L-1)

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90 compared to station H107. There were no significant differen ces found between the stations of Lake Hatchineha. y = -6.6443x 0.0006 R2 = 0.6402 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw =~0 mg L-1 y = -8.3402x 0.0586 R2 = 0.9334 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw = 0.007 mg L-1 Figure 3-10. Release/retention of P related to water column concentration for Lake Cypressstation C16 (top) and C15 (bottom).

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91 y = -11.547x + 0.0328 R2 = 0.9027 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 0.0000.0200.0400.0600.0800.1000.1200.140 Water column SRP (mg L-1)P retention/P release (mg m-2d-1) EPCw=0.003 mg L-1 y = -6.8991x + 0.0253 R2 = 0.5536 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention/ P release (mg m-2d-1) EPCW=0.004 mg L-1 Figure 3-11. Release/retention of P related to water column concentration for Lake Hatchineha-station H107 (t op) and H103 (bottom). Phosphorus fluxed from the sediment in La ke Kissimmee to the water column at EPCw less than 0.013 and 0.015 mg L-1 for stations (K1004) and (K1012), respectively (Figure 3-12). The mud stat ion of K1012 of Lake Kissimmee released P first compared to the sand station of K1004 at water colu mn SRP concentrations less than their respective EPCw. There were no statistical differe nces found between the stations of Lake Kissimmee, maybe due to small sample si ze. However, the mud station had greater amounts of metals, nutrients, and organic matter compared to the sand station of this lake.

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92 Phosphorus was released from the se diments in Lake Istokpoga at EPCw less than 0.044 mg L-1 and 0.024 mg L-1 at the mud station of I10007 and I10004, respectively (Figure 3-13). The mud stat ion of I10007 had greater amounts of organic matter, metals, and nutrients compared to the station I10004. y = -25.062x + 0.3237 R2 = 0.9979 -4 -3 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw = 0.013 mg L-1 y = -28.683x + 0.4425 R2 = 0.9912 -4 -3 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw = 0.015 mg L-1 Figure 3-12. Release/retention of P related to water column concentration for Lake Kissimmee-stations K1004 (t op) and K1012 (bottom).

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93 y = -17.585x + 0.7722 R2 = 0.9936 -3 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw = 0.044 mg L-1 y = -28.023x + 0.6703 R2 = 0.9642 -4 -3 -2 -1 0 1 2 0.000.020.040.060.080.100.120.14 Water column SRP (mg L-1)P retention / P release (mg m-2d-1) EPCw = 0.024 mg L-1 Figure 3-13. Release/retention of P related to water column concentration for Lake Istokpoga-station 10007 (top) and 10004 (bottom). In general, the stations with either low or ganic matter, low concentrations of metals or high bulk density tended to have a higher EPCw, in which the stations that met those characteristics were typically sand sedime nts. However, Lake Kissimmee was the exception, in which the sand station had a lower EPCw compared to the mud station. This

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94 may be due to the trapping of P at the aerob ic-anaerobic sediment water interface for the sand station (Keizer and Sinke 1992). The m ud station had high amounts of metal in the sediment, but greater amounts of phosphorus, su ggesting that sediment TP plays a major role. It appears that Lake Hatchi neha, Kissimmee and Cypress Lake have a low potential to release P to the water column at almost all water column concentrations; while Lakes Tohopekaliga and Istokpoga appear to be releasing P less than an average EPCw of 0.030 mg L-1. Overall Conclusion Internal sediment P load contributes heavily to the degradation of water quality in lakes even after external sources have b een reduced. Lake Tohopekaliga, Cypress, Hatchineha, Kissimmee, and Istokpoga are sh allow well mixed lakes that have been impacted by nonpoint and point sources of po llution since the 1970’s. Impacts in water quality within the Upper Chain of Lakes have influenced water quality levels in the downstream Lake Okeechobee. The sediments of each of the five lakes were characterized for bulk density, mass loss on ignition (LOI), total C, N, and P, as we ll as selected metals (Ca, Mg, Fe and Al). The bulk density ranged from 0.06-1.18 g cm-3 with sediment texture varying from organic mud to sand. The LOI values range d from 0-55% with the highest values representing the greatest cont ent of organic matter. The sands tended to have low organic matter and the muds typically had greater organic matter. The sites characterized as mud sediments, primarily had high nutrient levels (total P, total N, and total C) and organic matter c ontent. The sand sites typically had less nutrients (total P, total N a nd total C) and organic matter content. There were strong

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95 correlations of total P, N, C and bulk density to LOI. Total C and total N are generally found to be related to organic matter in se diments. A strong positive correlation between total P and LOI were found, but are generally not seen in lake sediments. This relationship suggests the importance of organics as a P reservoir a nd that the P source may be related to organic matter. Total P was well correlated with total N and total C, which also indicates that the P source may be related to organic matter. Th e mud sediments in each lake also contained greater amounts of Ca, Mg, Al, and Fe than the sands and are well correlated with total P. These selected metals are important to inor ganic P stability in many lake sediments. The inorganic P results suggest that the gr eatest portion of inorganic P was in the form most associated with Fe and Al (NaOH-Pi). The total organic P was proportionally greater in each lake than total inorganic P. The mud sediments contained the greatest amount of TP and P associated with organics and also had greater amounts of available or easily exchangeable P than the sands. Th e sand and mud sediments were not at all different in their distribution of P; however, the muds contained gr eater amounts of total P, so this sediment type may contribute more to P release to the overlying water column of a lake as shown from th e P characterization study. Phosphorus flux, at all P additions and the EPCw, were not significantly correlated with sediment characteristics, such as total P, N, and C, organic matter, bulk density, iron, aluminum, calcium, and magnesium. Howe ver, significant differences were found between some lakes. This difference may be due to the variability between the lakes due to both the mud and sand sediments.

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96 In general, the aerobic SRP flux rates sugge st that P release was highest at ambient water column SRP levels and decreased with an increase in P loading. However, an increase in P loading also maintained highe r water column SRP concentrations. Aerobic SRP flux rates indicate that sediments in all la kes, except Lake Hatchineha were releasing P to the water column at ambient water column SRP concentrations and retaining P at higher concentrations at day 7 and all lake were releasing P by the completion of the study (~25 days). Also, Lake Hatchineha and Cypress maintained a relatively low water column SRP concentration at no P additions at day 7 around 0.015 mg L-1 compared to concentrations greater than 0.095 mg L-1 at 120 ug L-1 P addition. The Equilibrium Water Column Phosphorus Concentration suggests that Cypress and Hatchineha have a low potential for releas e of SRP from the sediments as the water column SRP concentrations decrease over ti me and therefore may not be a potential source of P to downstream Lake Okeechobee. Therefore, the EPCw is a useful tool to determine which of these five lakes should be dredged or if focus should be aimed at other activities during restoration. It is important to note from the aerobic SRP flux and EPCw results that the stations with lower sediment TP were releasing P and had higher EPCw than the stations with higher sediment TP. The stations with the higher sediment TP and lower EPCw had a low potential to release SRP and te nded to be the muddier sedime nts. Therefore, just going out and measuring sediment TP does not give a good indication of wh ich sediments have potential to release P. So the EPCw can be a great tool to determine where future restoration activities should be focused.

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97 In general, the sandier lakes have the great est potential to release P compared to the muddier lakes. It should be recognized that the muddier lakes contained the greater amounts of organic matter, total C, N a nd P, as well as Ca, Mg, Fe, and Al.

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98 APPENDIX A PHOSPHORUS FRACTIONATION DATA Table A-1. Characterization of inorganic P forms (mg kg-1) in Tohopekaliga, Cypress, and Hatchineha raw data for sand sediments. Lake Station Labile-P Fe/Al-P Ca/Mg-P HA/FA-P Residue P Tohopekaliga 1 0.881 20.24 9.76 15.51 25.15 Tohopekaliga 4 0.421 12.04 5.30 6.61 20.36 Tohopekaliga 5 0.561 16.06 5.43 16.11 23.64 Tohopekaliga 6 1.647 15.52 4.87 19.85 13.62 Tohopekaliga 7 0.705 24.92 6.69 17.85 26.20 Tohopekaliga 9 3.057 24.29 9.15 16.38 13.47 Tohopekaliga 10 0.799 11.10 3.16 10.21 15.57 Cypress 11 0.587 12.57 13.33 5.26 17.48 Cypress 12 0.600 11.89 3.35 8.13 18.64 Cypress 14 0.544 18.71 4.03 19.81 21.51 Cypress 19 1.115 56.33 14.20 37.12 55.43 Hatchineha 102 0.660 16.03 9.12 24.20 21.08 Hatchineha 104 0.656 9.98 3.36 13.63 13.23 Hatchineha 105 0.742 14.36 9.03 24.60 15.87 Hatchineha 106 0.425 14.59 17.14 15.67 7.54 Hatchineha 108 0.504 22.45 7.49 31.44 6.08 HA=Humic Acid FA=Fulvic Acid

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99 Table A-2. Characterizati on of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga raw data for sand sediments. Lake Station Labile-P Fe/Al-P Ca/Mg-P HA/FA-P Residue P Kissimmee 1002 0.596 6.94 1.79 4.70 9.66 Kissimmee 1004 0.572 13.67 4.75 10.12 17.20 Kissimmee 1005 0.501 10.76 2.91 9.59 12.37 Kissimmee 1010 0.545 14.36 3.57 12.82 13.69 Istokpoga 10001 0.801 15.55 2.77 11.48 11.31 Istokpoga 10002 1.151 36.83 5.74 41.59 29.19 Istokpoga 10003 3.145 60.70 7.39 6.33 43.50 Istokpoga 10005 1.311 14.97 3.41 8.18 11.95 Istokpoga 10008 0.901 13.40 2.98 5.23 8.78 Istokpoga 10010 0.318 15.17 12.97 11.07 8.69 HA=Humic Acid FA=Fulvic Acid Table A-3. Characterizati on of inorganic P (mg kg-1) forms in Tohopekaliga, Cypress and Hatchineha raw data for mud sediments. Lake Labile-P Fe/Al-P Ca/Mg-P HA/FA-P Residue P Tohopekaliga 2 0.580 58.63 12.34 93.91 248.90 Tohopekaliga 3 1.381 151.23 42.75 150.29 202.02 Tohopekaliga 8 0.923 61.74 16.71 72.59 76.14 Cypress 13 1.322 67.53 19.88 92.47 99.07 Cypress 15 1.523 347.08 66.08 142.80 483.30 Cypress 16 1.622 571.77 9.95 238.13 705.06 Cypress 17 1.458 431.46 46.80 180.46 497.71 Cypress 18 0.858 52.44 10.85 62.53 172.65 Cypress 20 1.649 640.51 50.38 265.27 550.74 Hatch 101 2.168 274.50 106.72 357.25 360.87 Hatch 103 1.649 111.12 60.18 216.64 86.46 Hatch 107 1.574 375.71 62.10 233.68 498.17 Hatch 109 1.979 249.73 86.14 255.83 374.12 Hatch 110 1.609 414.77 33.29 86.25 555.43 HA=Humic Acid FA=Fulvic Acid

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100 Table A-4. Characterizati on of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga raw data for mud sediments. Lake Station Labile-P Fe/Al-P Ca/Mg-P HA/FA-P Residue P Kissimmee 1001 0.935 45.00 16.65 80.39 74.66 Kissimmee 1003 1.802 76.18 150.10 710.79 640.27 Kissimmee 1006 1.794 112.28 71.21 460.86 363.96 Kissimmee 1007 1.550 352.20 26.24 305.51 462.21 Kissimmee 1011 1.813 442.15 0.69 303.83 711.18 Kissimmee 1012 1.339 377.84 -1.27 248.10 614.24 Istokpoga 10004 1.197 281.44 51.19 174.76 191.21 Istokpoga 10006 2.126 78.92 20.88 116.14 65.16 Istokpoga 10007 3.175 169.96 30.17 206.56 164.72 Istokpoga 10009 1.784 185.15 38.37 338.19 223.52 HA=Humic Acid FA=Fulvic Acid

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101 APPENDIX B METALS DATA Table B-1. Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha raw data for sand sediments. Lake Station Ca Mg Fe Al Tohopekaliga 1 1158516841245124320 Tohopekaliga 4 951 17 672 774 Tohopekaliga 5 563 22 623 850 Tohopekaliga 6 547 42 1012 1071 Tohopekaliga 7 9619 16361364121335 Tohopekaliga 9 1236727561869636135 Tohopekaliga 10 9770 23691943631072 Cypress 11 988 19 993 1099 Cypress 12 242 0 705 780 Cypress 14 2222 30 672 929 Cypress 19 712 120 1911 2563 Hatchineha 102 641 63 801 1245 Hatchineha 104 951 17 672 774 Hatchineha 105 563 22 623 850 Hatchineha 106 547 42 1012 1071 Hatchineha 108 641 90 1745 1716 Table B-2. Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for sand sediments. Lake Station Ca MgFe Al Kissimmee 1002 204 0 1267 579 Kissimmee 1004 274 7 1403 801 Kissimmee 1005 196 0 954 517 Kissimmee 1010 273.53.6 1102.45630.2 Istokpoga 10001 1300 39 548 928 Istokpoga 10002 751 1201195 1612 Istokpoga 10003 1255 19 930 683 Istokpoga 10005 1404 72 880 817 Istokpoga 10008 278 20 424 539 Istokpoga 10010 3430 29 383 527

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102 Table B-3. Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha raw data for mud sediments. Lake Station Ca Mg Fe Al Tohopekaliga 2 3088 563 4800 10529 Tohopekaliga 3 1701 240 2549 5498 Tohopekaliga 8 1048 108 2207 2325 Cypress 13 1010 171 1988 2671 Cypress 15 6686 1360 17844 23532 Cypress 16 8221 1649 19970 28238 Cypress 17 7012 1590 18302 27209 Cypress 18 7125 1694 20049 29755 Cypress 20 935 127 1797 2653 Hatchineha 101 11585 1684 12451 24320 Hatchineha 103 4214 680 5510 8813 Hatchineha 107 9619 1636 13641 21335 Hatchineha 109 12367 2756 18696 36135 Hatchineha 110 9770 2369 19436 31072 Table B-4. Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for mud sediments. Lake Station Ca Mg Fe Al Kissimmee 1001 1631 206 3245 2597 Kissimmee 1003 8816 1225 26473 19372 Kissimmee 1006 5669 928 20217 13527 Kissimmee 1007 8180 1481 16544 26650 Kissimmee 1011 9044 1288 22000 17049 Kissimmee 1012 7303 1252 24150 20218 Istokpoga 10004 6257 1152 8238 10925 Istokpoga 10006 1702 363 2719 3262 Istokpoga 10007 3977 796 5653 6189 Istokpoga 10009 7400 1295 8161 9090

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103 APPENDIX C NUTRIENTS Table C-1. Characterizati on of nutrients (mg kg-1) in Tohopekaliga, Cypress, and Hatchineha raw data for sand sediments. Lake Station Total C Total N Total P Tohopekaliga 1 6.97 0.65 86.4 Tohopekaliga 4 4.08 0.32 52.8 Tohopekaliga 5 5.44 0.59 61.6 Tohopekaliga 6 6.20 0.63 48.2 Tohopekaliga 7 5.18 0.60 61.0 Tohopekaliga 9 7.56 0.83 88.5 Tohopekaliga 10 5.41 0.57 61.8 Cypress 11 7.87 0.79 59.1 Cypress 12 4.33 0.44 44.9 Cypress 14 6.09 0.63 64.2 Cypress 19 21.02 1.91 153.6 Hatchineha 102 7.84 0.72 84.8 Hatchineha 104 4.31 0.40 51.3 Hatchineha 105 12.95 1.29 40.2 Hatchineha 106 7.56 0.72 55.2 Hatchineha 108 11.99 1.02 111.0

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104 Table C-2. Characterizati on of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data for sand sediments. Lake Station Total C Total N Total P Kissimmee 1002 5.6 0.6 43.8 Kissimmee 1004 7.6 1.1 60.6 Kissimmee 1005 5.8 0.6 38.1 Kissimmee 1010 7.0 0.7 50.2 Istokpoga 10001 5.10 0.39 54.8 Istokpoga 10002 17.07 1.53 127.5 Istokpoga 10003 6.69 0.42 50.0 Istokpoga 10005 14.97 0.91 55.8 Istokpoga 10008 5.73 0.49 48.6 Istokpoga 10010 9.69 0.65 68.8 Table C-3. Characterizati on of nutrients (mg kg-1) in Tohopekaliga, Cypress and Hatchineha raw data for mud sediments. Lake Station Total C Total N Total P Tohopekaliga 2 57.87 4.54 422.9 Tohopekaliga 3 41.71 2.92 273.8 Tohopekaliga 8 22.07 2.01 224.2 Cypress 13 31.29 2.90 216.5 Cypress 15 139.9 12.43 1036.5 Cypress 16 200.52 19.43 1693.54 Cypress 17 164.7 14.57 1304.1 Cypress 18 201.6 18.36 1669.7 Cypress 20 21.37 2.19 181.0 Hatchineha 101 187.70 16.10 1121.3 Hatchineha 103 72.80 6.81 494.3 Hatchineha 107 180.5 17.77 1126.5 Hatchineha 109 127.5 13.67 1205.7 Hatchineha 110 197.1 19.60 1514.4

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105 Table C-4. Characterizati on of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data for mud sediments. Lake Station Total C Total N Total P Kissimmee 1001 51.77 4.32 225.3 Kissimmee 1003 272.5 26.52 1641.0 Kissimmee 1006 175.8 17.64 866.2 Kissimmee 1007 176.8 17.08 1232.03 Kissimmee 1011 293.6 26.42 1539.0 Kissimmee 1012 244.8 22.10 1332.9 Istokpoga 10004 127 8.51 721.37 Istokpoga 10006 56.67 4.51 294.8 Istokpoga 10007 95.66 7.68 555.23 Istokpoga 10009 179.3 13.69 778.4

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106APPENDIX D AEROBIC WATER COLUMN SRP DATA Table D-1. Water Column SRP for Lake Tohopekaliga under aerobic conditions for 25 days for st ation T10 (Coordinate x (461809 meters), y (3116800 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Station Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------ug L-1 0 0.1 1 4 7 12 18 25 T10 0 0.005 0.008 0.009 0.013 0.014 0.031 0.015 0.018 T10 0 0.005 0.007 0.008 0.013 0.017 0.030 0.023 0.037 T10 0 0.005 0.007 0.007 0.010 0.010 0.016 0.012 0.026 T10 15 0.020 0.024 0.023 0.018 0.014 0.023 0.015 0.018 T10 15 0.020 0.034 0.024 0.030 0.035 0.042 0.023 0.050 T10 15 0.020 0.024 0.025 0.029 0.032 0.037 0.012 0.038 T10 30 0.035 0.041 0.045 0.064 0.080 0.104 0.105 0.106 T10 30 0.035 0.034 0.033 0.032 0.033 0.042 0.035 0.036 T10 30 0.035 0.034 0.032 0.028 0.043 0.046 0.038 0.040 T10 60 0.065 0.064 0.061 0.061 0.055 0.066 0.065 0.065 T10 60 0.065 0.063 0.061 0.052 0.051 0.048 0.041 0.042 T10 60 0.065 0.062 0.059 0.049 0.042 0.036 0.028 0.028 T10 120 0.125 0.129 0.116 0.103 0.094 0.086 0.069 0.069 T10 120 0.125 0.126 0.112 0.101 0.091 0.084 0.067 0.070 T10 120 0.125 0.124 0.115 0.102 0.088 0.088 0.074 0.075

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107Table D-2. Water Column SRP for Lake T ohopekaliga under aerobic conditions for 25 days for station T2. (Coordinate x (460252 meters), y (3125825 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Station Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------ug L-1 0 0.1 1 4 7 12 18 25 T2 0 0.005 0.009 0.006 0.011 0.018 0.088 0.165 0.153 T2 0 0.005 0.008 0.010 0.020 0.027 0.026 0.008 0.013 T2 0 0.005 0.006 0.005 0.004 0.006 0.023 0.004 0.006 T2 15 0.020 0.020 0.019 0.011 0.015 0.021 0.005 0.009 T2 15 0.020 0.021 0.020 0.021 0.020 0.027 0.060 0.058 T2 15 0.020 0.020 0.020 0.013 0.012 0.019 0.024 0.035 T2 30 0.035 0.042 0.036 0.011 0.035 0.044 0.052 0.063 T2 30 0.035 0.034 0.033 0.021 0.012 0.010 0.011 0.014 T2 30 0.035 0.034 0.034 0.013 0.028 0.035 0.049 0.051 T2 60 0.065 0.059 0.060 0.052 0.039 0.023 0.009 0.012 T2 60 0.065 0.067 0.064 0.050 0.039 0.031 0.005 0.017 T2 60 0.065 0.072 0.063 0.057 0.053 0.041 0.014 0.015 T2 120 0.125 0.138 0.113 0.095 0.078 0.065 0.059 0.060 T2 120 0.125 0.115 0.111 0.111 0.081 0.089 0.049 0.065 T2 120 0.125 0.117 0.112 0.098 0.054 0.035 0.002 0.037

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108Table D-3. Water Column SRP for Cypress La ke under aerobic conditions for 25 days for station C16. Coordi nate x (469875 meters ), y (3106370 meters). All coordinates are Universal Mercat or, North American Datum 1983, Units meters, UTM Zone 17. Station Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------ug L-1 0 0.1 1 4 7 12 18 25 C16 0 0.009 0.017 0.014 0.019 0.023 0.035 0.031 0.041 C16 0 0.009 0.009 0.010 0.012 0.012 0.012 0.011 0.010 C16 15 0.024 0.023 0.022 0.021 0.017 0.015 0.013 0.014 C16 15 0.024 0.029 0.025 0.033 0.027 0.020 0.022 0.053 C16 15 0.024 0.026 0.025 0.024 0.017 0.015 0.019 0.054 C16 30 0.039 0.043 0.034 0.030 0.022 0.023 0.052 0.049 C16 30 0.039 0.044 0.037 0.036 0.035 0.032 0.032 0.037 C16 30 0.039 0.042 0.041 0.033 0.036 0.031 0.056 0.096 C16 60 0.069 0.076 0.063 0.068 0.056 0.058 0.052 0.040 C16 60 0.069 0.069 0.062 0.050 0.043 0.038 0.043 0.041 C16 60 0.069 0.069 0.062 0.054 0.047 0.042 0.039 0.082 C16 120 0.120 0.126 0.116 0.110 0.105 0.097 0.091 0.116 C16 120 0.120 0.128 0.122 0.128 0.108 0.102 0.097 0.083 C16 120 0.120 0.124 0.119 0.119 0.104 0.098 0.088 0.085

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109Table D-4. Water Column SRP for Cypress La ke under aerobic conditions for 25 days for station C15. Coordi nate x (468261 meters ), y (3105828 meters). All coordinates are Universal Mercat or, North American Datum 1983, Units meters, UTM Zone 17. Station Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------ug L-1 0 0.1 1 4 7 12 18 25 C15 0 0.009 0.008 0.007 0.010 0.009 0.009 0.009 0.011 C15 0 0.009 0.011 0.013 0.015 0.007 0.006 0.009 0.010 C15 15 0.024 0.028 0.022 0.018 0.016 0.015 0.012 0.026 C15 15 0.024 0.023 0.019 0.015 0.015 0.015 0.014 0.013 C15 30 0.039 0.037 0.035 0.037 0.030 0.028 0.034 0.025 C15 30 0.039 0.036 0.035 0.039 0.032 0.032 0.030 0.036 C15 30 0.039 0.038 0.036 0.039 0.019 0.021 0.018 0.025 C15 60 0.069 0.060 0.050 0.037 0.024 0.023 0.026 0.024 C15 60 0.069 0.067 0.062 0.066 0.040 0.024 0.034 0.114 C15 60 0.069 0.063 0.064 0.064 0.058 0.056 0.053 0.065 C15 120 0.120 0.122 0.107 0.091 0.074 0.054 0.040 0.037 C15 120 0.120 0.120 0.109 0.109 0.098 0.095 0.089 0.072 C15 120 0.120 0.120 0.115 0.111 0.097 0.084 0.068 0.050

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110Table D-5. Water Column SRP for Lake Ha tchineha under aerobic conditions for 25 da ys for station H107. Coordinate x (461341 meters), y (3098421 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------Station ug L-1 0 0.1 1 4 7 12 18 25 H107 0 0.011 0.013 0.009 0.012 0.008 0.006 0.010 0.006 H107 0 0.011 0.014 0.006 0.010 0.005 0.005 0.005 0.034 H107 0 0.011 0.012 0.004 0.011 0.015 0.041 0.092 0.082 H107 15 0.026 0.028 0.020 0.023 0.019 0.015 0.015 0.059 H107 15 0.026 0.025 0.023 0.026 0.021 0.035 0.034 0.067 H107 15 0.026 0.026 0.019 0.015 0.014 0.021 0.016 0.015 H107 30 0.041 0.041 0.033 0.036 0.029 0.029 0.040 0.148 H107 30 0.041 0.042 0.030 0.031 0.023 0.017 0.011 0.004 H107 30 0.041 0.039 0.034 0.036 0.034 0.042 0.065 0.126 H107 60 0.071 0.067 0.062 0.048 0.039 0.039 0.050 0.127 H107 60 0.071 0.066 0.054 0.044 0.033 0.028 0.032 0.092 H107 60 0.071 0.064 0.054 0.047 0.033 0.025 0.023 0.030 H107 120 0.131 0.124 0.115 0.113 0.120 0.127 0.147 0.148 H107 120 0.131 0.180 0.169 0.162 0.154 0.141 0.159 0.143 H107 120 0.131 0.120 0.110 0.091 0.034 0.067 0.064 0.058

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111Table D-6. Water Column SRP for Lake Ha tchineha under aerobic conditions for 25 da ys for station H103. Coordinate x (458082 meters), y (3100650 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Station Spike level ---------------------------Water Co lumn SRP (mg L-1)-----------------------------ug L-1 0 0.1 1 4 7 12 18 25 H103 0 0.011 0.012 0.011 0.013 0.014 0.016 0.045 0.075 H103 0 0.011 0.011 0.006 0.011 0.006 0.006 0.007 0.003 H103 0 0.011 0.017 0.008 0.013 0.010 0.011 0.028 0.022 H103 15 0.026 0.025 0.022 0.018 0.012 0.014 0.016 0.015 H103 15 0.026 0.027 0.025 0.029 0.022 0.020 0.016 0.012 H103 15 0.026 0.026 0.024 0.027 0.022 0.017 0.016 0.011 H103 30 0.041 0.038 0.036 0.037 0.052 0.079 0.058 0.041 H103 30 0.041 0.041 0.034 0.032 0.024 0.022 0.014 0.008 H103 30 0.041 0.041 0.037 0.035 0.051 0.080 0.103 0.074 H103 60 0.071 0.068 0.060 0.068 0.056 0.060 0.074 0.110 H103 60 0.071 0.069 0.061 0.064 0.039 0.030 0.024 0.016 H103 60 0.071 0.066 0.055 0.047 0.024 0.018 0.014 0.014 H103 120 0.131 0.120 0.109 0.104 0.093 0.076 0.060 0.043 H103 120 0.131 0.122 0.113 0.114 0.108 0.112 0.118 0.177 H103 120 0.131 0.129 0.119 0.117 0.102 0.090 0.177 0.207

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112Table D-7. Water Column SRP for Lake Kissimmee under aerobic conditions for 25 days for station K1004. Coordinate x (472394 meters), y (3084179 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Station Spike level -----------------------------------------Water Co lumn SRP (mg L-1)--------------------------------------------ug L-1 0 0.1 1 4 7 12 18 25 33 K1004 0 0.002 0.009 0.010 0.008 0.015 0.013 0.013 0.015 0.012 K1004 0 0.002 0.010 0.009 0.010 0.015 0.013 0.016 0.014 0.017 K1004 0 0.002 0.009 0.010 0.010 0.016 0.014 0.013 0.012 0.015 K1004 15 0.017 0.019 0.010 0.012 0.015 0.013 0.016 0.024 0.027 K1004 15 0.017 0.018 0.009 0.015 0.015 0.014 0.012 0.018 0.029 K1004 15 0,017 0.020 0.011 0.012 0.019 0.019 0.018 0.017 0.014 K1004 30 0.032 0.033 0.023 0.018 0.018 0.018 0.018 0.014 0.012 K1004 30 0.032 0.031 0.019 0.020 0.021 0.019 0.016 0.015 0.012 K1004 30 0.032 0.030 0.022 0.019 0.020 0.019 0.016 0.025 0.018 K1004 60 0.062 0.059 0.045 0.031 0.029 0.021 0.020 0.019 0.021 K1004 60 0.062 0.058 0.047 0.029 0.025 0.020 0.025 0.024 0.020 K1004 60 0.062 0.059 0.048 0.038 0.035 0.023 0.017 0.017 0.017 K1004 120 0.120 0.112 0.086 0.067 0.051 0.041 0.040 0.038 0.033 K1004 120 0.120 0.116 0.087 0.048 0.034 0.024 0.018 0.017 0.015 K1004 120 0.120 0.111 0.086 0.065 0.047 0.034 0.024 0.022 0.019

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113Table D-8. Water Column SRP for Lake Kissimmee under aerobic conditions for 25 days for station K1012. Coordinate x (473188 meters), y (3088426 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Spike level -----------------------------------------Water Co lumn SRP (mg L-1)--------------------------------------------Station ug L-1 0 0.1 1 4 7 12 18 25 33 K1012 0 0.002 0.011 0.013 0.011 0.015 0.016 0.016 0.019 0.020 K1012 0 0.002 0.010 0.010 0.011 0.017 0.014 0.014 0.016 0.020 K1012 0 0.002 0.008 0.010 0.008 0.012 0.015 0.014 0.015 0.017 K1012 15 0.017 0.017 0.010 0.015 0.018 0.019 0.015 0.015 0.016 K1012 15 0.017 0.019 0.011 0.009 0.015 0.014 0.015 0.014 0.009 K1012 15 0,017 0.018 0.010 0.015 0.018 0.015 0.016 0.016 0.013 K1012 30 0.032 0.034 0.020 0.015 0.020 0.016 0.013 0.014 0.010 K1012 30 0.032 0.031 0.021 0.019 0.022 0.021 0.018 0.017 0.018 K1012 30 0.032 0.031 0.021 0.019 0.023 0.018 0.014 0.014 0.016 K1012 60 0.062 0.055 0.043 0.022 0.019 0.017 0.015 0.016 0.014 K1012 60 0.062 0.058 0.043 0.031 0.029 0.020 0.015 0.014 0.012 K1012 60 0.062 0.060 0.047 0.027 0.026 0.024 0.021 0.019 0.017 K1012 120 0.120 0.108 0.089 0.062 0.052 0.040 0.028 0.020 0.014 K1012 120 0.120 0.110 0.090 0.055 0.038 0.026 0.023 0.020 0.017 K1012 120 0.120 0.108 0.088 0.033 0.029 0.019 0.018 0.018 0.016

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114Table D-9. Water Column SRP for Lake Is tokpoga under aerobic conditions for 25 da ys for station I10007. Coordinate x (472779 meters), y (3026915 meters). All coordi nates are Universal Mercator, North Am erican Datum 1983, Units meters, UTM Zone 17. Spike level -----------------------------------------Water Co lumn SRP (mg L-1)--------------------------------------------Station ug L-1 0 0.1 1 4 7 12 18 25 33 I10007 0 0.003 0.011 0.012 0.016 0.030 0.064 0.074 0.101 0.098 I10007 0 0.003 0.009 0.012 0.014 0.027 0.040 0.053 0.054 0.042 I10007 0 0.003 0.008 0.010 0.010 0.015 0.020 0.022 0.022 0.025 I10007 15 0.018 0.018 0.015 0.022 0.032 0.048 0.052 0.050 0.037 I10007 15 0.018 0.014 0.009 0.011 0.016 0.018 0.019 0.019 0.015 I10007 15 0.018 0.019 0.018 0.027 0.032 0.023 0.032 0.038 0.028 I10007 30 0.033 0.027 0.025 0.024 0.026 0.031 0.035 0.042 0.035 I10007 30 0.033 0.030 0.029 0.034 0.046 0.062 0.074 0.077 0.088 I10007 30 0.033 0.029 0.024 0.024 0.026 0.033 0.040 0.033 0.028 I10007 60 0.063 0.059 0.058 0.044 0.050 0.061 0.073 0.078 0.062 I10007 60 0.063 0.056 0.047 0.046 0.045 0.043 0.039 0.029 0.022 I10007 60 0.063 0.054 0.048 0.049 0.055 0.051 0.049 0.043 0.037 I10007 120 0.123 0.108 0.093 0.082 0.072 0.053 0.043 0.026 0.032 I10007 120 0.123 0.110 0.097 0.083 0.078 0.075 0.074 0.107 0.118 I10007 120 0.123 0.108 0.093 0.075 0.074 0.075 0.063 0.043 0.024

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115 Table D 10. Water Column SRP for Lake Istokpoga under aerobic conditions for 25 days for station I10004. Coordinate x (469916 meters), y (3030750 meters). All coordinates are Universal Mercator, North American Datum 1983, Units meters, UTM Zone 17. Spike level -----------------------------------------Water Column SRP (mg L 1 ) ----------------------------------Station ug L 1 0 0.1 1 4 7 12 18 25 33 I10004 0 0.003 0.014 0.018 0.017 0.021 0.018 0.013 0.016 0.019 I10004 0 0.003 0.012 0.017 0.014 0.017 0.016 0.015 0.016 0.014 I10004 0 0.003 0.012 0.0 13 0.014 0.018 0.019 0.015 0.018 0.014 I10004 15 0.018 0.013 0.012 0.017 0.020 0.024 0.020 0.018 0.017 I10004 15 0.018 0.016 0.014 0.015 0.019 0.018 0.015 0.018 0.017 I10004 15 0.018 0.013 0.012 0.015 0.018 0.015 0.017 0.017 0.024 I10004 30 0.033 0.025 0.018 0.020 0.022 0.020 0.019 0.020 0.017 I10004 30 0.033 0.031 0.024 0.027 0.032 0.035 0.039 0.045 0.063 I10004 30 0.033 0.029 0.024 0.019 0.022 0.018 0.017 0.020 0.021 I10004 60 0.063 0.058 0.050 0.047 0.045 0.042 0.035 0.043 0.036 I10004 60 0.063 0 .052 0.041 0.034 0.029 0.031 0.024 0.021 0.011 I10004 60 0.063 0.055 0.035 0.029 0.027 0.017 0.019 0.025 0.024 I10004 120 0.123 0.107 0.090 0.062 0.051 0.029 0.021 0.020 0.019 I10004 120 0.123 0.106 0.088 0.051 0.037 0.028 0.026 0.027 0.028 I10004 120 0.123 0.108 0.082 0.041 0.031 0.021 0.019 0.016 0.013

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116 APPENDIX E PRELIMINARY SURVEY Figure E-1. Sediment thickness map for Cypress Lake.

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117 Figure E-2. Sediment thickne ss map for Lake Hatchineha.

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118 Figure E-3. Sediment thickness map for Lake Istokpoga.

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119 Figure E-4. Sediment thickne ss map for Lake Kissimmee.

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120 Figure E-5. Sediment thickness map for Lake Tohopekaliga.

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121 Table E-1. Coordinates (x and y), water dept h, sediment depth and thickness for Cypress Lake. Units Meters. All coordinate s are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17. LAKE POINT_ID x y WATER_DEPT SED_DEPTH THICKNESS Cypress 1 468394 3107936 1.7 1.8 0.17 Cypress 2 468124 3107392 1.5 1.5 0.00 Cypress 3 468319 3107604 1.8 1.9 0.06 Cypress 4 468903 3107592 1.7 1.7 0.00 Cypress 6 467786 3107020 1.3 1.3 0.00 Cypress 7 468319 3106995 2.0 2.0 0.00 Cypress 8 468764 3106995 2.2 2.2 0.00 Cypress 9 469272 3106995 2.0 2.0 0.00 Cypress 11 467646 3106588 1.6 1.6 0.00 Cypress 12 468306 3106563 2.1 2.3 0.20 Cypress 13 468776 3106576 2.0 2.5 0.41 Cypress 14 469272 3106576 2.0 2.3 0.27 Cypress 15 469754 3106588 1.8 3.2 1.39 Cypress 17 466973 3106068 1.7 1.9 0.16 Cypress 18 467582 3106068 2.0 2.0 0.00 Cypress 19 468306 3106106 2.1 2.6 0.46 Cypress 20 468891 3106093 2.1 2.8 0.69 Cypress 21 469437 3106118 2.1 2.5 0.42 Cypress 22 466504 3105594 1.3 1.3 0.00 Cypress 23 467052 3105606 1.6 1.7 0.13 Cypress 24 467720 3105679 2.1 2.4 0.29 Cypress 25 468306 3105661 1.9 2.5 0.67 Cypress 26 468751 3105674 2.1 2.5 0.36 Cypress 27 469246 3105674 2.6 3.0 0.39 Cypress 28 469792 3105699 2.0 2.2 0.16 Cypress 30 467350 3105305 2.0 2.1 0.12 Cypress 31 468294 3105090 2.2 2.6 0.40 Cypress 32 469259 3105090 2.1 3.1 0.97 Cypress 33 470224 3105128 2.1 2.7 0.56 Cypress 34 466760 3104640 1.4 1.4 0.00 Cypress 35 467430 3104632 1.9 1.9 0.00 Cypress 36 468306 3104645 2.0 2.1 0.06 Cypress 37 469132 3104632 2.2 2.2 0.00 Cypress 38 469945 3104658 2.1 3.6 1.51 Cypress 39 467204 3104346 1.6 1.6 0.00 Cypress 40 468294 3104163 1.6 1.6 0.00 Cypress 41 468916 3104239 1.6 1.6 0.00 Cypress 42 469653 3104277 1.7 1.7 0.00

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122 Table E-2. Coordinates (x and y), water dept h, sediment depth and thickness for Lake Hatchineha. Units Meters. All c oordinates are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17. LAKE POINT_ID x y WATER_DEPT SED_DEPTH THICKNESS Hatchineha 43 455556 3102621 2.3 2.6 0.31 Hatchineha 44 455638 3101536 1.7 1.8 0.02 Hatchineha 45 455851 3101856 1.5 2.2 0.66 Hatchineha 46 456065 3102222 1.3 3.6 2.22 Hatchineha 47 456354 3102709 2.6 3.5 0.90 Hatchineha 48 456629 3103197 2.3 2.8 0.44 Hatchineha 49 457156 3100995 1.6 1.6 0.00 Hatchineha 50 457620 3101555 1.9 1.9 0.00 Hatchineha 51 457391 3101216 2.7 2.8 0.07 Hatchineha 52 457756 3100286 1.7 1.7 0.00 Hatchineha 53 458305 3100728 2.6 2.6 0.06 Hatchineha 54 458752 3101186 1.6 1.6 0.00 Hatchineha 55 458305 3099463 2.7 2.7 0.00 Hatchineha 56 458778 3099753 1.9 1.9 0.00 Hatchineha 57 459296 3100042 1.9 1.9 0.00 Hatchineha 58 459691 3100236 1.4 1.4 0.00 Hatchineha 59 458747 3098503 2.0 2.5 0.47 Hatchineha 60 459174 3098777 2.0 2.0 0.00 Hatchineha 61 459661 3099113 2.5 3.0 0.51 Hatchineha 62 460119 3099494 2.6 3.2 0.60 Hatchineha 63 460454 3099783 0.8 2.3 1.46 Hatchineha 64 460848 3100033 1.1 1.7 0.63 Hatchineha 65 459373 3097829 1.4 1.4 0.00 Hatchineha 66 459890 3098031 2.1 2.6 0.47 Hatchineha 67 460362 3098473 2.3 4.0 1.76 Hatchineha 68 460820 3099021 2.5 3.2 0.67 Hatchineha 69 461109 3099311 1.6 1.9 0.27 Hatchineha 70 461216 3098183 2.5 3.5 0.95 Hatchineha 71 461536 3098564 2.6 4.0 1.41 Hatchineha 72 461780 3098823 2.3 3.3 0.91 Hatchineha 73 462463 3097855 2.2 2.4 0.18 Hatchineha 74 462923 3098366 2.1 2.1 0.00 Hatchineha 75 463837 3098427 2.8 5.9 3.10 Hatchineha 76 463426 3098808 3.1 5.5 2.43 Hatchineha 78 463909 3099344 1.9 2.3 0.41 Hatchineha 79 463959 3099799 1.8 2.3 0.48 Hatchineha 81 464556 3100131 1.8 3.3 1.47 Hatchineha 82 456370 3101429 1.9 1.9 0.00 Hatchineha 83 456796 3102298 2.5 2.5 0.00

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123 Table E-3. Coordinates (x and y), water dept h, sediment depth and thickness for Lake Istopokga. Units Meters. All coordinate s are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17. LAKE POINT_ID x y WATER_DEPT SED_DEPTH THICKNESS Istokpoga 84 473078 3035417 1.0 1.0 0.02 Istokpoga 85 472897 3034454 1.1 1.2 0.10 Istokpoga 86 471814 3033592 1.3 1.4 0.04 Istokpoga 87 472697 3033552 1.7 1.8 0.14 Istokpoga 88 473539 3033532 1.5 1.6 0.07 Istokpoga 89 474281 3033532 1.4 1.9 0.44 Istokpoga 90 469990 3032489 2.0 2.3 0.36 Istokpoga 91 471153 3032489 1.7 2.4 0.70 Istokpoga 92 472456 3032629 1.8 1.9 0.07 Istokpoga 93 473774 3032152 2.0 2.2 0.21 Istokpoga 94 472236 3031667 0.7 0.7 0.00 Istokpoga 95 467543 3031085 2.0 2.3 0.35 Istokpoga 96 469148 3030985 2.0 3.7 1.70 Istokpoga 97 470712 3030905 2.1 2.6 0.59 Istokpoga 98 472075 3030845 1.5 1.6 0.08 Istokpoga 99 473419 3030845 1.4 1.5 0.03 Istokpoga 100 474602 3030824 1.5 1.6 0.05 Istokpoga 101 471835 3029882 2.1 2.2 0.10 Istokpoga 102 469316 3028875 1.5 1.8 0.30 Istokpoga 103 470459 3028913 2.1 2.5 0.38 Istokpoga 104 471554 3028959 2.1 2.2 0.12 Istokpoga 105 472974 3029028 2.1 2.1 0.01 Istokpoga 106 474193 3029104 1.1 1.1 0.02 Istokpoga 107 471313 3028017 1.9 1.9 0.04 Istokpoga 108 471454 3027074 2.4 2.7 0.30 Istokpoga 109 470090 3026513 1.5 1.6 0.07 Istokpoga 110 471514 3026272 2.4 3.4 1.05 Istokpoga 111 473118 3025972 1.2 1.3 0.06 Istokpoga 112 474450 3025598 2.0 2.1 0.19 Istokpoga 113 475785 3025410 1.6 1.6 0.07 Istokpoga 114 471566 3025789 1.3 1.7 0.42 Istokpoga 115 469767 3024829 2.5 3.1 0.53 Istokpoga 116 474155 3024151 1.0 1.0 0.00 Istokpoga 117 471066 3023704 2.0 2.7 0.71 Istokpoga 118 473126 3023312 2.1 2.3 0.20 Istokpoga 119 471333 3022763 2.2 2.7 0.46 Istokpoga 120 469308 3021881 2.5 2.7 0.24 Istokpoga 121 470319 3021619 2.0 2.1 0.10 Istokpoga 122 471113 3021821 2.0 2.1 0.10 Istokpoga 123 472075 3021780 2.4 3.1 0.70 Istokpoga 124 470932 3020717 2.1 3.1 0.98

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124 Table E-4. Coordinates (x and y), water dept h, sediment depth and thickness for Lake Kissimmee. Units Meters. All coordinates are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17. LAKE POINT_ID x y WATER_DEPT SED_DEPTH THICKNESS Kissimmee 125 466885 3092614 1.6 1.8 0.20 Kissimmee 126 467751 3092117 2.5 2.7 0.22 Kissimmee 127 467337 3090009 2.2 2.4 0.21 Kissimmee 128 467955 3090834 2.6 2.9 0.30 Kissimmee 129 469123 3091164 2.7 3.7 0.98 Kissimmee 130 469148 3091961 2.7 3.6 0.92 Kissimmee 131 469761 3092623 2.7 2.9 0.21 Kissimmee 132 470493 3090191 2.0 2.0 0.04 Kissimmee 133 472885 3090012 3.1 3.2 0.10 Kissimmee 134 475676 3090011 2.9 2.9 0.00 Kissimmee 135 471859 3088226 2.3 2.3 0.06 Kissimmee 136 473171 3088393 3.8 5.0 1.27 Kissimmee 137 474532 3088570 3.2 3.9 0.67 Kissimmee 138 476611 3087923 3.3 3.3 0.00 Kissimmee 139 472285 3087011 3.1 3.1 0.00 Kissimmee 140 477283 3086160 4.1 4.4 0.30 Kissimmee 141 470218 3086059 4.2 6.5 2.25 Kissimmee 142 472077 3085831 4.1 7.6 3.56 Kissimmee 143 473257 3085659 3.8 5.4 1.59 Kissimmee 144 474686 3085478 4.2 5.7 1.45 Kissimmee 145 476235 3085236 5.4 6.2 0.77 Kissimmee 146 477552 3085059 3.8 4.6 0.78 Kissimmee 147 470790 3084821 3.4 3.7 0.26 Kissimmee 148 471695 3084287 4.1 6.0 1.92 Kissimmee 149 473123 3084582 3.8 5.8 1.98 Kissimmee 150 471457 3083011 4.0 4.4 0.35 Kissimmee 151 477810 3084249 4.4 5.1 0.75 Kissimmee 152 478152 3083335 4.4 4.7 0.31 Kissimmee 153 478476 3082382 3.9 3.9 0.00 Kissimmee 155 479143 3080496 3.2 3.3 0.09 Kissimmee 156 478755 3078961 2.7 2.8 0.09 Kissimmee 157 477731 3080796 3.0 3.1 0.03 Kissimmee 158 476838 3091203 3.5 4.3 0.80 Kissimmee 159 475989 3091795 3.6 5.6 2.05 Kissimmee 160 475078 3092491 2.7 4.8 2.15 Kissimmee 161 474382 3093312 1.8 4.3 2.58 Kissimmee 162 473495 3093945 2.3 3.1 0.80 Kissimmee 163 472382 3094668 2.4 2.8 0.39 Kissimmee 164 471467 3095158 3.1 5.0 1.94 Kissimmee 165 470599 3095775 2.8 6.0 3.18

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125 Table E-5. Coordinates (x and y), water depth, sediment depth and thickness for Lake Tohopekaliga. Units Meters. All co ordinates are Universal Transverse Mercator, North American Datum 1983, UTM Zone 17. LAKE POINT_ID x y WATER_DEPT SED_DEPTH THICKNESS Tohopekaliga 166 460511 3128715 2.3 2.7 0.41 Tohopekaliga 167 460966 3129050 1.8 1.8 0.00 Tohopekaliga 168 462024 3128594 1.4 2.6 1.23 Tohopekaliga 169 460627 3127155 3.0 3.4 0.35 Tohopekaliga 170 461781 3126352 2.6 3.5 0.92 Tohopekaliga 171 459865 3125631 2.7 2.8 0.12 Tohopekaliga 172 461347 3125038 2.8 2.8 0.02 Tohopekaliga 173 459250 3124176 2.5 2.8 0.26 Tohopekaliga 174 461601 3124191 2.7 2.7 0.00 Tohopekaliga 175 459759 3123696 2.2 2.2 0.00 Tohopekaliga 176 460621 3123639 2.3 2.3 0.00 Tohopekaliga 177 461516 3123472 2.3 2.3 0.00 Tohopekaliga 178 462621 3124422 2.5 2.8 0.29 Tohopekaliga 179 463900 3124294 2.6 3.0 0.40 Tohopekaliga 180 464463 3123579 2.9 3.1 0.15 Tohopekaliga 181 465244 3123220 2.3 2.3 0.00 Tohopekaliga 182 461431 3122710 2.2 2.2 0.00 Tohopekaliga 183 460366 3122075 3.5 3.6 0.16 Tohopekaliga 184 461377 3121896 3.4 3.4 0.00 Tohopekaliga 185 462417 3121800 2.4 2.4 0.00 Tohopekaliga 186 461304 3121016 2.5 2.5 0.00 Tohopekaliga 187 459992 3120127 3.3 3.5 0.21 Tohopekaliga 188 461220 3120127 2.8 2.8 0.00 Tohopekaliga 189 462363 3120127 2.6 2.6 0.00 Tohopekaliga 190 461220 3119154 3.5 4.2 0.74 Tohopekaliga 191 462278 3118519 2.9 2.9 0.00 Tohopekaliga 192 461389 3118265 3.2 3.2 0.00 Tohopekaliga 193 460500 3118053 3.2 3.2 0.00 Tohopekaliga 194 461897 3117460 2.9 2.9 0.00 Tohopekaliga 195 462490 3116867 3.0 3.0 0.00 Tohopekaliga 196 464183 3116825 2.7 2.7 0.05 Tohopekaliga 197 463297 3116263 3.0 3.0 0.00 Tohopekaliga 198 462827 3115015 2.5 2.6 0.05 Tohopekaliga 199 463844 3115682 3.4 3.5 0.13 Tohopekaliga 200 465856 3116942 2.3 2.3 0.01 Tohopekaliga 201 465538 3116275 2.8 3.0 0.17 Tohopekaliga 202 465241 3115682 3.0 4.3 1.29 Tohopekaliga 203 464733 3115089 3.0 4.8 1.75 Tohopekaliga 204 464268 3114497 2.9 4.0 1.01 Tohopekaliga 205 463675 3113819 2.6 2.8 0.14 Tohopekaliga 206 465834 3114624 2.8 4.3 1.49

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126 APPENDIX F SEDIMENT TYPE AND COORDINATES Table F-1. Coordinates (x and y) and sediment type for stations chosen to sample for Lake Tohopekaliga and Cypress Lake. n= 10. All coordinates are Universal Transverse Mercator, North American Datum 1983, units meters, UTM zone 17. x_coordy_coord Sediment Lake Station m m Type Tohopekaliga 1 460428 3128014sand Tohopekaliga 2 460252 3125825mud Tohopekaliga 3 463507 3124122sand Tohopekaliga 4 465599 3122677muddy sand Tohopekaliga 5 461210 3120234muddy sand Tohopekaliga 6 462578 3115288sand Tohopekaliga 7 467040 3116082sand Tohopekaliga 8 465283 3113566sand Tohopekaliga 9 464884 3116960N/A Tohopekaliga 10 461809 3116800sand Cypress 11 466763 3105596muddy sand Cypress 12 467652 3106625sand Cypress 13 468416 3108126organic floc Cypress 14 469384 3107171organic sand Cypress 15 468261 3105828organic Cypress 16 469875 3106370organic Cypress 17 469281 3105777organic Cypress 18 469875 3104912organic sand Cypress 19 468454 3104563organic sand Cypress 20 467125 3104718organic sand

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127 Table F-2. Coordinates (x and y) and sediment type for stations chosen to sample for Lake Hatchineha and Kissimmee Lake. n=10. All coordinates are Universal Transverse Mercator, North American Datum 1983, units meters, UTM zone 17. x_coord y_coord Sediment Lake Station m m Type Hatchineha 101 456093 3102454 organic Hatchineha 102 456867 3101718 muddy sand Hatchineha 103 458082 3100650 organic/sand Hatchineha 104 459555 3098090 sand Hatchineha 105 459997 3099084 sand Hatchineha 106 460421 3099802 muddy sand Hatchineha 107 461341 3098421 organic Hatchineha 108 462305 3098079 muddysand Hatchineha 109 464275 3100018 organic Hatchineha 110 463478 3098587 organic Kissimmee 1001 479734 3078286 organic sand Kissimmee 1002 478183 3081336 muddy sand Kissimmee 1003 477253 3084902 organic floc Kissimmee 1004 472394 3084179 organic floc Kissimmee 1005 474410 3086763 muddy sand Kissimmee 1006 476219 3088882 organic Kissimmee 1009 468156 3091828 organic Kissimmee 1010 471937 3094508 muddy sand Kissimmee 1011 474824 3092707 organic Kissimmee 1012 473188 3088426 organic

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128 Table F-3. Coordinates (x and y) and sediment type for stations chosen to sample for Lake Istokpoga Lake. n=10. All coor dinates are Universal Transverse Mercator, North American Datu m 1983, units meters, UTM zone x_coord y_coord Sediment Lake Station m m Type Istokpoga 10001 472488 3033861 muddy sand Istokpoga 10002 474604 3032492 organic sand Istokpoga 10003 466847 3030833 muddy sand Istokpoga 10004 469916 3030750 organic Istokpoga 10005 473484 3030211 muddy sand Istokpoga 10006 476553 3028469 organic Istokpoga 10007 472779 3026915 organic Istokpoga 10008 470858 3024780 organic/sand Istokpoga 10009 471368 3021417 organic floc Istokpoga 10010 474147 3024196 muddy sand

PAGE 145

129 LIST OF REFERENCES Anderson, J.M. 1976. An ignition method fo r determination of phosphorus in lake sediments. Water Resource 10:329-331. Backer, L. 2002. Cyanobacterial harmful algal blooms (CyanoHABs): developing a public health response. Lake Reservoir Management 18(1):20-31. Barbanti, A., M.C. Bergamini, F.Frascari, S. Miserocchi, and G.Rosso. 1994. Critical aspects of sedimentar y phosphorus chemical fractionation. J. Environ. Qual. 23:1093-1102. Bostrom, B. and K. Pettersson. 1982. Di fferent patterns of P release from lake sediments in laboratory experi ments. Hydrobiologia 92:415-529. Carpenter, S. 1983. Submersed macrophyte comm unity structure and internal loading: relationship to lake ecosystem productivity and succession. In Lake Restoration Protection and Management. Proceedings of the 2nd Annual Conference, North American Lake Management Societ y. October 1983. Vancouver, British Columbia. Carpenter, S., N.F. Caraco, D.L. Correll, R. Howarth, A.N. Sharpley, and N.H. Smith. 1998. Nonpoint pollution of surface wate r with phosphorus and nitrogen. Issues in Ecology no. 3. Change, S.C. and M.L. Jackson. 1957. Fract ionation of soil phosphorus. J. Soil Sci. 84:13-144. Edmondson, W.T. and J.T. Lehman. 1981. The e ffect of changes in the nutrient income on the condition of Lake Washingt on. Limnol. Oceanogr. 26:1-29. Effler, S.W., S.M. O’Donnell, D.A. Mathews, and C.M. Mathews. 2002. Limnological and loading information and a phosphor us total maximum daily load (TMDL) analysis for onondaga lake. Lake an d Reservoir Management. 18(2):87-108. Farnham, R.S. and M.R. Finney. 1965. Classi fication and properties of organic soils. Adv. Agron. 17:115-162.

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130 Faulkner, S.P. and C.J. Richardson. 1989. P hysical and chemical characteristics of freshwater wetland soils. In D.A. Hammer (ed) Constructed Wetlands for Wastewater Treatment: Municipal, Industr ial and Agricultural. Lewis Publishers, Chelsea, MI. Fisher, M.M. and K.R. Reddy. 2001. Phosphor us flux from wetland soils affected by long-term nutrient loading. J. Environ. Qual. 30:261-271. Gachter, R. and J.S. Meyer. 1993. The ro le of microorganism in mobilization and fixation of phosphorus in sediments. Graetz, D. and V. Nair. 1999. Inorganic form s of phosphorus in soils and sediments. In Phosphorus Biogeochemistry of Subtropi cal Ecosystems. CRC Press, Boca Raton, FL. p. 171-186. Havens, K.E. 1997. Water levels and tota l phosphorus in Lake Okeechobee. Lake and Reservoir Management. 13(1):16-25. Havens, K.E. and R.T. James. 1997. A crit ical evaluation of phos phorus management goals for Lake Okeechobee, Florida, USA. Lake and Reserv. Manage. 13(4): 292-301. Havens, K.E., T.L. East, J. Marcus, P. Essex, B. Bolan, S. Raymond, J. R. Beaver. 2000. Dynamics of the exotic Daphnia lumho ltzii and native macrozooplankton in a subtrophical chain of lakes in Florida, USA. Freshwater Biology. Volume 45(1) page 21. Havens, K.E. and W.W.Walker, Jr. 2002. Development of a total phosphorus concentration goal in the TDML pr ocess for Lake Okeechobee, Florida USA). Lake and Reserv. Manage. 18(3):227-238. Hieltjes, A.H.M. and L. Lijklema. 1980. Fractionation of inor ganic phosphates in calcareous sediments. J. Environ. Qual. 9:405-407. Holdren, G.C. Jr. and Armstrong, D.E. 1980. Factors affecting phosphorus release from intact lake sediment cores. Envi ronmental Science and Technology. 14:79-87. Istvanovics, V. 1988. Seasonal variation of phosphorus release from the sediments of shallow Lake Balaton (Hungary). Wat. Res. Vol 22(12):1473-1481. Ivanoff, D.B., K.R. Reddy, and S. Robinson. 1998. Chemical fractionation of organic phosphorus in selected histosol s. Soil Science 163(1):36-45.

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131 James, R. T., K. O’Dell, and B. Jones. 1992. Water quality improvements of Lake Tohopekaliga in response to lake ma nagement. Kissimmee and Okeechobee Systems Research Division, Research a nd Appraisal Division, Department of Research, South Florida Water Manageme nt District, 3301 Gun Club Road, West Palm Beach, Florida 33416-4680. JMP Statistics, Version 4. 2001. SAS Institute Inc., Cary, NC. Kamp-Nielsen, L. 1974. Mud-water exchange of phosphate and other ions in undisturbed sediment cores and factors affecting exchange rates. Arch. Hydrobiol. 73:218-237. Keizer, P. and A.J.C. Sinke. 1992. Phosphorus in the sediment of the Loosdrecht lakes and its implications for lake restorat ion perspectives. Hydrobiologia 233:39-50. Lijklema, L., Gelenscer, P. and Szilagyi, F. 1983. Sediments and sediment-water interaction: In: L. Somlyody, S. Herodek and J. Fischer (Editors), Eutrophication of Shallow Lakes: Modeling and Management. Internatl. Institute for Applied Systems Analysis, Laxenburg, Austria, pp. 81-100. Lofgren, S. and B. Bostrom. 1989. Intersti tal water concentrati on of phosphorus, iron, and manganese in a shallow eutrophic Swedish lake-Implications for phosphorus cycling. Wat. Res. Vol 23(9):1115-1125. Marsden, M.W. 1989. Lake restoration by re ducing the external P loading: The influence of sediment P releas e. Freshwater Biol. 21:139-162. McArthur, W. M. 1991. Refe rence soils of south-western Australia. Department of Agriculture, Western Australia, Perth. Australia. Moore, P.A. Jr., K.R. Reddy, and D.A. Graet z. 1991. Phosphorus geochemistry in sediment-water column of a hypereutr ophic lake. J. Envi ron. Qual. 20:869-875. Moore, P.A. Jr., K.R. Reddy, and M.M. Fisher. 1998. Phosphorus flux between sediment and overlying water in Lake Okeechobee, Florida: Spatial and Temporal Variations. J. Environ. Qual. 27:1428-1439. Mortimer, C.H. 1941. The exchange of dissolv ed substances between mud and water in lakes. I. J. Ecol. 29:280-329. Noges, P. and A. Kisand. 1999. Horizontal distribution of sediment phosphorus in shallow eutrophic Lake Vortsjarv (Est onia). Hydrobiolog ia 408/409: 167-174.

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132 Nordin, R.N. 1983. Changes in water quality of Skaha Lake, British Columbia, following reduction in phosphorus loading. In Lake Restora tion Protection and Management. Proceedings of the 2nd Annual Conference, North American Lake Management Society. October 1983. Vancouver, British Columbia. Olila, O.G. and K.R. Reddy. 1993. Phosphrus sorption characteristics of sediments in shallow eutrophic lakes of Florid a. Arch. Hydrobiol 129(1):45-65. Olila, O.G., K.R. Reddy, and W.G. Harris. 1995. Forms and distri bution of inorganic phosphorus in sediments of two shal low eutrophic lakes in Florida. Hydrobiologia 302:147-161. Oui, S. and A. McComb. 2000. Properties of sediment phosphorus in seven wetlands of Swan Coastal Plain, South-Western Au stralia. Wetlands 20(2):267-279. Patrick, W.H. and R.A. Khalid. 1974. P hosphate release and sorption by soils and sediments: Effects of Aerobic an Anaerobic Conditions. Science 53-55 Penn, M.R. and M.T. Auer. 1997. Seasonal variability in phosphorus speciation and deposition in a calcareous, eutroph ic lake. Marine Geology 139:47-49. Pettersson, K. 1998. Mechanisms for inte rnal loading of phosphorus in lakes. Hydrobiologia 373/374: 21-25. Petterson, K. and B. Bostrom. 1985. Phosphor us exchange between sediment and water in Lake Balaton. In Sediments and Water Interactions. P. 427-435. Pierzynksi G.M., Sims J.T., and Vance G.F. 2000. Soils and Environmental Chemistry 2nd ed. Boca Raton. CRC Press Chapter 5. Premazzi, A. and A. Provini. 1985. Internal load ing in lakes: A different approach to its evaluation. Hydrobiologia 120:23-33. Reddy, K.R., M.M. Fisher, and D. Ivanoff. 1996. Resuspension and diffusive flux of nitrogen and phosphorus in a hypereutrophi c lake. J. Environ. Qual. 25:363-371. Reddy, K.R., O.A. Diaz, L.J. Scinto, and M. Agami. 1995. Phosphorus dynamics in selected wetlands and streams of th e Lake Okeechobee basin. Ecological Engineering 5:183-207. Reddy, K.R., R.H. Kadlec, E. Flaig and P. M. Gale. 1999. Phosphorus retention in streams and wetlands: A review: Critical Reviews in Environ. Sci. and Tech. 29(1):83-146.

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133 Reddy, K.R., Y. Wang, M.M. Fisher, J.R. White 2002. Influence of simulated sediment dredging on internal phosphorus load in a subtropical shallow lake. In Potential Impacts of Sediment Dredging on Internal Phosphorus Load in Lake Okeechobee. Summary Report Prepared for the South Florida Water Management District, 3301 Gun Club Road, West Palm Beach, Florida 33416-4680. Reddy, K.R., Y. Wang, W.F. DeBusk, M.M. Fi sher, and S. Newman. 1998. Forms of soil phosphorus in selected hydrologic units of the Florida ever glades. Soil Sci. Soc. Am. J. 62:1134-1147. Ruttenberg, K.C. 1992. Development of a sequential extraction method for different forms of phosphorus in marine sedime nts. Limnol. Oceanogr. 37:1460-1482. Rydin, E. 2000. Potentially mobile phosphorus in Lake Erken sediment. Wat. Res. 34(7):2037-2042. Sharpley, A.N., T. Daniel, T. Sims, J. Lemunyon, R. Stevens, and R. Parry. 1999. Agricultural phosphorus and eutrophicati on. U.S. Department of Agriculture, Agricultural Research Service, ARS-149, 42 pp. Smith, V.H., and J. Shapiro. 1981. Chlorophyllphosphorus relations in individual lakes. Their importance to lake restoration st rategies. Environ. Sci. Technol. 15:444451. South Florida Water Management Dist rict (SFWMD). 2001. Surface water improvement and management (SWIM) pl an update for Lake Okeechobee. South Florida Water Management Dist rict, West Palm Beach, FL. Syers, J.K., R.F. Harris, and D.E. Arms trong. 1973. Phosphate chemistry in lake sediments. Journal of Environmental Quality 2:1-14. United States Army Corps of Engineers (USA CE). 1996. Central and southern Florida project, Kissimmee River headwater revitalization pr oject-integrated project modification report and supplement to the fi nal environmental impact statement. U.S. Army Corps of Engineers, Jack sonville District, Jacksonville, FL. United States Environmental Protection Agency (USEPA) 600/4-79-020. 1983. Methods of chemical analyses of water and wastes. Environ. Monit. Support Lab., Cincinnati, OH. United States Environmental Protecti on Agency (USEPA) 600/R-93/100. 1993. Methods of chemical analysis of water and wastes. Environ. Monit. Support Lab., Cincinnati, OH.

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134 United States Environmental Protection Agency (USEPA). 1991a. Guidance for water quality-based decisions: Th e TMDL process. EPA 440-4-91-001. Office of Water, Washington, D.C. United States Environmental Protection Ag ency (USEPA). 1996. Environmental indicators of water quality in the United States. EPA 841-R-96-002. United States Environmental Protection Agency (USEPA). 2002 Section 303 (d) list of Water quality limited segments. State Water Resource Board Resolution no. 2003-0009. Approval of the 2002 Federal Clean Water Act Section. Walker, W.W. and K.E. Havens. 2002. Development and application of a phosphorus balance model for Lake Istokpoga, Flor ida. Lake and Reserv. Manage. 19(1):79-91. Welch, E.B.and G.D.Cooke. 1995. Internal phosphorus loading in shallow lakes: Importance and control. Lake and Reservoir Management. 11(3):273-281. Wetzel, R.G. 1999. Organic phosphorus minera lization in soils and sediments. In Phosphorus Biogeochemistry and Subtr opical Ecosystems. CRC Press, Boca Raton, FL. p. 225-245. Wetzel, R.G. 2001. Fundamental processes within natural and constructed wetland ecosystems: short term versus long -term objectives. Water Science and Technology, 44:1-8. White, J.R. and K.R. Reddy. 1999. Influence of nitrate and phosphorus loading on denitrifying enzyme activity in the everglade wetland soils. Soil Sci. Soc. Am. J. 63:1945-1954. White, J.R. and K.R. Reddy. 2000. Influence of phosphorus loading on organic nitrogen mineralization of everglades soils. Soil Sci. Soc. Am. J. 64:1525-1534. Williams, V.P. 2001. Effects of point-sour ce removal on lake water quality: A case history of Lake Tohopekaliga, Florida. Lake and Reserv. Manage. 17(4):315-329.

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135 BIOGRAPHICAL SKETCH Chakesha S. Martin was born in Pine Bluff, AR, in 1979. After graduating high school in 1997, she moved to Fayetteville, AR, to attend the University of Arkansas. She graduated with a degree in environmental scie nce in May 2001. While at the University of Arkansas, she interned at the United St ates Environmental Protection Agency in the Clean Water Act Enforcement Section, work ing with the stormwater team. After graduation, she worked for Walmart Corpor ate Office in Bentonville, AR, for a few months. Shortly thereafter, she entered the master’s program in environmental science with the Wetlands Biogeochemistry Laboratory in January 2002 to work with research related to lake restoration. In the future, she hopes to work to shape the environmental policies of the United States.


Permanent Link: http://ufdc.ufl.edu/UFE0004866/00001

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Title: Phosphorus Flux from the Sediments in the Kissimmee Chain of Lakes
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Copyright Date: 2008

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Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
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Permanent Link: http://ufdc.ufl.edu/UFE0004866/00001

Material Information

Title: Phosphorus Flux from the Sediments in the Kissimmee Chain of Lakes
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
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PHOSPHORUS FLUX FROM THE SEDIMENTS IN THE
KISSIMMEE CHAIN OF LAKES















By

CHAKESHA S. MARTIN


A THESIS PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE

UNIVERSITY OF FLORIDA


2004

































Copyright 2004

by

Chakesha S. Martin


































This thesis is dedicated to my parents and brothers. I thank them all for their continued
patience, love, and support.















ACKNOWLEDGMENTS

I would like to especially thank my committee chair, Dr. John R. White, for giving

me the opportunity to study under him and learn so much from his wisdom and guidance.

AN additional thanks go to my committee members, Dr. Jana Newman and Dr. K.R.

Reddy, for their support and encouragement.

I appreciate Matt Fisher's expertise in the field and for creating the maps used for

this project. I am grateful for Dr. Marco Belmont's help in the field, as well as Paul

Washington. Special thanks go to Ms. Yu Wang for her guidance in the laboratory. I

would also like to especially thank Alicia Callery for her invaluable assistance with

experiments. This project would not have been possible without funding from the South

Florida Water Management District.

I really appreciate all the encouragement I have received from my fellow graduate

students, professors and friends. Special thanks go to my family for being so

instrumental in shaping the person I am today. Above all, I would like to thank God, who

without, none of this would have been achievable.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TABLES ...................... ............................... .... vii

L IST O F F IG U R E S .... ......................................................... .. .......... .............. xii

A B S T R A C T .......................................... ..................................................x v

CHAPTER

1 IN TR OD U CTION ............................................... .. ......................... ..

Study R rationale .............................................. 6
O bjectiv e s ................................................................... ................................. . 8
Site D description ....................................................... 8

2 SEDIMENT CHARACTERIZATION.................................13

In tro d u ctio n ........................................................................................13
H y p o th e sis ................................................................16
O b j e ctiv e ..........................................................................................1 6
Field M methods ........................................................................ ........ 16
Laboratory Techniques ................................. ........................... ... ...... 21
Physical and Chem ical ................................................. ........ 21
Inorganic P Fractionation ................. ...............................23
D ata A nalysis................................................... 25
R e su lts ....................... ......................................................................2 6
Physical and Chem ical ................................................. ........ 26
M etals ....................................................................27
Inorganic P Fractionation ................. ...............................28
D iscu ssio n .................. .......................................................... 3 3
Physical and Chem ical ................................................. ........ 33
M etals ....................................................................39
Inorganic P Fractionation ................. ...............................45
C o n c lu sio n ................................................... .......................................... .................. 4 9





v










3 PHOSPHORUS FLUX OF SEDIMENTS UNDER DIFFERENT SIMULATED
L O A D IN G C O N D ITIO N S ......... ................. ........................................................51

In tro d u ctio n .............. ..... .......... ........................................................................... 5 1
Hypothesis ............ ...... ......... ... ...............54
Objectives ............... ......... .................... 54
Site Selection ........................................................................... ........................... 54
M materials an d M eth od s .......................................................................................... 60
D ata A nalysis.................................................. 61
Results ............. ..................... ............. ...............61
D iscu ssion ......... ...... ............ .................................... ............................83
Overall Conclusion ................ ........ ........ .. ........94

APPENDIX

A PHOSPHORUS FRACTIONATION DATA ..............................98

B M E T A L S D A T A ................................................................................................. 10 1

C N U T R IE N T S ....................................................... 103

D AEROBIC WATER COLUMN SRP DATA .................. ... ...........106

E PR ELIM IN A R Y SU R V EY .............. ..... ............ .............................................. 116

F SEDIMENT TYPE AND COORDINATES .................................... .....126

L IST O F R E F E R E N C E S ............................................................................................ 129

BIOGRAPHICAL SKETCH .............................................................................135















LIST OF TABLES


Table pge

2-1 Average Bulk Density (BD), Loss on Ignition (LOI), Total C, Total N, and Total
P for Lakes Tohopekaliga, Cypress, Hatchineha, Kissimmee, and Istokpoga.
n= 10 per lake. .......................................................................... 27

2-2 HC1 extractable Ca and Mg concentrations and oxalae extractable Fe and Al
concentrations for Lakes Tohopekaliga, Istokpoga, Cypress, Kissimmee, and
Hatchineha. Values are reported as mean and standard deviation (n=10) per lake.28

2-3 Mean and standard deviations for P forms: KC1- Pi, NaOH Pi, HCl-Pi, TPi,
NaOH Pi, residue P, total Po and total P (n=10) for each lake in mg kg-1 for all P
fo rm s .......................................................................... 3 2

2-4 Mean and standard deviations for P forms for sand sediments: bulk density (BD),
mass loss on ignition (LOI), total carbon (TC), total nitrogen (TN), total
phosphorus (TP) per lake in mg kg-1 for all P forms..............................................34

2-5 Mean and standard deviations for P forms for mud sediments: bulk density (BD),
mass loss on ignition (LOI), total carbon (TC), total nitrogen (TN), total
phosphorus (TP) per lake in mg kg-1 for all P forms ..............................................35

2-6 Pearson correlations for selected metals and total P ................................................40

2-7 Mean and standard deviations for P forms for sand sediments: HCl-Ca and Mg
and Oxalate Fe and Al m g kg-1 for all lakes.................................. ............... 41

2-8 Mean and standard deviations for P forms for mud sediments: HCl-Ca and Mg
and Oxalate Fe and Al m g kg-1 for all lakes.................................. ............... 41

2-9 Mean and standard deviations for P forms for sand sediments: KC1- Pi, NaOH Pi,
HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P per lake in mg kg-1 for all
P form s. .......................................................... ................ 4 7

2-10 Mean and standard deviations for P forms for mud sediments: KC1- Pi, NaOH Pi,
HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P ........................................47

3-1. X and Y coordinates of each station. All coordinates are Universal Mercator,
North American Datum 1983, Units meters, UTM Zone 17. ............................59









3-2. Percent change in Water Column SRP (mg L1) under no P additions, for all
lakes, at day 2, 7, and 25. A negative (-) percent (%) change indicates a decrease
in SRP concentration while a positive (+) percent change indicates an increase in
SRP concentrations. n=6 for all lakes except Cypress in which n=4.....................63

3-3 Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at no P additions at 2, 7, and 25 days. n=6
for all lakes except Cypress (n=4) ................................................ ....... ........ 63

3-4 Sediment characteristics of all stations for each lake for bulk density, mass loss
on ignition (LOI), and total C, N, and P (mg kg-1). N=10.................................... 64

3-5 Sediment characteristics of all stations for each lake for oxalate-Fe and Al and
H Cl-C a and M g. n= 10........... ...... ............................... ..........65

3-6 Correlation between sediment properties with the Pearson correlation on top
and the P-value on the bottom in parentheses. All correlations are significant to
P < 0 .0 5 n= 10 .........................................................................67

3-7 Correlation between P flux and EPCw with sediment properties with the Pearson
correlation on top and the P-value on the bottom in parentheses. All correlations
are significant to P<0.05. n= 10 ........................................ .......................... 68

3-8 Percent change in SRP mg L-1 at 15 ug L-1 P additions, for all lakes, at day 2, 7,
and 25. A negative (-) percent (%) indicates a decrease in SRP concentration
while a positive (+) percent change indicates an increase in SRP concentrations.
n=6 for all lakes except Cypress in which n=5 ............ ............. ............... 70

3-9 Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 15 ug L-1 P additions at 2, 7, and 25 days.
n=6 for all lakes except Lake Cypress n=5 ................................... ..................72

3-10 Percent change in SRP mg L-1 at 30 ug L-1 P additions, for all lakes, at day 2, 7,
and 25. A negative (-) percent (%) change indicate a decrease in SRP
concentration while a positive (+) percent change indicate an increase in SRP
concentrations. n=6 .......................... ......... .. .. ..... ............ 74

3-11 Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 30 ug L-1 P additions at 2, 7, and
2 5 d a y s ......................................................................... 7 6

3-12 Percent change in SRP mg L-1 at 60 ug L-1 P additions, for all lakes, at day 2, 7,
and 25. A negative (-) percent (%) change indicates a decrease in SRP
concentration while a positive (+) percent change indicates an increase in SRP
concentrations. n=6. ........................... ......... .. .. ..... ............ 78

3-13 Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 60 ug L-1 P additions at 2, 7, and 25 days..80









3-14 Percent change in SRP mg L-1 at 120 ug L-1 P additions, for all lakes, at day 2,
7, and 25. A negative (-) percent (%) change indicates a decrease in SRP
concentration while a positive (+) percent change indicates an increase in SRP
concentrations. n=6. ........................... ........ .... .. .... ............ 82

3-15 Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 120 ug L-1 P additions at 2, 7, and
2 5 d a y s ......................................................................... 8 3

3-16 Ranges of sediment-water SRP fluxes (mg m-2 d-1)................ .......... .........86

3-17 Correlation between Porewater Equilbrators (Peepers) and P flux rate with the
Pearson correlation on top and the P-value on the bottom in parentheses. All
correlations are significant to P<0.05. n=10 .................................... ..................... 87

3-18 Equilibrium Water Column Phosphorus Concentrations (EPCw) values
determined at two stations in each lake. Water column concentrations below
these concentrations indicate conditions favorable for release of P n=3 ................88

A-i Characterization of inorganic P forms (mg kg-1) in Tohopekaliga, Cypress, and
Hatchineha raw data for sand sediments. ...................................... ...............98

A-2 Characterization of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga
raw data for sand sedim ents. ............................................ ............................ 99

A-3 Characterization of inorganic P (mg kg-1) forms in Tohopekaliga, Cypress and
Hatchineha raw data for mud sediments. ..................................... ............... 99

A-4 Characterization of inorganic P (mg kg-1) forms in Kissimmee and Istokpoga
raw data for mud sedim ents. ............................................................................100

B-l Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha
raw data for sand sedim ents. ........................................... ........................... 101

B-2 Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for
san d sedim ents.............................................................................. ............... 10 1

B-3 Characterization of metals (mg kg-1) for Tohopekaliga, Cypress, Hatchineha raw
data for m ud sedim ents. ............................................... .............................. 102

B-4 Characterization of metals (mg kg-1) for Kissimmee and Istokpoga raw data for
m ud sedim ents.............. .... .......................................................................... 102

C-1 Characterization of nutrients (mg kg-1) in Tohopekaliga, Cypress, and
Hatchineha raw data for sand sediments. ..................................... ............... 103

C-2 Characterization of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data for
san d sedim ents................................................. .............. 104









C-3 Characterization of nutrients (mg kg-1) in Tohopekaliga, Cypress and
Hatchineha raw data for mud sediments. .................................... .................104

C-4 Characterization of nutrients (mg kg-1) in Kissimmee and Istokpoga raw data
for m ud sedim ents. ........................................... ................ ........ 105

D-1 Water Column SRP for Lake Tohopekaliga under aerobic conditions for 25
days for station T10 (Coordinate x (461809 meters), y (3116800 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units meters,
U TM Zone 17 .............. ................................... ...... ..... ......... 106

D-2 Water Column SRP for Lake Tohopekaliga under aerobic conditions for 25
days for station T2. (Coordinate x (460252 meters), y (3125825 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units meters,
U TM Zone 17 .............. ................................... ...... ..... ......... 107

D-3 Water Column SRP for Cypress Lake under aerobic conditions for 25 days
for station C16. Coordinate x (469875 meters), y (3106370 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units meters,
U TM Z one 17 .................................................... ......................... ....... 108

D-4 Water Column SRP for Cypress Lake under aerobic conditions for 25 days
for station C15. Coordinate x (468261 meters), y (3105828 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units meters,
U TM Z one 17 .................................................... ......................... ....... 109

D-5 Water Column SRP for Lake Hatchineha under aerobic conditions for 25 days
for station H107. Coordinate x (461341 meters), y (3098421 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units meters,
U T M Z one 17 .................................................... ......................... ....... 110

D-6 Water Column SRP for Lake Hatchineha under aerobic conditions for 25 days
for station H103. Coordinate x (458082 meters), y (3100650 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units
m eters, UTM Zone 17. .................. .......................... .. ......... ............ ... 111

D-7 Water Column SRP for Lake Kissimmee under aerobic conditions for 25 days
for station K1004. Coordinate x (472394 meters), y (3084179 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units
m eters, U TM Zone 17. ........... .. ................. ....... ... .... .. ...... .... 112

D-8 Water Column SRP for Lake Kissimmee under aerobic conditions for 25 days
for station K1012. Coordinate x (473188 meters), y (3088426 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units
m eters, U TM Zone 17. ........... .. ................. ....... ... .... .. ...... .... 113









D-9 Water Column SRP for Lake Istokpoga under aerobic conditions for 25 days
for station 110007. Coordinate x (472779 meters), y (3026915 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units
meters, UTM Zone 17. ................ ........ .... .. ................. .... .. ............ 114

D-10 Water Column SRP for Lake Istokpoga under aerobic conditions for 25 days
for station 110004. Coordinate x (469916 meters), y (3030750 meters). All
coordinates are Universal Mercator, North American Datum 1983, Units
m eters, UTM Zone 17. ................ ........ .... .. ................. .... .. ............ 115

E-1 Coordinates (x and y), water depth, sediment depth and thickness for Cypress
Lake. Units Meters. All coordinates are Universal Transverse Mercator, North
American Datum 1983, UTM Zone 17. ...................................... ............... 121

E-2 Coordinates (x and y), water depth, sediment depth and thickness for Lake
Hatchineha. Units Meters. All coordinates are Universal Transverse Mercator,
North American Datum 1983, UTM Zone 17.......................................................122

E-3 Coordinates (x and y), water depth, sediment depth and thickness for Lake
Istopokga. Units Meters. All coordinates are Universal Transverse Mercator,
North American Datum 1983, UTM Zone 17.............. ............... 123

E-4 Coordinates (x and y), water depth, sediment depth and thickness for Lake
Kissimmee. Units Meters. All coordinates are Universal Transverse Mercator,
North American Datum 1983, UTM Zone 17....................................................... 124

E-5 Coordinates (x and y), water depth, sediment depth and thickness for Lake
Tohopekaliga. Units Meters. All coordinates are Universal Transverse
Mercator, North American Datum 1983, UTM Zone 17. ..............................125

F-l Coordinates (x and y) and sediment type for stations chosen to sample for Lake
Tohopekaliga and Cypress Lake. n=10. All coordinates are Universal Transverse
Mercator, North American Datum 1983, units meters, UTM zone 17. ................126

F-2 Coordinates (x and y) and sediment type for stations chosen to sample for Lake
Hatchineha and Kissimmee Lake. n=10. All coordinates are Universal
Transverse Mercator, North American Datum 1983, units meters,
U TM zone 17. ........................................................................127

F-3 Coordinates (x and y) and sediment type for stations chosen to sample for Lake
Istokpoga Lake. n=10. All coordinates are Universal Transverse Mercator,
North American Datum 1983, units meters, UTM zone............. ..............128















LIST OF FIGURES


Figure pge

1-1 Location of Lake Istokpoga and Upper Chain of Lakes in relation to Lake
O keechobee. .......................................... ............................. .. 7

1-2 The percent of landuse by county area for Osceola and Highlands for which the
lakes are located. The total acres for Osceola and Highlands are 620,016 and
487,207, respectively ........ ............................................................... ........ .. .. ...

1-3 Historical TP levels (mg L1) for Kissimmee upper chain of lakes (personal
com m unication w ith SFW M D ). ..................................................... .....................12

2-1 Sampling stations for Lake Tohopekaliga............... ..........................17

2-2 Sam pling stations for Cypress Lake ................ ................. ............ .. ............. 18

2-3 Sampling stations for Lake Hatchineha. ...................................... ............... 19

2-4 Sampling stations for Lake Kissimmee......................................... ............... 20

2-5 Sam pling stations for Lake Istokpoga ........................................... ............... 21

2-6 Inorganic P fractionation scheme after Reddy et al. 1998. .....................................25

2-7 Amount of metals, HCl-Mg, HCl-Ca, Oxalate-Fe, and Oxalate Al, in mg kg-1
for all lakes. ...........................................................................29

2-8 Distribution of P forms in Lakes Tohopekaliga and Hatchineha...........................31

2-9 Distribution of P forms in Lakes Cypress and Kissimmee. ....................................32

2-10 Regression between concentrations of total C (g kg-1) to loss on ignition (%).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ............................................ ............................. 35

2-11 Regression between concentrations of total N (g kg1) to loss on ignition (%).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ............................................ ............................. 36









2-12 Regression between concentrations of total P (g kg-1) to loss on ignition (%). The
mud sediments values are located at top graph and the sand sediments are located
at th e b o tto m g rap h ........................................................................ ..................... 3 7

2-13 Regression between concentrations of total P (mg kg-1)and with total C (g kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ..................................................................38

2-14 Regression between concentrations of total P (mg kg-1) and with total N (g kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ..................................................................39

2-15 Regression between concentrations of oxalate-Al (mg kg-1) with total P (mg kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ........................... ......................................42

2-16 Regression between concentrations of oxalate-Fe (mg kg-1) with total P (mg kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ..................................................................43

2-17 Regression between concentrations ofHCl-Ca (mg kg-1) with total P (mg kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ..................................................................44

2-18 Regression between concentrations of HCl-Mg (mg kg-1) with total P (mg kg-1).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph. ..... ..................................................................45

2-19 The mean percent of mean TP (mg kg-1) of each P fractions (KCl-Pi, NaOH-Pi,
HCl-Pi, NaOH-Po, and Residue P) for both mud and sand sediments for all the
lakes ................................................. ..................................... 4 8

3-1 Location of sampling stations for Lake Tohopekaliga .........................................55

3-2 Location of sampling station for Cypress Lake. ................................................ 56

3-3 Location of sampling stations for Lake Hatchineha.................... ... .............57

3-4 Location of sampling stations for Lake Kissimmee ...............................................58

3-5 Location of sampling stations for Lake Istokpoga. .............................................59

3-6 Phosphorus retention by sediments from station T2 of Lake Tohopekaliga at 60
ug L -1 P additions. .....................................................................77

3-7 Phosphorus retention by sediments from station 110007 of Lake Istokpoga at
120 ug L-1 P additions. ..................... .............. ................ ........ .... 1









3-8 Water Column SRP (mg L-1) versus spike concentration ug L-1 for each lake at
day 2, 7, and 25. .................................................... ................. 84

3-9 Release/retention of P related to water column concentration for Lake
Tohopekaliga-stations-T10 (top) and T2 (bottom)........................................89

3-10 Release/retention of P related to water column concentration for Lake Cypress-
station C16 (top) and C15 (bottom). ............. ................................. ...............90

3-11 Release/retention of P related to water column concentration for Lake
Hatchineha-station H107 (top) and H103 (bottom). ..............................................91

3-12 Release/retention of P related to water column concentration for Lake
Kissimmee-stations K1004 (top) and K1012 (bottom). ................ ............. .....92

3-13 Release/retention of P related to water column concentration for Lake Istokpoga-
station 10007 (top) and 10004 (bottom )........................................ ............... 93

E-1 Sediment thickness map for Cypress Lake. .......................................................116

E-2 Sediment thickness map for Lake Hatchineha. .............................................. 117

E-3 Sediment thickness map for Lake Istokpoga.................................. ... ................ 118

E-4 Sediment thickness map for Lake Kissimmee. ............... .........................119

E-5 Sediment thickness map for Lake Tohopekaliga. .............................................120















Abstract of Thesis Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Master of Science

PHOSPHORUS FLUX FROM THE SEDIMENTS IN THE
KISSIMMEE CHAIN OF LAKES

By

Chakesha S. Martin

May 2004

Chair: John R. White
Major Department: Soil and Water Science

Phosphorus (P) coming from wastewater treatment plants and runoff from urban

and agricultural areas have impacted water quality in many Florida lakes over the last few

decades. The continual input of P into lakes can lead to poor water quality, which can

result in massive fish kills and harm to humans and animals through drinking water.

Bottom sediments also control the trophic status of a lake, even after the external load has

been reduced. The P flux study examined the response of lake sediments to changes in

water column SRP concentrations in 5 contributory lakes of Lake Okeechobee in Florida.

The objectives of this study were to characterize the pools of inorganic and organic

P, determine the SRP flux rates using intact sediment cores, and determine the

equilibrium water column P concentration (EPCw) of the sediment.

Sediments were collected from 10 stations per lakes for the P characterization

study. Sediment samples were collected from the top 10 cm and analyzed for moisture









content, bulk density, mass loss on ignition (LOI), HC1 extractable Ca and Mg, oxalate Fe

and Al, inorganic and organic P fractions, as well as total C, N, P.

Intact cores were taken from two stations per lake and 15 cores per station (total of

150 cores) to determine the SRP flux rate for a range of mud and sand sediments and to

calculate the EPCw. Five water column concentrations (0, 15. 30, 60, 120 ug L1) were

added once and evaluated in triplicate for the SRP flux rate measurements and incubated

in the dark under aerobic conditions for 25 days.

The sediment P characterization revealed that the mud sediments contained greater

amounts of organic matter, total C, N, and P, as well as Ca, Mg, Fe, and Al. Total P

concentrations ranged from 38 to 1812 mg kg-1 for the sediments. There was a strong

positive correlation found between TP and organic matter (R2=0.94), suggesting that P is

a consistent portion in the organic fraction. Most of the inorganic P was associated with

the Fe/Al portion. The total organic P fraction was the greatest overall pool, suggesting

that the TP coming into the lakes may be associated with organic matter.

The aerobic SRP flux rates suggest that P release was highest at ambient water

column SRP (6 + 4 ug L1) and decreased with an increase in P loading. However, an

increase in P loading also maintained high water column SRP concentrations. Flux rates

results indicate that sediments in 4 of the 5 lakes are releasing P to the water column at

ambient water column SRP concentrations and retaining P at higher concentrations. The

EPCw showed that 2 of the 5 lakes have a low potential for release of SRP from the

sediments as the water column SRP concentrations decrease over time. Results from this

study will assist water managers in determining the internal load of P during efforts to

reduce P export to downstream Lake Okeechobee.














CHAPTER 1
INTRODUCTION

For years there have been concerns about the impact of excess nutrients

(phosphorus (P), nitrogen (N) and carbon (C)) entering lakes from wastewater treatment

plants and runoff from urban and agricultural areas on deteriorations to surface water

quality (Carpenter et al. 1998, Sharpley et al. 1999). Phosphorus, N, and C are all

macronutrients essential for growth of organisms but P is often considered one of the

most limiting nutrients in freshwater systems (i.e., lakes, and rivers) throughout the

world. Phosphorus is documented as a major source influencing phytoplankton mass in

freshwater and is generally derived from controllable point sources (Marsden 1989).

However, for N and C there are difficulties in controlling the exchange of N and C

between the atmosphere and the water and the fixation of atmospheric N by some blue-

green algae (Sharpley et al. 1999). Alternatively, as salinity increases, as in estuarine

systems, N is sometimes considered the limiting nutrient controlling aquatic productivity

(Sharpley et al. 1999).

In Florida, there is a particular concern in water quality because of surface water

eutrophication from excess P coming from external sources (i.e., wastewater treatment

plants, agriculture, and urban sources). Eutrophication can be described as an increase in

the fertility status of natural waters that cause accelerated growth of algae as well as

aquatic weeds (Pierzynski et al. 2000). The growth of undesirable algae and weeds that

later die off and decompose cause oxygen depletion that can result in massive fish kills

and harm to humans and animals through drinking water (Backer 2002, Carpenter et al.









1998). A few examples of degrading water systems due to continual external inputs of P

are Loosdrecht lakes (Netherlands); Skaha Lake (British Columbia), Lake Okeechobee,

Florida (USA); and the Everglades (USA) (Keizer and Sinke 1992, Nordin 1983, Reddy

et al 1995, White and Reddy 1999).

Phosphorus Forms

Phosphorus enters the surface water of lakes in both organic and inorganic forms

and can be in either soluble or insoluble forms. Phosphorus can be classified into four

forms: i). soluble reactive P (SRP); ii) dissolved organic P; iii) particulate inorganic P;

and particulate organic P (Reddy et al. 1999). Soluble reactive P is the form most

available for plants and microbes. The other three forms must be transformed into the

bioavailable form through decomposition processes regulated by enzymatic hydrolysis.

Phosphorus Cycling

Inorganic P enters primarily in the form of orthophosphate (P043-) and can enter the

water column of a lake by four pathways: i) settling of insoluble (particulate) inorganic

and organic P, ii) uptake of soluble reactive P (SRP) by primary producers (algae) and its

subsequent settling, iii) sorption of soluble inorganic or organic P onto particles that settle

onto the sediments, and iv) sorption of soluble inorganic and organic P directly onto

sediment particles (Reddy et al. 1999). Sediments act as a net sink of P; however, when

porewater P concentrations exceed the overlying water column concentration, SRP can be

released from the sediment to the water (Moore et al. 1991).

The exchange of P between the sediment and water column may depend on

processes such as i) diffusion and advection (wind/wave action, flow, and bioturbation),

ii) processes within the water column (biotic uptake and release, mineralization, and









sorption by particulate matter), iii) diagenetic processes mineralizationn, sorption,

precipitation, and dissolution) in bottom sediments, iv) redox conditions (oxygen

content), v). organic matter content, vi) pH, vii) temperature, and viii) the presence of

metals bound to P (Bostrom and Pettersson 1982, Holdren and Armstrong 1980, Moore et

al. 1991, Wetzel 2001). Inorganic P is most associated with crystalline or amorphous

compounds such as iron (Fe), aluminum (Al), calcium (Ca) and magnesium (Mg).

Organic P is mostly associated with undecomposed residues, microbes, and organic

matter (Sharpley et al. 1999).

Phosphorus Retention Mechanisms

Understanding the forms and properties of P in lake sediments are important to

identify factors that control P release from the sediment to the overlying water column.

Inorganic P is usually found as i) labile or loosely sorbed P, ii) Al and Fe bound P; and

iii) Ca and Mg bound P (Reddy et al. 1995). The most available form of P is labile P or

exchangeable P, which is essential for plant growth. The slowly available form of P is

associated with Fe/Al, Ca/Mg, and labile organic compounds. The very slowly available

P is associated with discrete mineral forms ofFe, Al, and Ca, and highly decomposed

organic matter.

Metals (Fe, Al, Ca, and Mg) play a important role in inorganic P retention. The

ability of P to be retained by Fe/Al and Ca/Mg compounds depend on pH and/ or redox

conditions of the sediments (Patrick and Khalid 1974). Phosphorus is retained by Fe/Al

compounds under acidic conditions and is more stable under low pH conditions. The

reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous iron (Fe2+) compound

can lead to P released from the sediments (Patrick and Khalid 1974). When there is a









dominance of Ca/Mg P in the sediments, P is more stable under high pH or alkaline

conditions (Patrick and Khalid 1974). Organic acids from settling or deposited

decomposing organic matter can lower pH short term and lead to dissolution of Ca bound

P (Marsden 1989).

Phosphorus External Load Reduction

Over the years, improvements in water quality have focused on external

phosphorus load reductions. The response of a lake after external load reductions

depends on the recycling of phosphorus from the sediment to water column (Marsden

1989). Some studies have shown that reducing the external P loading can significantly

improve water quality in lakes (Smith and Shapiro 1981). However, other studies have

shown that a reduction in external P load does not always result in a decrease in TP in the

water column of a lake due to high internal sediment P load (Marsden 1989, Nordin

1983, Welch and Cooke 1995). The idea of internal loading is based on the recycling of

nutrients from bottom sediment in lakes to the overlying water column (Carpenter 1983).

After load reductions, the internal load of sediments will determine the trophic status of a

lake and the amount of lag time for recovery (Petterson 1998).

Many studies have investigated the diffusive release of phosphorus from the

sediments measured from intact sediment cores in the laboratory (Fisher and Reddy 2001,

Petterson and Bostrom 1985). Phosphorus release rates are stimulated by low redox

potential (Istvanovics 1988, Marsden 1989, Mortimer 1941) and high temperature

(Holdren and Armstrong 1980, Kamp-Nielsen 1974). In shallow lakes, sediments

resuspension can be important for internal loading (Reddy et al 1996, Welch and Cooke

1995). The mobilization of this internal P load in the sediment is determined by the









forms of P in the sediment (Keizer and Sinke 1992). Sediments characterized with a

dominance of iron (Fe) associated P can release P under low redox, as well as high pH

conditions (Petterson and Bostrom 1985). In other instances, sediments characterized by

a dominance of calcium (Ca) may release P under low pH conditions (Marsden 1989).

In eutrophic lakes, macrophyte species with high annual biomass turnover can be a

potential internal source of nutrients to the overlying water column (Carpenter 1983). In

oligotrophic lakes biomass turnover and the biomass of macrophytes are not as large and

there may not be a great release of P to the water column from the senescenes of

macrophytes. Macrophytes release phosphorus as well as other nutrients from living

shoots, but most of the phosphorus released occurs after the shoot dies and decays

(Carpenter 1983). The decay of macrophytes at the sediment surface lowers the oxygen

concentration and redox potential which can cause a flux of P from the sediment to water

column of a lake (Carpenter 1983). One management suggestion to reduce the flux of P

is to spray with herbicides; however, this may not be an effective control method

(Carpenter 1983). Harvesting macrophytes may be a more effective in removing

nutrients and reducing internal nutrient loads because it removes the nutrients from the

system.

The equilibrium phosphorus concentration (EPC) can be used to determine the

extent to which the internal load will be released during restoration of a lake after

external load reductions. The EPC is defined as the P in solution that is in equilibrium

with the P in the solid phase or the point where P is neither being retained nor released

from the sediment to the water column (Olila and Reddy 1993). At water column SRP









concentration above the EPC, P is retained by the sediments, and at concentrations below,

the sediments serve as P source.

Study Rationale

Lake Okeechobee, a large (1800 km2), shallow (mean depth -2.7 m) eutrophic lake,

located in south Florida, has been impacted by nutrient loads from point and nonpoint

sources of pollution for over 30 years (Havens 1997; Havens and Walker 2002; Reddy et

al. 1995). Lake Okeechobee serves as a primary source of water for surrounding cities,

recharge water for the South Florida aquifer, source of irrigation water for agriculture,

source of habitat for wildlife, and as a source of recreational and commercial fishing

(Havens and James 1997). Since the early 1970's to present, the total phosphorus

concentrations in Lake Okeechobee have more than doubled from around 50 ug L-1 to

100 ug L-1 (Havens 1997). Lake Okeechobee, located in south Florida is a large (1800

km2), shallow (mean depth -2.7 m) eutrophic lake

Recognizing the need for restoration of water quality in Lake Okeechobee, Florida,

the Florida Legislature in 1987 adopted the Surface Water Improvement and

Management (SWIM) Act (sections 373.451 to 373.4595 FL statues) that states that the

South Florida Water Management District (SFWMD) must create and implement a

program to protect the quality of water in Lake Okeechobee (Havens and James 1997).

The SWIM Act also mandated a P loading target for Lake Okeechobee.

In 1998, the Florida Department of Environmental Protection (FDEP) submitted

Lake Okeechobee on a list of impaired waters to the United States Environmental

Protection Agency (USEPA) (Havens and Walker 2002). In 2000 FDEP began the

process of developing a TMDL for Lake Okeechobee. The TMDL goal to Lake









Okeechobee is established at 198 metric tons of TP and the in-lake P concentration is 40

ug L-1 within the pelagic region.

Phosphorus load to Lake Okeechobee from water discharging from the Kissimmee

upper chain of lakes have increased in phosphorus over the last five years from 23-91

metric tons (personal communication with SFWMD). Thus, quantifying P load from

these major contributory lakes (Tohopekaliga, Cypress, Hatchineha, Kissimmee, and

Istokpoga) is vital for Lake Okeechobee's restoration (Figure 1-1). This study fulfills

parts of the requirements of the Lake Okeechobee Protection Act (Chapter 373.4595),

which required an assessment of P sources from the Kissimmee upper chain of lakes and

their contribution to the quality of water in Lake Okeechobee (Walker and Haven 2002).


0 20 40 60 Kilometers

Figure 1-1. Location of Lake Istokpoga and Upper Chain of Lakes in relation to Lake
Okeechobee.









In considering factors affecting water quality in the upper chain of lakes and P

export to downstream Lake Okeechobee, several questions arose, including: i) What are

the physical and chemical characteristics of surface sediments, with particular emphasis

on the forms of P and compounds that can affect P sorption or release? ii) What is the

current contribution of phosphorus (internal loading) from the sediments to the water

column of these lakes? iii) What are the Equilibrium Phosphorus Concentrations of the

sediments in these lakes? These questions focus on whether P is being stored in organic

or inorganic forms, the relative availability of P forms, and the extent to which the

internal load will be released as external P loads decline and the water column P

concentrations are reduced.

Objectives

The objectives of this study were to i) characterize and quantify the forms of

inorganic P and organic P in the sediment, ii) determine the P flux rate from the

sediment to the water column and iii) determine the equilibrium P concentration of the

sediment.

Site Description

Lakes Tohopekaliga (98.4 km2) Cypress (22 km2), Hatchineha (71.6 km2),

Kissimmee (179 km2) and Istokpoga (112 km2) are shallow, eutrophic lakes located in the

Upper Kissimmee River Basin (Walker and Havens et al. 2002; Williams 2001). The

mean depths are 2.6, 1.9, 2.1, 3.4, and 2.7 m respectively for Lakes Tohopekaliga,

Cypress, Hatchineha, Kissimmee, and Istokpoga (Havens et al. 2000, Walker and Havens

2002). The surface water pH ranges from 6-8, and secci depth ranges from 0.6-1.2 m for

all lakes (Havens et al. 2000, Walker and Haven 2002). The entire Kissimmee River










Basin (KRB) comprises 3,013 square miles; however, the upper basin covers 1600 square

miles (USACE 1996)

Lake Tohopekaliga is at the headwaters of the KRB, proximal to Walt Disney

World, and about 25 km south of the city of Orlando and Kissimmee (James et al. 1992).

These hydrological connected lakes in Central Florida flow throughout the counties of

Osceola and Highlands in a heavily populated and intensively developed part of the

watershed (Figure 1-2). The lakes are located in an area that is the hub of the cattle

industry in central Florida, St. Cloud, and Haines City (USACE 1996). Citrus farming,

tourism and sod farming, as well as the cattle industry are economic bases for the

surrounding communities. Citrus industry dominates north of Lake Cypress and sod

farming is prevalent within the Kissimmee Upper Basin.


300000
250000
200000
Figure 1-2. The percent oflanduse by county area for Osceola
150000
10 Highlands
100000
50000





Landuse

Figure 1-2. The percent of landuse by county area for Osceola and Highlands for which
the lakes are located. The total acres for Osceola and Highlands are 620,016
and 487,207, respectively.

The lakes are used for recreation, irrigation and flood control. There are less urban

and residential development located around Lakes Kissimmee, Cypress, and Hatchineha

in comparison to Lake Tohopekaliga (Havens et al. 2000, USACE 1996). Each of the









five lakes receives flow contributions from other water systems within the KRB: Lake

Tohopekaliga (Shingles Creek and East Lake Tohopekaliga), Lake Cypress (Canoe Creek

and Dead River), Lake Hatchineha (Reedy and Catfish Creek), Lake Kissimmee (Lake

Tiger), and Lake Istokpoga (Josephine Creek and Arbuckle Creek) (Walker and Haven

2002, Williams 2001).

Under natural conditions, prior to significant alterations to the watershed, the lake

stages fluctuated seasonally from about 0.6-3.1 m (2-10 ft) and stored water in the wet

summer season overflowing into the marshes connected to each lake (USACE 1996).

There were no hydrologic connections between the lakes during the dry season.

Currently, lake levels are regulated and maintained by the South Florida Water

Management District (SFWMD) through a series of water control structures and canals.

Some nuisance or problem vegetation is hydrilla (Hydrilla verticillate), water

hyacinth (Pistia stratiotes), water lettuce (Eichhornia crassipes) and the American lotus

(Nelumbo luteal). The dominant vegetation in the littoral zone of the lakes includes

vegetations such as willow (Salix spp), buttonbush (Cephalanthus occidentalis), topedo

grass (Panicum repens), maidencane (Panicum hemitomon), sawgrass (Claidium

jamaicense), cattail (Typha spp.), and pickerel weed (Pontederia cordata), (USACE

1996). The lakes are surrounded by pine flatwoods, dry and wet praires and cypress

domes.

The water quality in the lakes have been affected by Waste Water Treatment

Effluent (WWT) coming from four waste treatment plants via canals and streams into

Lake Tohopekaliga, since the late 1950's (Williams 2001). The water discharged from

Lake Tohopekaliga has contributed to the degradation of water quality in the downstream









lakes. The lakes have not only been affected by nutrients coming from wastewater

treatment plants, but also pollution coming from agricultural and urban sources. Since

the lake 1960's, a few lake drawdowns, muck removal projects, and control of invasive

plants by use of herbicide applications have been utilized as a way to restore water

quality and habitat for endangered species within the Kissimmee upper chain of lakes

(USACE 1996, Williams 2001). In the mid 1980's the nutrients levels coming from

wastewater treatment plants to Lake Tohopekaliga were diverted.

In general, TP levels in the water column of the Kissimmee upper chain of lakes

have declined over time; since 1980's (Figure 1-3). In reviewing past water quality data

collected by the South Florida Water Management District, since the 1980's (no water

quality data available prior to 1980), the average TP concentrations were greater than 100

ug L-1 in Cypress, Tohopekaliga, and Hatchineha; however, the concentrations were

much lower in Kissimmee and Istokpoga at less than 50 ug L-1. In the 1990's, the water

column TP concentrations decreased to less than about 65 ug L-1 in Tohopekaliga,

Cypress, and Hatchineha, but concentrations nearly double to over 100 ug L-1 for Lake

Kissimmee. The water column TP concentration for Istokpoga remained the same as in

the 1980's. Currently, the water column TP concentrations have remained relatively the

same for most all lakes since the 1990's, except concentrations have nearly doubled in

Istokpoga to 60 ug L-1 and concentrations have declined in Kissimmee from over 100 ug

L-1 to 60 ug L-1. However, it should be noted that although water column TP

concentrations have declined, in general, the concentrations in the lakes are well above

the in-lake P concentration goal of 40 ug L-1 in the pelagic region of Lake Okeechobee.












200
180
160 Cypress
a) 140 Hatchineha











Years
S120 Tohopekaliga
SKissimmee
PE t Istokpoga
S80
60


20
0
80-89 90-99 00-03
Years



Figure 1-3. Historical TP levels (mg L-1) for Kissimmee upper chain of lakes (personal
communication with SFWMD).

In efforts to restore water quality in the Kissimmee upper chain of lakes and reduce

P effort to downstream Lake Okeechobee there have been efforts made to control water


quality deteriorations coming from nonpoint and point sources of pollution by

implementing Best Management Practices (BMP's). Some management practices to

reduce the external load ofP entering a lake include retention or infiltration areas, wet

detention ponds, constructed wetlands, sand filters, and bio-retention areas. The main

BMP's are usually efficient fertilizers applications (directed in some part to educating

citizens), effective stormwater systems, and control of erosion and sediment.














CHAPTER 2
SEDIMENT CHARACTERIZATION

Introduction

Over the years there have been concerns about the impact of excess P leaving

urban and agricultural areas on water quality in many Florida lakes (i.e., Lake Apopka

and Lake Okeechobee). Although, P is a limiting nutrient essential for plant growth, too

much P can lead to eutrophic conditions, resulting in harm to the quality of water within

an aquatic system including declines in fish populations, changes in vegetation, and

limitations to recreation (Carpenter et al. 1998). Chemical, physical, and microbial

processes control the exchange of P between the sediment and water column. Thus, for

restoration to occur in a lake, it is important to understand the forms and properties of P

in lake sediments to identify the factors that control P release from the sediment to the

overlying water column.

Phosphorus in soils and sediments exists in both organic and inorganic forms.

External inputs of P from such entities as urban and agricultural sources and wastewater

treatment plants can be in soluble or insoluble particulate forms. P can be classified into

four forms: i) soluble reactive P (SRP) or dissolved inorganic P; ii) dissolved organic P;

(iii) particulate inorganic P; and (iv) particulate organic P (Reddy et al. 1999). Soluble

reactive P is the form most available for plants and microbes. The other three forms must

be transformed into the bioavailable form through decomposition processes regulated by

enzymatic hydrolysis.









Inorganic P primarily enters into lakes in the form of orthophosphate and can be

transported to the sediments first by uptake by phytoplankton (biological) and through

subsequent settling of particulate inorganic and organic P (Faulkner and Richardson,

1989, Syers et al. 1973). The forms of inorganic P which exist in sediments include the

ions PO43-, HPO42- and H2P04- with the dominant form dependent on pH. Sediment in

lake systems in Florida typically range from 6-8, with the HPO42- and H2P04- forms most

dominant. Inorganic phosphorus is usually found as (i) labile or loosely absorbed P; ii)

Al and Fe bound P; and (iii) Ca and Mg bound P (Reddy et al. 1995). The most available

form of P is the labile P or exchangeable P. The slowly available P is associated with

Fe/Al, Ca/Mg and labile organic compounds. The very slowly available P is associated

with discrete mineral forms ofFe, Al, and Ca. and highly decomposed organic matter.

Factors that regulate inorganic P retention are pH, redox (Eh), organic matter

content, calcium carbonate content, temperature, and amounts of Fe, Al, Ca and Mg

compounds. The ability of P to be retained by Fe/Al and Ca/Mg depends on the pH

and/or redox conditions of the sediments (Patrick and Khalid 1974). Phosphorus is

retained by Fe/Al compounds under acidic conditions and is more stable under low pH

conditions. The reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous iron

(Fe2+) compound can lead to P released from the sediment (Patrick and Khalid 1974).

When there is a dominance of Ca/Mg P in the sediments, P is more stable under high pH

or alkaline conditions (Patrick and Khalid 1974). Organic acids from settling or

deposited decomposing organic matter can lower the pH short term and lead to

dissolution of Ca bound P (Marsden 1989).









Organic P is contained in undecomposed residues, microbes and organic matter

(Sharpley 1999). The most common form of organic P is inositol phosphates, which are

found as hexaphosphates (Ivanoff et al. 1998). Inositols are high molecular weight

phosphates (up to 60% of total Po) that are the most stable or resistant to degradability;

thus microbes do not readily have access to inositols (Anderson 1976, Ivanoff et al.

1998). Other forms of organic P compounds are phospholipids, nucleic acids, glucose-l-

phosphate, glycerophosphate, and phosphoproteins, which make up only 2% of total

organic P (Ivanoff et al. 1998). Phospholipids are commonly found in plant material and

animal waste, or found through the process of microbial synthesis (Ivanoff et al. 1998).

Since much of organic P is contained in sediment particles and organisms, it is not readily

available to microbes and plants. Therefore, organic P must be transformed into the

bioavailable form of phosphorus (Wetzel 1999).

Chemical fractionation schemes have been used to distinguish and quantify the

various forms of P in sediments (Graetz and Nair 1999). There are several methods that

have been developed to quantify the various forms of P; but, there is not a widely

accepted method to measure organic P content (Change and Jackson 1957, Hieltjes and

Lijklema 1980, Ruttenberg 1992). Organic P can be measured indirectly through

inorganic P fractionation schemes.

There have been criticisms of the sequential fractionation schemes. It is

important to keep in mind that various chemical reagents only extract a pool of P related

to a given chemical group. Therefore, it is critical that adequate tests of sequential

extraction methods be calibrated (Ruttenberg 1992). Phosphorus extraction methods are

often considered operationally defined and therefore subject to broad interpretations









(Graetz and Nair 1999). It can be difficult to compare data between researchers who use

vastly different P fractionation methods thus complicating data interpretation obtained

among literary sources (Graetz and Nair 1999). Nevertheless, sequential fractionation

schemes do provide a method of determining various pools of P in lake sediments.

Hypothesis

Recently accreted mud sediments will contain significantly higher P than the

natural sand sediment bottom.

Objective

The objective of this study was to characterize and quantify the forms of P in the

sediments.

Field Methods

We performed a preliminary sediment survey of the lakes (August/2002) that

provided information for selection of each sampling station. A jet probe rod was used to

determine where soft sediments were located and how thick (Appendix E). During the

initial survey, coordinates, water depth, sediment depth, and thickness were recorded

(Appendix E). In addition, sediment type was recorded in which there were clean sand to

organic muds for all lakes. After reviewing the preliminary sediment survey observations

and measurements, 10 stations per lake were chosen to be sampled and were

representative of the major sediment types in each lake (Figure 2-1 to Figure 2-5).

Using GPS equipment, each station was located within +/- 5 m of the true

coordinates and sediment type was recorded (Appendix F). Dissolved oxygen and

temperature measurements were taken at three depths: 30cm below the water surface,

mid-depth, and 30 cm from the bottom using a YSI hand-held DO meter. In general, the

dissolved oxygen levels were greater than 5 (mg L1) in the top 30 cm and decrease with









an increase in depth. The temperature measure was relatively the same at all depth a

mean of 29.9 + 1.21 for all lakes.

Sediment samples (0-10cm) were collected from each site for analysis of various

forms of P and a number of physical and chemical properties. Samples were extruded in

the field using plexiglas tubes and immediately sectioned immediately into 10 cm

intervals. Immediately following sectioning, the sediment samples were transferred to air

tight pre-weighted glass jars, purged with nitrogen gas to maintain anaerobic conditions,

and placed on ice. Samples were stored at 40C upon return to the laboratory until

analysis.


Figure 2-1. Sampling stations for Lake Tohopekaliga





18



N
13


14

^ 12 16

15 17
11

18
,?

20 18
19






0 1 2 3 4 Kilometers

Cypress Lake

Figure 2-2. Sampling stations for Cypress Lake.







19






S\ N



102


103
109
103 \ / V

106 1

105
110
107
S 104 108






0 1 2 3 4 Kilometers

L. Hatchineha


Figure 2-3. Sampling stations for Lake Hatchineha.










\1010

1009 11011
1009 X -


1012
S,, 1006
1 005Q

1003
1004 f


1002


1001
0 1 2 3 4 Kilometers l
L. Kissimmee


Figure 2-4. Sampling stations for Lake Kissimmee














10001 N

S10002

10003 10004
S' 10005


10006


10007

10008
S10010



10009 0 1 2 3 4 Kilometers

L. Istokpoga


Figure 2-5. Sampling stations for Lake Istokpoga.


Laboratory Techniques

Physical and Chemical

All sediment sub-samples were measured for a number of physical and chemical

properties: water content, bulk density, mass loss on ignition (LOI), and total C, N, and

P. Percent moisture was determined after drying a known amount of moist sediment at

700C to a constant dry weight. Total C and N were determined on dried, ground sub-









samples and analyzed on the Carlo-Erba NA-1500 C-N-S Analyzer (Haak-Buchler

Instruments, Saddlebrook, NJ) (White and Reddy 2000).

For the measurement of sediment total P, 0.5 g dried ground sub-samples were

weighed and placed in a muffle furnace initially at 2500C and increased to 5500C for 4

hours. The remaining ash was treated with 20 mL of 6 M HC1 and placed on a hot plate

at approximately 1200C (Anderson 1976). The samples were cooled and filtered through

Whatman #41 filter paper. The total P concentrations were determined using an

automated ascorbic acid colorimetric technique (Method 365.4, USEPA, 1993). The

organic matter content was determined by LOI.

Oven dried sub-samples were weighed out to approximately 0.5 g for analyses of

total inorganic P using 25 mL of a 1 M HC1 extraction on oven dried sediment (Reddy et

al. 1998). The samples were shaken on a mechanical shaker for 3 hours and the

supernatant was filtered with 0.45 um filter paper. Total inorganic P concentrations were

analyzed using an automated ascorbic acid colorimetric method (Method 365.4, USEPA,

1993). The same 1 M HC1 extraction was analyzed for metals, which were Ca and Mg

(Reddy et al. 1998). Sub-samples of approximately 0.25 g of dry ground sediment were

weighed and treated with 20 mL of oxalate reagent. Samples were shaken in the dark for

about 4 hours, centrifuged for 10 minutes, and filter through with 0.45 um filter paper.

The oxalate extraction was used to determine the Fe and Al bound P, which is the

reactive fraction of amorphous Fe-Al oxides. Metal analyses were determined by

inductively coupled argon plasma spectrometry (model Spectro Ciros CCD,

manufactured by Spectro AI, Inc, Fitch burg, MA). Analyses were determined using a









modified version of EPA Method 200.7 (EPA 1983). Total organic P was calculated as

the difference between total P and total inorganic P.



Inorganic P Fractionation

The fractions of inorganic P were determined based on a scheme by Change and

Jacksons 1957 in which acid and alkaline reagents were used to extract various pools of P

in the soil. In this study, a modified version of Change and Jacksons' scheme by Reddy

et al. 1998 was used to determine the various inorganic P fractions (Figure 2-6). It is

important to keep in mind that various chemical reagents only extract a pool of P related

to a given chemical group. The chemicals used in this study were 1.0 Mpotassium

chloride (KCL), 0.1 M sodium hydroxide (NaOH), and 0.5 M, 6.0 M hydrochloric acid

(HCL) in which, (i) bioavailable or loosely adsorbed Pi; ii) Pi associated with Fe and Al;

and iii) Pi associated with Ca and Mg were extracted, respectively. The remaining

sediment P was considered to be the residual, recalcitrant organic P.

For the KCl-Pi extraction, samples were weighed out to a 0.5 g dry weight

equivalent and placed in centrifugation tubes in an oxygen-free gloved box to maintain

anaerobic conditions. Dissolved oxygen readings were less than 0.10 mg L-1. Samples

were placed in centrifuge tubes with caps outfitted with rubber septa. Using a syringe

needle, 25 mL of 1 MKC1 were added. The samples were placed on a mechanical shaker

for 2 hours, followed by centrifugation at 6000 (reps per minute) rpm for 10 minutes.

The supernantant of the solutions were filtered through with 0.45 um Whatman filter

paper under anaerobic conditions. Extracts were analyzed for soluble reactive

phosphorus (SRP), using a Shimadzu UV-160 visible spectrophotometer (Method 365.1,

USEPA 1993).









The residual sediment sample was treated with 25 mL of 0.1 MNaOH. Sediment

suspensions were agitated on a mechanical shaker, followed by centrifugation for 10

minutes. The supernatant solution were filtered through with 0.45 um filter paper. For

analysis of SRP (NaOH-Pi), concentrated sulfuric acid (H2SO4) was added to each

solution. This portion is represented as the Fe-Al bound P. The solutions were also

analyzed for total phosphorus (NaOH-TP) by digestion with 11 N sulfuric acid (H2SO4)

and potassium persulfate (K2S208) at 3800C. Extraction with 0.1 MNaOH also removed

the P associated with humic and fulvic acids. The difference between NaOH-TP and

NaOH-Pi is alkali extractable organic P (NaOH-Po) associated with both fulvic and

humic acids.

The residual soils from the NaOH extraction were treated with 25 mL of 0.5 M

HC1. Sediment solutions were shaken continuously for 24 hrs, followed by centrifugation

for 10 minutes. The supernatants were filtered through 0.45um filters. Filtered solutions

were analyzed for HCL-Ca-Mg bound P fraction.

The residue from the 0.5 MHCL extraction was combusted at 5500C for 4 hours.

Samples were filtered with Whatman #41 filter paper and the ash was dissolved in 6 M

HC1. All supernatants, except the KC1 extractions, were analyzed by using the automated

ascorbic acid colorimetric method (EPA 365.1, 1993).































Figure 2-6. Inorganic P fractionation scheme after Reddy et al. 1998.


Data Analysis

A variance check was conducted to test for normality. The data was not normal, so

we transformed the data using two transformations (log and square root). However, the

transformations were found not to be normal. A Wilcoxon/Kruskal-Wallis test was

performed to compare the medians instead of the means using JMP Statistics, Version 4

(SAS Institute). Microsoft excel (Microsoft 2000) was used to performed any regression

analyses and correlations.


Soil 'Wet samples weighed out to a 0.5 g dry weight equivalent
1 M KCI [2 hrs] Readily available Pi [SRP]



Residue

0.1 M NaOH [17 hrs] H-P
I [TP]- [SRP]-NaOH-Po
Fe-AI bound Pi [SRP]
Residue (acidified)


a Ca-Mg bound Pi [SRP]
1 0.5 M HC [24 hrs] Ca-Mgbound P SRP]
Residue Ashed ( 550C Residual Po [TP]
6 M HCI digestion









Results

Physical and Chemical

Several physical and chemical sediment properties were measured for each

sample station including bulk density and organic matter. Bulk density ranged from

0.06-1.18 g cm-3, for all the lakes, with sediment texture varying from organic mud to

sand. Lake Tohopekaliga had the highest average bulk density (0.83 0.3 g cm-3) and

Lake Kissimmee had the lowest (0.42 0.47 g cm-3) of all the lakes (Table 2-1). The

loss on ignition (LOI), which estimates organic matter content, ranged from 0-55%. The

higher percent values represent the greatest content of organic matter in the sediment.

Lake Kissimmee had the highest average LOI value (26.3 25.1%) and Lake

Tohopekaliga had the lowest (3.2 3.6%). There were no significant differences found

between the lakes for bulk density and LOI due to high standard deviations, an artifact of

the different sediment types.

Total analyses of macroelements were conducted for the sediments of each lake

(Table 2-1). Total carbon values for the sediments ranged from 4-293 g kg-1 for all lakes,

with an overall mean of 70.6 + 85.9g kg-1. The mean total C values were higher in Lake

Kissimmee (124 121 g kg-1) and lowest in Lake Tohopekaliga (16.3 18.8 g kg-1).

Total nitrogen values ranged from 0.32-26.5 g kg-1 with an overall mean of 6.4 7.98 g

kg-1. The highest value of total N was in Lake Kissimmee (11.7 11.3 g kg-1) and the

lowest was Lake Tohopekaliga (1.37 1.38 g kg-1).

The total P values ranged from 38.1-1811 mg kg-1 with an overall mean of 468 +

557 mg kg-1. The highest total P levels were found in Lake Kissimmee (703 + 685 mg

kg-1) and lowest levels were found in Lake Tohopekaliga (138 127 mg kg-1). There









were no significant differences found between the lakes for total C, N, and P due to high

standard deviations, an artifact of the different sediment types.

Table 2-1. Average Bulk Density (BD), Loss on Ignition (LOI), Total C, Total N, and
Total P for Lakes Tohopekaliga, Cypress, Hatchineha, Kissimmee, and
Istokpoga. n=10 per lake.

Lake BD LOI Total C Total N Total P
-3 1-
gcm % g kg1 g kg1 mg kg 1
Tohopekaliga 0.83 0.31 3.2 3.6 16.3 18.8 1.37+ 1.38 138 127
Cypress 0.47 + 0.43 17.8 17.8 79.8 + 85.5 7.36 + 7.87 642 + 700
Hatchineha 0.51 0.47 17.8 18.6 51.8 83.7 7.8 8.1 581 594
Kissimmee 0.42 0.47 26.3 25.1 124 121 11.7 11.3 703 685
Istokpoga 0.63 0.44 10.7 12.6 51.8 61.9 3.88 4.63 276 297


Metals

Sediments were analyzed for select metals using a 1 MHC1 extraction to

determine Calcium (Ca) and Magnesium (Mg) and an oxalate extraction was used to

determine the iron (Fe) and aluminum (Al) concentrations (amorphous & poorly-

crystalline). The range of Ca values was from 11585-12367 mg kg-1 with an overall

mean of 3290 3601 mg kg-1 (Table 2-2). Lake Hatchineha had the higher average Ca

value (5090 5123 mg kg-1) while Lake Tohopekaliga had the lowest (912 918 mg kg

1). There was no significant difference in Ca among the lakes, due to the high standard

deviation, an artifact of different sediment types.

The mean value of Mg was 549 + 731 and ranged from 0-2756 mg kg-1. Lake

Hatchineha had the higher amount (936 1077 mg kg-1) and Lake Tohopekaliga was

found to have the least amount of Mg (102 79 mg kg-1). There was no significant

difference in Mg between the lakes. The mean Fe amount was 6409 8082 mg kg-1

ranging from 383-26473 mg kg-1. Lake Kissimmee had the highest mean value of Fe

(11736 11003 mg kg-1) and Lake Tohopekaliga had the lowest (1515 1333 mg kg-1).









The Fe concentration in Lake Tohopekaliga was significantly lower than in Lake

Kissimmee (P < .05). Aluminum ranged from 517-36135 mg kg-1 with a mean value of

8180 10541 mg kg-1. Lake Hatchineha had the highest amount of Al (12733 14068)

mg kg-1) and Lake Tohopekaliga had the lowest (2578 3166 mg kg-1). There was no

significant difference found for Al between the lakes. Overall, Al was higher in all lakes

(8180 10541 mg kg-1) while Mg had the lowest concentration (549 + 731 mg kg-1)

(Figure 2-7).

Table 2-2. HC1 extractable Ca and Mg concentrations and oxalae extractable Fe and Al
concentrations for Lakes Tohopekaliga, Istokpoga, Cypress, Kissimmee, and
Hatchineha. Values are reported as mean and standard deviation (n=10) per
lake.

Lake Ca Mg Fe Al
mg kg1 mg kg' mg kg-1 mg kg1
Tohopekaliga 912 918 102 79 1515 1333 2578 3166
Cypress 3515 3283 676 779 8423 9174 11943 13224
Hatchineha 5090 5123 936+ 1077 7458 7803 12733 14068
Kissimmee 4159 3970 639 645 11736+ 11003 10194+ 10204
Istokpoga 2775 2432 390 + 502 2913 3208 3457+ 3895


Inorganic P Fractionation

Inorganic P extracted with 1 M KC1 is identified as the labile Pi portion that is most

bioavailable and readily released to the overlying water column of a lake (Reddy et al.

1998). The proportions of the P fractions were relatively similar across all five lakes

(Figure 2-8 and Figure 2-9). The KCl-Pi represented <1% of total P in all 5 lakes. The

NaOH-Pi fraction, considered to represent Fe and Al bound P, ranged from 21 to 37% of

total P with a mean of 29%. The greatest concentration of Fe and Al bound P was found

in Lake Cypress (221 250 mg kg-1) while the lowest concentration was found in Lake

Tohopekaliga (39.6 43.3 mg kg-1) (Table 2-3).












16000-
Tohopekaliga
Cypress
12000- Hatchinea
0 Kissimmee
Istokpoga
a 8000



4000



0.
HCI-Mg HCI-Ca Oxa-Fe Oxa-AI

Figure 2-7. Amount of metals, HCI-Mg, HCI-Ca, Oxalate-Fe, and Oxalate Al, in mg kg-1
for all lakes.

The HCl-Pi fraction which represents the Ca and Mg bound P ranged from 4 to 8%

of total P with a mean of 5%. Calcium and Mg bound P were found to be the highest in

Lake Hatchineha (39.5 37.1 mg kg-1) and the lowest in Lake Tohopekaliga (11.6 11.7

mg kg-1). Total inorganic phosphorus (TPi) was calculated by summing the KC1, NaOH,

and HC1 extract values, and represented between 26-39% of total P. Lake Cypress was

found to have the highest amount of total inorganic P (246 265 mg kg-1) while Lake

Tohopekaliga had the least amount (52.3 54.9).

Some organic P fractions such as NaOH Po, which is associated with humic and

fulvic acids were identified. The distribution of NaOH Po ranged from 17 to 34% of total

P with a mean of 26%. Lake Kissimmee had the highest amount (214 238 mg kg-1) of

humic and fulvic acids while Lake Tohopekaliga had the least amount (40.9 46.8 mg

kg-1). The residual organic P, which is considered the most recalcitrant fraction ranged,

from 28-43% of total P with a mean of 40% with Lake Kissimmee having the higher









amount (291 296 mg kg-1) while Lake Tohopekaliga had the least of amount (51.0

59.9 mg kg-1) of residual organic P. Total organic P, calculated by summing NaOH-Po

and residual organic P, represented between 59-74% of total P. The highest amount of

total organic P was found in Lake Kissimmee (506 508 mg kg-1) and the least amount

was found in Lake Tohopekaliga (91.9 106 mg kg-1). The percent of total organic P

was much higher than total inorganic P at 65 and 35%, respectively.

Sediment total P values for the lakes were 144, 274, 511, 660, and 680 mg kg-1 for

lakes Tohopekaliga, Istokpoga, Hatchineha, Cypress, and Kissimmee, respectively.

There was no significant difference found between each lake for each P forms

determined, which may be due to the high standard deviations, an artifact of different

sediment types.











Lake Tohopekaliga


0.76%


* KCI-Pi
* NaOH-Pi
O HCI-Pi
O NaOH-Po
* Residue-P


7 8%


28%


TP=144 mg kg-1


Lake Cypress


0.18%


* KCI-Pi
* NaOH-Pi
O HCI-Pi
O NaOH-Po
* Residue-P


TP=600 mg kg-1


17%


Lake Hatchineha


0.23%


38%







TP=510 mg kg-1


* KCI-Pi
* NaOH-Pi
O HCI-Pi
O NaOH-Po
* Residue-P


85 %

25%


Figure 2-8. Distribution of P forms in Lakes Tohopekaliga and Hatchineha.











Lake Kissimmee


0.16%


* KCI-Pi
SNaOH-Pi
O HCI-Pi
O NaOH-Po
* Residue-P


TP=680 mg kg-1


Lake Istokpoga


0.58%


28%


TP=274 mg kg-1


36%
33%


Figure 2-9. Distribution of P forms in Lakes Cypress and Kissimmee.

Table 2-3. Mean and standard deviations for P forms: KC1- Pi, NaOH Pi, HCl-Pi, TPi,
NaOH Pi, residue P, total Po and total P (n=10) for each lake in mg kg-1 for all
P forms.


Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga

P forms
KCI-Pi 1.1 0.8 1.1 0.4 1.2 0.7 1.1 0.6 1.6 1.0
NaOH-Pi 39.6 43.3 221 250 150 162 145 174 87.2 93.4
HCl-Pi 11.6 11.7 23.9 22.1 39.5 +37.1 27.7 48.3 17.6 17.1
TPi 52.3 54.9 246 265 191 + 190 173 174 106 110
NaOH-Po 40.9 46.8 103 97.4 125 127 214 238 92.0 114
ResidueP 51.0 59.9 251 272 193 225 291 296 75.8 84.1
Total Po 91.9 106 354 366 319 322 506 508 167 196
Total P 144 160 600 629 510 510 680 660 274 298


* KCI-Pi
SNaOH-Pi
O HCI-Pi
O NaOH-Po
* Residue-P









Discussion


Physical and Chemical

The lakes characterized as mud had less than 62 um of clay and silt in the

sediments of the lakes and all other lakes were defined as sand (>63 um) (Oui and

McComb 2000). The lakes, such as Cypress, Kissimmee, and Hatchineha, with a high

mean total P contained primarily mud sediments with low bulk density and high

concentrations of total C, N and organic matter. Lake sediments with low total P, high

bulk density, and low total C, N and organic matter, such as Istokpoga and Tohopekaliga

were dominantly sand sediments. These results are comparable to the mud and sand

sediments of Lake Okeechobee, Florida (McArthur 1991, Olila and Reddy 1993).

Typically, nutrient content tends to increase with an increase in organic matter (Farnham

and Finney 1965).

The sample data was divided into sand and mud sediment type to compare the

distribution of bulk density, LOI, and total P, N, and C between the two major types.

There were 26 sand stations and 24 mud stations for all lakes combined (Table 2-4 and

Table 2-5). When looking at the individual stations and their respective sediment type,

the muds had bulk densities ranging from 0.04 to 0.50 g cm-3 while the sands had bulk

densities ranging from 0.56 to 1.18 g cm-3. The muds had higher organic matter content

and nutrients compared the sands.

There were no differences found between the sand stations of each lake.

However, Tohopekaliga's mud stations were significantly higher in bulk density

compared to the mud sediments of Hatchineha; and Kissimmee (P<0.007). Lake

Kissimmee's mud stations were significantly higher in LOI, total C and N compared to

the mud sediments of Tohopekaliga (P<0.05). The mud stations (n=24) were









significantly higher in bulk density, LOI, and total C, N, and P compared the sand

stations (n=26) for all lakes combined (P<0.05).

Total P, C, and N were highly correlated to LOI with R2 = 0.87, 0.99, and 0.98

respectively for the mud sediments (Figure 2-10 to Figure 2-12). However, total P, C, N

were not highly correlated with LOI for the sand sediments with R2=0.24, 0.57 and 0.48

respectively. A strong positive correlation between sediment total P and LOI suggests

that organic are important as a P reservoir (Oui and McComb 2000). Total N and C

were well correlated to P with R2= 0.84 and 0.87, respectively, indicating that the P

source in these mud sediments may be related to organic matter (Figure 2-13 and Figure

2-14). However, there was not a strong relationship found between total C and N to P

with R2=0.54 and 0.55, respectively. The strong correlation of nutrient content with

organic matter demonstrates the importance of organic matter in nutrient cycling in lake

sediments.



Table 2-4. Mean and standard deviations for P forms for sand sediments: bulk density
(BD), mass loss on ignition (LOI), total carbon (TC), total nitrogen (TN), total
phosphorus (TP) per lake in mg kg-1 for all P forms.

Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
n=7 n=4 n=5 n=4 n=6
Sand
BD 1.0 + 0.1 0.9 0.3 0.9 0.2 0.9 0.02 1.0 + 0.2
LOI 1.2 0.4 2.9 + 1.9 1.7 0.7 1.7 + 1.7 2.4 + 1.0
TC 5.8 + 1.2 9.8 + 7.6 9.0 + 4.0 6.5 + 1.0 9.9 + 5.1
TN 0.6 + 0.2 0.9 + 0.7 0.8 + 0.3 0.7 + 0.2 0.7 0.4
TP 66 16 81 49 69 29 48 10 68 30










Table 2-5. Mean and standard deviations for P forms for mud sediments: bulk density
(BD), mass loss on ignition (LOI), total carbon (TC), total nitrogen (TN), total
phosphorus (TP) per lake in mg kg-1 for all P forms.


Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
n=3 n=6 n=5 n=6 n=4
mud
BD 0.4 0.1 0.2 0.2 0.1 0.05 0.1 0.1 0.2 0.1
LOI 7.8 3.4 27 17 34 11 42.7 18 23 12
TC 41 18 127 81 153 52 203 88 115 52
TN 3.2+ 1.3 12 8.0 15 5.0 19 8.0 9.0 + 4.0
TP 307+ 104 1016+ 679 1092 371 1139 523 587+ 217


y = 4.70x + 0.03
R2 = 0.99


S 300

200

0 100

0
0


25

20

15
,
0
o 54

0


0 10 20 30 40 50 60 70
Loss on Ignition (%)



y = 2.65x + 3.00
R2 = 0.57


Loss on Ignition (%)


Figure 2-10. Regression between concentrations of total C (g kg-1) to loss on ignition (%).
The mud sediments values are located at top graph and the sand sediments are
located at the bottom graph.











y = 0.44x- 0.63
R2 = 0.98


0 10 20 30 40 50 60 70

Loss on Ignition (%)




y= 0.21x+ 0.34
R2 = 0.48


2


1I
.
*'


Loss on Ignition (0/)

Figure 2-11. Regression between concentrations of total N (g kg-1) to loss on ignition
(%). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.


z
0-
Ia
"5











2000


200

S150




I-
E 100 -

0 50,


y = 28.8x + 52.7
R2 = 0.87


0 10 20 30 40 50 60 70
Loss on Ignition (%)



y = 11.2x + 44.7
R2 = 0.24


**
",*


Loss on Ignition (%)


Figure 2-12. Regression between concentrations of total P (g kg-') to loss on ignition
(%). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.


- 1600

S1200
E
C. 800

o 400
I-

































400 y = 4.83x + 27.28
SR2 = 0.54
300


200


100 -
I 0 -


0 5 10 15 20 25

Total C (g kg1)


Figure 2-13. Regression between concentrations of total P (mg kg-')and with total C (g
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.


2000 y=6.02x + 69.1
R2 = 0.84
- 1600 -

1 1200-

S800 wl

S400

0
0 ,-----,-----------------------

0 50 100 150 200 250 300 350

Total C (g kg-1)











2000 y = 64.0x + 98.2
600 R2 = 0.87
1600 -

a 1200 -
E
a. 800 "

o 400-

0
0 5 10 15 20 25 30
Total N (g kg -1)


y = 55.9x + 24.3
200R2 = 0.55

c 150 *

.100

I 50 *
o 4 *

0
0 --
0 1 2 3
Total N (g kg -1)

Figure 2-14. Regression between concentrations of total P (mg kg-1) and with total N (g
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.

Metals

Metals may increase the capacity of sediments to retain P under certain

conditions. The ability of P to be retained by Fe/Al and Ca/Mg depends on the pH and/or

redox conditions of the sediments. Phosphorus is retained by Fe/Al compounds under

acidic conditions and therefore is more stable under low pH conditions. Depending on

redox conditions, the reduction of insoluble ferric iron (Fe3+) to a more soluble ferrous

iron (Fe2+) compound can lead to P released from the sediment. When there is a

dominance of Ca/Mg P in the sediments, P is more stable under high pH or alkaline









conditions. Organic acids from settling or deposited decomposing organic matter can

lower the pH short term and lead to dissolution of Ca.

The sandier lakes, such as Lake Tohopekaliga and Istokpoga had lower amounts

of Ca, Mg, Fe, and Al, compared to the muddier sediments of Cypress, Kissimmee, and

Hatchineha (refer to Figure 2-10). Phosphorus accretion in these lakes is significantly

associated with Ca, Mg, Fe, and Al; thus the presence of these metals play a very

important role in inorganic P retention in lake sediments (Table 2-6).

Table 2-6. Pearson correlations for selected metals and total P

Total P Ca Mg Fe
Ca 0.924
(<0.001)
Mg 0.924 0.962
(<0.001) (<0.001)
Fe 0.969 0.887 0.879
(<0.001) (<0.001) (<0.001)
Al 0.943 0.929 0.970 0.908
(<0.001) (<0.001) (<0.001) (<0.001)


Samples were again divided into muds and sands to look at the difference in the

relationship between metals with total P amongst the mud and sand sediments (Table 2-7

and Table 2-8). The mud sediments in each of the five lakes contain greater amounts of

Ca, Mg, Fe and Al compared to the sand sediments. Total phosphorus concentrations

were regressed against Ca, Mg, Fe and Al for the mud sediments Both Ca, Mg, and Al

were significantly correlated with phosphorus with a R2=0.72, 0.68 and 0.77 respectively

(P<0.001) (Figure 2-18 to Figure 2-21). Oxalate-Fe was highly correlated with

phosphorus with R2=0.88, which suggest that Fe plays a greater role in inorganic P

stability. Calcium, Mg, Fe and Al were also regressed against total P for the sand









sediments and did not correlate well with phosphorus with a R2=0.01, 0.68, 0.58 and 0.39

respectively (Figure 2-15 to Figure 2-18).

There were no significant differences in metals found between the sand stations of

each lake. However, there was a difference found in the mud stations in Mg between

Tohopekaliga and Hatchineha (P<.05). There was also a significant difference found in

the mud stations in Fe content between Lake Kissimmee and Tohopekaliga (P<0.03).

There were also significant differences found between the mud and sand sediments

within each lake for all metals (Ca, Mg, Fe, Al) (P<0.05).


Table 2-7. Mean and standard deviations for P forms for sand sediments: HCl-Ca and
Mg and Oxalate Fe and Al mg kg-1 for all lakes

Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
n=7 n=4 n=5 n=4 n=6
Sand
Ca 470 375 1041 846 669 164 237 42.8 1403 1080
Mg 14.9 + 17.7 42.2 + 53.4 46.7 + 30.2 2.7 + 3.5 49.7 + 39.4
Fe 800 114 1070 579 971 458 1182 195 727 324.2
Al 1060 +616 1343 824 1131 376 632 122 851 +404


Table 2-8. Mean and standard deviations for P forms for mud sediments: HCl-Ca and
Mg and Oxalate Fe and Al mg kg-1 for all lakes

Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
n=3 n=6 n=5 n=6 n=4
mud
Ca 1946 1042 5165 3288 9511 3186 6774 2802 4834 2527
Mg 304 234 1098 745 1825 7795 1063 456 902 416
Fe 3185 1409 13325 8899 13947 +5617 18772 +8328 6193 2609
Al 61117 4137 19010+ 12828 24335 10423 16569 +8093 7366 3360










y = 17.8x -140
R2 = 0.77


* U


500 1000 1500
Total P (mg kg-1)


y = 14.6x + 33.6
R2 = 0.58

*
."*


Total P (mg kg-1)


Figure 2-15. Regression between concentrations of oxalate-Al (mg kg-1) with total P (mg
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.


40000
32000
24000
16000
8000
0


2000


3000

S2000

S1000
O
o0











y = 14.6x -835
R2 = 0.88


* S


-.


500 1000 1500

Total P (mg kg"1)



y = 8.1832x + 373.97
R2 = 0.3928



*


Total P (mg kg1)


Figure 2-16. Regression between concentrations of oxalate-Fe (mg kg-') with total P (mg
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.


30000
24000

18000
12000

6000

0


2000


3000


2000


1000







44



16000 y = 5.58x + 968
SR2 = 0.72
S12000 -

E 8000 -

S4000

0
0 500 1000 1500 2000
Total P (mg kg-1)



4000 y = 2.78x + 590
R2 = 0.01
3000

S2000 *
9 S
5 1000 *
I 5- *

0 50 100 150 200
Total P (mg kg1)

Figure 2-17. Regression between concentrations of HCl-Ca (mg kg-1) with total P (mg
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.











3000 y = 1.11x + 105
S2500 R2 = 0.68
2000
-1500 -
M 1000 -
500
0 Ma
0 500 1000 1500 2000
Total P (mg kg-1)



160 y= 1.05x 38.1
R2 = 0.68
S120 *

E 80 -

40 -
I *

0 50 100 150 200
Total P (mg kg-1)

Figure 2-18. Regression between concentrations of HCl-Mg (mg kg-1) with total P (mg
kg-1). The mud sediments values are located at top graph and the sand
sediments are located at the bottom graph.

Inorganic P Fractionation

The sandier lakes, such as Tohopekaliga and Istokpoga had less inorganic and

organic P compared to the lakes characterized as muds (Kissimmee, Hatchineha, and

Istokpoga). There were no differences found between these any of these lakes due to a

high standard deviation, an artifact of different sediment types. The sample data was

divided into sand and mud sediment type to compare the distribution of P between the

two types (Table 2-9 and Table 2-10).

The proportions of P fractions were relatively the same for both sediment type

(Figure 2-19). However, the mean total P concentrations for the sand sediments were









much less than for the mud sediment 61 30 and 855 459 mg kg1, respectively.

Although, the sand sediments had the greater percentage of available P (KCl-Pi) than was

found in the mud sediments, the muddier sediments may release more P, due to their

greater amount of total P. These results are similar to those found in Lake Okeechobee

for these major sediment types, in which greater concentrations of total P was found in

the muds compared to the sands (Olila and Reddy 1993).

Sand sediment had a slightly greater percent ofNaOH-Pi (Fe and Al-P) fraction

(31%) than the mud sediments (29%). A similar trend was found for HCl-Pi (Ca and

Mg-P) and NaOH-Po humicc and fulvic acids) fractions. Residue P distribution was

greater in the mud sediments than in the sand sediments.

There were no significant differences found between the sand stations of each lake

for each P fractions. For the mud sediments of Lake Istokpoga, concentration of KCl-Pi

(labile P) fraction was significantly higher than Tohopekaliga and Kissimmee (P<0.05).

Total organic P was found to be significant higher in Kissimmee compared to

Tohopekaliga for the muds (P<0.05). There were also significant differences found

between the mud and sand sediments within each lake for all parameters (P<0.05).









Table 2-9. Mean and standard deviations for P forms for sand sediments: KC1- Pi, NaOH
Pi, HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P per lake in mg kg-1
for all P forms.

Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
Sand n=7 n=4 n=5 n=4 n=6
P forms
KCI-Pi 1.2 + 0.9 0.7 + 0.3 0.6 + 0.1 0.6 0.04 1.3 + 0.8
NaOH-Pi 17.7 5.6 24.9 21.2 15.5 4.5 11.4 3.4 26.1 19.1
HCl-Pi 6.3 + 2.4 8.7 + 5.8 9.2 + 5.0 3.3 1.2 5.9 + 3.9
TPi 25.2 + 8.0 34.3 + 25.3 25.3 + 7.1 15.2 + 4.5 33.2 + 21.0
NaOH-Po 14.6 + 4.6 17.6 + 14.5 21.9 + 7.3 9.3 + 3.4 14 + 13.8
Residue P 19.7 5.5 28.3 18.2 12.8 6.1 13.2 3.1 18.9 + 14.3
Total Po 34.4 7.2 45.8 32.1 34.7 9.3 22.5 5.9 32.9 22.4
Total P 59.6 + 3.3 80.2 56.8 60.0 + 12.2 37.8 10.4 66.1 + 40.4


Table 2-10. Mean and standard deviations for P forms for mud sediments: KC1- Pi,
NaOH Pi, HCl-Pi, TPi, NaOH Pi, residue P, total Po and total P.

Tohopekaliga Cypress Hatchineha Kissimmee Istokpoga
mud n=3 n=6 n=5 n=6 n=4
P forms
KCl-Pi 1.5 + 0.4 1.4 + 0.3 1.8 + 0.3 1.5 + 0.4 2.1 + 0.8
NaOH-Pi 234 175 352 248 285 119 234 175 179 82.9
HCl-Pi 43.9 + 58.3 34 + 23.6 69.7 + 27.9 43.9 + 58.3 35.2 + 12.9
TPi 279 145 384 263 356 112 280 145 216 95.1
NaOH-Po 351 214 163 80.0 230 + 97.1 352 214 209 94.0
Residue P 478 235 418 234 375 181 478 235 161 + 68.4
Total Po 191 + 145 553 350 605 175 829 392 370 155
Total P 1109 483 948 591 962 281 1109 483 586 +220











Sand Sediments


1%


S33% KCL-Pi
NaOH-Pi
HCL-Pi
NaOH-Po
Residue P
11%
25%
TP = 61 + 30 mg kg-1



Mud Sediment



0.2%


2 KCL-Pi
4 NaOH-Pi
HCL-Pi
NaOH-Po
5% 0 Residue P


26%
TP = 855 459 mg kg-1


Figure 2-19. The mean percent of mean TP (mg kg-1) of each P fractions (KCl-Pi,
NaOH-Pi, HCl-Pi, NaOH-Po, and Residue P) for both mud and sand
sediments for all the lakes









Conclusion

Lake sediments can function as a source or sink for dissolved P coming from

nonpoint and point sources. Chemical, physical, and microbial processes control the

exchange of P between the sediment and water column. For any planned restoration to

occur in these lakes, it is important to understand the forms and properties of P in lake

sediments to identify the factors that control P release from the sediment to the overlying

water column.

The sediments of each of the five lakes were characterized for bulk density, mass

loss on ignition (LOI), total C, N, and P, as well as selected metals (Ca, Mg, Fe and Al).

The bulk density ranged from 0.06-1.18 g cm3 with sediment texture varying from

organic mud to sand. The LOI values ranged from 0-55% with the highest values

representing the greatest content of organic matter. The sand stations tended to have low

organic matter and high bulk density and the mud stations typically had greater organic

matter and low bulk density. The lakes characterized as sandy lakes (Tohopekaliga and

Istokpoga) exhibit the characteristics of low organic matter and high bulk density while

the muddier lakes had the greater amount of organic matter and low bulk density

The lakes characterized as muds, primarily had high nutrient levels (total P, total N,

and total C) and organic matter content. The sandy lakes typically had less nutrients

(total P, total N and total C) and organic matter. There were strong correlations of total

P, N, C and bulk density to LOI for the mud station within each lake. Total C and total N

are generally found to be related to organic matter in sediments. A strong positive

correlation between total P and LOI were found, which suggest the importance of

organic as a P reservoir.









The muddier lakes also contained greater amounts of Ca, Mg, Al, and Fe than the

sandier lakes and are well correlated with total P. The mud stations of each lake

contained the greatest amount of iron compared to the sand stations and is significantly

and positively correlated with total P, which indicates that Fe plays a greater role in

inorganic P stability. The sand stations were not well correlated with any of the metals,

suggesting these selected metals may not play a great role in inorganic P stability.

The inorganic P results suggest that the greatest portion of inorganic P was in the

form most associated with Fe and Al (NaOH-Pi). The total organic P was proportionally

greater in each lake than total inorganic P. The mud stations contained the greatest

amount of TP and P associated with organic and also had greater amounts of available or

easily exchangeable P than the sands. The sand and mud stations were not at all different

in their distribution of P; however, the muds contained greater amounts of total P, so this

sediment type may contribute more to P release to the overlying water column of a lake.














CHAPTER 3
PHOSPHORUS FLUX OF SEDIMENTS UNDER DIFFERENT SIMULATED
LOADING CONDITIONS

Introduction

Phosphorus is essential for plant growth, but excessive amounts entering lakes can

lead to eutrophic conditions resulting in harm to the quality of water in many freshwater

systems such as Lake Okeechobee and Lake Apopka. Harm to fisheries, changes in

vegetation, and recreation can be some of the results of excessive quantities of P entering

into lakes. Phosphorus enters the surface water of freshwater lakes primarily by way of

nonpoint and point source pollutions from entities such as wastewater treatment plants

and from surface runoff from agricultural and urban areas.

Reducing nutrient inputs from nonpoint and point sources of pollution are essential

to restoring lake water quality. However, even after external P load to lakes have been

curtailed, internal P flux from the sediment to the water column can occur, contributing

heavily to the degradation of water quality in lakes (Welch and Cooke 1995). The idea of

internal loading is based on the recycling of nutrients from bottom sediments in lakes to

the overlying water column (Carpenter 1983). After load reduction, the internal load of

sediments will determine the trophic status of a lake and the amount of lag time for

recovery (Petterson 1998).

The equilibrium phosphorus concentration (EPC) can be used to determine the

extent of which the internal load will be released during restoration of a lake after

external load reductions. The EPC is defined as the P in solution that is in equilibrium









with P in the solid phase or the point where P is neither being retained nor released from

the sediment to the water column (Olila and Reddy 1993). At water column SRP

concentrations above the EPC, P is retained by the sediments and at concentrations

below, the sediments serve as a P source. The EPC can be a useful tool for water

managers to determine the water column SRP concentration for which sediments may act

as a potential source of P to the overlying water column of a lake. Water managers can

manage for the internal sediment P load by determining the EPC of aquatic systems. For

example, water managers may consider dredging a lake as a component of a restoration

plan; however dredging is very cost and labor intensive. Therefore, it is important to

look at the EPC of a lake to determine if this lake should be dredged or if focus should be

aimed at other activities during restoration.

There are four pathways for the exchange of P from the sediment to water column

of a lake: i) settling of insoluble (particulate) inorganic and organic P, ii) uptake of

soluble reactive P (SRP) by primary producers (algae) and its subsequent settling, iii)

sorption of soluble inorganic or organic P onto particles that settle onto the sediments,

and iv) sorption of soluble inorganic or organic P directly onto sediment particles (Reddy

et al. 1999). Sediments act as a net sink of P; however, when porewater P concentration

exceed the overlying water column concentration, SRP can be released from the sediment

(Moore et al. 1991).

The flux of P from the sediment to the water column can depend on processes such

as: i) diffusion and advection (wind/wave action, flow, and bioturbation), ii) processes

within the water column (biotic uptake and release, mineralization, and sorption by

particulate matter), iii) diagenetic processes mineralizationn, sorption, precipitation, and









dissolution) in bottom sediments, and iv) redox conditions (oxygen content), organic

matter content, pH, temperature and the presence of metal bound to P (Fe, Al, Ca, and

Mg) (Bostrom and Pettersson 1982, Holdren and Armstrong 1980, Moore et al 1991,

Wetzel 2001).

Wind/wave action can induce sediment resuspension and cause event driven large P

release from the sediment to the water column and thereby available for uptake by

primary producers (Pettersson and Bostrom 1985). Bioturbation can also increase the

release of P. However, P release may not occur over the entire lake sediment surface,

thus bioturbation may not be sufficient to perpeturate eutrophic conditions (Holdren and

Armstrong 1980). Diagenetic processes such as sorption (P release from soil mineral

surfaces or retention of P onto soil mineral surfaces), precipitation (formation of

amorphous precipitates), dissolution (solubilization of the precipitates), and

mineralization (breakdown of organic matter) can also mediate the release of P from the

sediments.

A decrease in dissolved oxygen of the water column can result in an increase in P

release from the sediments in freshwater lakes. However, oxygenation of the sediments

can result in a decrease in P release to the water column (Holdren and Armstrong 1980,

Patrick and Khalid 1974). It is important to note that for shallow and eutrophic lakes that

are well mixed, anaerobic conditions rarely persist for any extended periods of time

(Welch and Cooke 1995). However, these ephemeral anaerobic events can significantly

after water quality.

The release of P may result from the reduction of ferric iron (Fe3+) to ferrous iron

(Fe2+) in sediments or from the decomposition of organic matter (Holdren and Armstrong









1980). The ability of P to be retained by Fe/Al and Ca/Mg depends on pH. Phosphorus

is retained by Fe/Al compounds under low pH or acidic conditions (Patrick and Khalid

1974). When there is a dominance of Ca/Mg P in sediments, P is more stable under high

pH or alkaline conditions (Patrick and Khalid 1974). Organic acids from settling or

deposited decomposing organic matter can lower pH short term and lead to dissolution of

Ca bound P (Marsden 1989). Studies have also shown that temperature plays an

important role in P release from sediments, in which P release increased with increases in

temperature due in part to increased mineralization rates (Holdren and Armstrong 1980).

Hypothesis

The equilibrium P concentration will be higher in sediments with higher TP and

therefore provide a greater internal release of P during lake restoration as water quality

continues to improve.

Objectives

The objectives of this study were to: i) determine the release rate of P from the

sediments to the water column and ii) determine the equilibrium P concentration of the

sediments.

Site Selection

Data collected from the P characterization study provided the information for

selection of each site for the phosphorus flux study. Two stations per lake were chosen

from the P characterization study based on a range of sediment TP concentrations and

organic matter content (Figure 3-1 to Figure 3-5). Geographical Positioning Satellite

(GPS) equipment was used to locate each site within +/-5m of the true coordinates for the

stations chosen. The sampling location and latitude/longitude were documented at each

station (Table 3-1).


















































) 2 4 6 8 Kilometers
I


L. Tohopekaliga


Figure 3-1. Location of sampling stations for Lake Tohopekaliga.





56












16
j \

\ \

S15












0 1 2 3 4 iaTrtes


Figure 3-2. Location of sampling station for Cypress Lake.























103


0 1 2 3 4 Kilometers
II


L. Hatchineha


Figure 3-3. Location of sampling stations for Lake Hatchineha.














N






1012




1004








0 1 2 3 4 Kilometers

L. Kissimmee


Figure 3-4. Location of sampling stations for Lake Kissimmee.
























"10004




r\

"10007








S0 1 2 3 4 Kilometers

L. Istokpoga


Figure 3-5. Location of sampling stations for Lake Istokpoga.


Table 3-1. X and Y coordinates of each station. All coordinates are Universal Mercator,
North American Datum 1983, Units meters, UTM Zone 17.


Lake Station x_coord y_coord
Toho 2 460252 3125825
Toho 10 461809 3116800
Cypress 15 468261 3105828
Cypress 16 469875 3106370
Hatch 103 458082 3100650
Hatch 107 461341 3098421
Kissimmee 1004 472394 3084179
Kissimmee 1012 473188 3088426
Istokpoga 10004 469916 3030750
Istokpoga 10007 472779 3026915









Materials and Methods

Intact sediment cores were taken from two stations per lake (10 station total) by a

SCUBA diver using 7.5 cm wide plexiglas tube to collect 15 cores per site (-30 cores per

lake; -150 cores total). The cores were carefully driven approximately 30 cm into the

sediment with minimal impact to the sediment-water interface. Stoppers were inserted

into both ends of the cores and secured with tape for transport back to Gainesville,

Florida. Surface water from each lake was collected in 30 L containers for purposes of

re-flooding each core with lake water.

Upon arrival to the laboratory, the surface water was filtered with 0.45 um

Whatman filter paper to remove any particulates. The water column of each core was

slowly drained and replaced with 1 L of filtered lake surface water for a 30 cm water

column. The SRP concentration of the surface water was determined during analysis

using the Murphy and Riley Method (1962). All cores were spiked with SRP to yield

concentrations of 0, 15, 30, 60, 120 ug L-1 at the beginning of the experiment. Three

replicates per loading concentration for each site and flux measurements were

determined.

Water columns in each core were constantly aerated with room air using aquarium

pumps to maintain dissolved oxygen levels close to 5 mg L-1 for 25 days. Aluminum

shrouds were placed over the cores so that light could not penetrate and the cores were

incubated in a water bath to maintain a constant temperature (22 0.340C).

Water was periodically removed for analysis with a 10 mL plastic syringe fitted

with tubing to withdraw samples from the middle of the water column, in which, 10 ml

were taken and filtered with a 0.45 um syringe filter and analyzed for SRP using a









segmented flow colorimetric analyzer (USEPA 1993, Method 365.4). The water column

levels (1 L or 30 cm) were maintained after sampling by adding 10 ml of lake water back

into each core. Background water column SRP concentrations were an average of 6 4

ug L-1. Filtered water samples were immediately frozen until analysis.

Data Analysis

Data were analyzed using a one way analysis of variance (ANOVA) with a p value

of 0.05. The Tukey-Kramer test was used to evaluate differences between means. Data

were analyzed using JMP statistics version 4. Microsoft excel (Microsoft 2000) was used

to perform regression analyses and correlations.

Results

No P Addition

Water column SRP concentrations. In general, water column SRP

concentrations (filtered water with no P addition) tended to increase over time,

suggesting P flux from the sediment. The initial site water was 0.002, 0.003, 0.005,

0.009 and 0.011 for Lakes Kissimmee, Istokpoga, Tohopekaliga, Cypress and

Hatchineha, respectively.

Water column SRP concentrations increased over the first 2 days in all lakes,

except Lake Hatchineha, in which concentrations declined slightly at a rate of -36.4%

(Table 3-2). Concentrations increased in all the other lakes between 22% in Lake

Cypress to 400% in Lake Kissimmee. The mean water column SRP concentrations at

day 2 ranged from a low in Lake Hatchineha (0.007 0.002 mg L1) to a high in Lake

Istokpoga (0.014 0.003 mg L-) at day 2.

Mean water column SRP concentrations ranged from a low of 0.013 0.006 mg L-1

in Cypress Lake to higher concentrations in Lake Istokpoga at 0.022 0.007 mg L-1 at









day 7 (Table 3-2). Between day 2 and 7 water column SRP concentrations increased for

all lakes, however, Lake Cypress and Hatchineha values were close to their initial water

column SRP concentration at day 7. The change in water column SRP concentrations

ranged from a high of 650%in Lake Kissimmee to 27% in Lake Hatchineha.

After 7 days, the SRP concentrations, for the most part, increased over the course

of the experiment (Table 3-2). Water column SRP concentrations ranged from a high in

Lake Tohopekaliga (0.045 0.059 mg L-1) to 0.015 0.003 mg L-1 in Lake Kissimmee

by the end of the study (-25 days). The change in concentration increased between

1233% from the initial concentration in Lake Istokpoga to 100% in Cypress Lake.

P flux rates. The SRP flux rate was determined based on the slope of the curve

of water column SRP concentration over time. At 2 days, the mean P flux ranged from a

rate of -1.668 0.885 (mg m-2 d-1) in Lake Hatchineha to a positive rate of 0.784 0.458(

mg m-2 d-1) in Lake Istokpoga (Table 3-3). The positive P flux rates of Lakes

Tohopekaliga, Kissimmee and Istokpoga suggest that the lakes are releasing phosphorus

to the water column, while the negative flux rates of Lake Cypress and Hatchineha

suggest P retention by sediments. There was a difference in P flux rates at day 2, in

which, rates were lower in Lake Hatchineha compared to the other lakes (Istokopoga,

Tohopekaliga, Kissimmee and Cypress P<0.0001). This difference may be due to

differences in the sediment characteristics of the lakes (sediment type) or past nutrient

loading (Table 3-4 and Table 3-5).

The mean 7 day P flux rate for the lakes ranged from -0.036 0.168 mg m-2 d-1 in

Lake Hatchineha to a high of 0.439 0.296 mg m-2 d-1 in Lake Istokpoga (Table 3-3).












Table 3-2. Percent change in Water Column SRP (mg L1) under no P additions, for all lakes, at day 2, 7, and 25. A negative (-)
percent (%) change indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in
SRP concentrations. n=6 for all lakes except Cypress in which n=4.

Initial ---------------SRP (mg L-)------------- --------Percent Change (%)---------
SRP
Lake (mg L1) 2 d 7 d 25 d 2 d 7 d 25 d
Tohopekaliga 0.005 0.008 0.002 0.017 0.012 0.045 0.059 60 240 800
Cypress 0.009 0.011 + 0.003 0.013 + 0.006 0.018 + 0.015 22 44 100
Hatchineha 0.011 0.007 0.002 0.014 0.007 0.033 0.033 -36 27 200
Kissimmee 0.002 0.010 + 0.001 0.015 + 0.002 0.015 + 0.003 400 650 650
Istokpoga 0.003 0.014 0.003 0.022 0.007 0.040 + 0.036 367 633 1233


Table 3-3. Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee, Istokpoga, Cypress, and Hatchineha at no P
additions at 2, 7, and 25 days. n=6 for all lakes except Cypress (n=4).


--------------------P flux mg m-2 d-1------------------


Lakes 2 day 7 day 25 day
Tohopekaliga 0.103 0.430 0.311 0.255 0.418 0.734
Cypress -0.003 0.520 0.085 + 0.180 0.070 + 0.142
Hatchineha -1.67 + 0.885 -0.036 + 0.168 0.298 + 0.412
Kissimmee 0.192 + 0.271 0.249 0.255 0.065 0.019
Istokpoga 0.784 + 0.458 0.439 0.296 0.295 0.403












Table 3-4. Sediment characteristics of all stations for each lake for bulk density, mass loss on ignition (LOI), and total C, N, and P (mg
kg-1). N=10


Sediment Bulk DensityLOI TC TN TP
Lake Station Type G cm % g kg g kg mg kg
Tohopekaliga T2 organic mud 0.25 11.2 57.9 4.54 423
Tohopekaliga T10 sand 1.06 1.4 5.41 0.57 61.8
Cypress C15 organic mud 0.08 32.6 140 12.4 1036
Cypress C16 organic mud 0.06 42.7 201 19.4 1694
Hatchineha H103 organic mud 0.17 15.0 72.8 6.81 494
Hatchineha H107 organic mud 0.06 38.8 180 17.8 1126
Kissimmee K1004 sand 0.57 1.94 7.59 1.09 60.6
Kissimmee K1012 organic mud 0.05 51.9 245 22.1 1333
Istokpoga 110004 organic mud 0.13 25.8 127 8.51 721
Istokpoga 110007 organic mud 0.13 19.7 95.7 7.68 555












Table 3-5. Sediment characteristics of all stations for each lake for oxalate-Fe and Al and HCl-Ca and Mg. n=10



Lake Station Fe Al Ca Mg
Tohopekaliga T2 4800 10529 3088 563
Tohopekaliga T10 760.3 721.3 288.4 0.0
Cypress C15 17844 23532 6686 1360
Cypress C16 19970 28238 8221 1649
Hatchineha H103 5510 8813 4214 680
Hatchineha H107 13641 21335 9619 1636
Kissimmee K1004 1403 801 274 7
Kissimmee K1012 24150 20218 7303 1252
Istokpoga 110004 8238 10925 6257 1152
Istokpoga 110007 5653 6189 3977 796









The positive P flux values of Lakes Istokpoga, Kissimmee, Tohopekaliga and

Cypress suggest P release to the overlying water column, while the negative P flux rates

of Lake Hatchineha suggest retention by the sediments. The P flux rates were

significantly lower in Lake Hatchineha compared to Lake Istokpoga (P<0.05). This

dissimilarity may be due to differences in sediment characteristics. Lake Istokpoga

sediments are characterized mostly by sand compared to the muddier sediments of Lake

Hatchineha, with greater potential binding sites.

There were no significant correlations between P flux and any of the sediment

characteristics, however, TP was significantly and negatively correlated to bulk density

and significantly and positively correlated to Ca, Mg, Fe, and Al (Table 3-6 and Table 3-

7).

At day 25, the mean P flux ranged from a low rate of 0.065 0.019 mg m-2 d-1 in

Lake Kissimmee to a high of 0.418 0.734 mg m-2 d-1 in Lake Tohopekaliga (Table 3-3).

The positive P flux rates of all these lakes suggest P release from the sediments. There

were no significant differences in P flux rates at day 25 at no P additions.












Table 3-6. Correlation between sediment properties with the Pearson correlation on top and the P-value on the bottom in parentheses.
All correlations are significant to P<0.05. n=10


Bulk
Density LOI total C total N total P Fe Al Ca Mg

LOI -0.76
(<0.05)
total C -0.77 1.00
(<0.05) (<0.001)
total N -0.73 0.99 0.99
(<0.05) (<0.001) (<0.001)
total P -0.74 0.95 0.95 0.96
(<0.05) (<0.001) (<0.001) (<0.001)
Fe -0.67 0.96 0.95 0.95 0.94
(<0.05) (<0.001) (<0.001) (<0.001) (<0.001)
Al -0.72 0.89 0.88 0.90 0.96 0.92
(<0.05) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001)
Ca -0.82 0.92 0.92 0.91 0.91 0.83 0.90
(<0.001) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001)
Mg -0.83 0.92 0.91 0.90 0.93 0.84 0.93 0.99
(<0.001) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001) (<0.001)












Table 3-7. Correlation between P flux and EPCw with sediment properties with the Pearson correlation on top and the P-value on
the bottom in parentheses. All correlations are significant to P<0.05. n=10


Bulk
Density LOI total C total N total P EPCw Fe Al Ca Mg
P Flux
No P 0.184 -0.307 -0.274 -0.329 -0.314 0.488 -0.357 0.465 -0.437 -0.385
(0.611) (0.388) (0.444) (0.353) (0.377) (0.153) (0.312) (0.176) (0.207) (0.272)
15 -0.014 0.046 0.081 -0.006 -0.079 0.423 -0.136 -0.291 -0.003 -0.010
(0.968) (0.899) (0.823) (0.987) (0.828) (0.223) (0.707) (0.415) (0.994) (0.977)
30 0.568 -0.426 -0.422 -0.439 -0.464 0.105 -0.480 -0.559 -0.425 -0.435
(0.087) (0.220) (0.225) (0.204) (0.176) (0.773) (0.161) (0.093) (0.220) (0.208)
60 0.221 -0.360 -0.358 -0.390 -0.247 0.208 -0.396 -0.261 -0.256 -0.168
(0.540) (0.306) (0.309) (0.266) (0.491) (0.563) (0.258) (0.467) (0.475) (0.643)
120 -0.010 -0.041 -0.064 0.023 0.155 -0.410 -0.008 0.252 0.128 0.174
(0.979) (0.910) (0.861) (0.949) (0.668) (0.239) (0.982) (0.483) (0.726) (0.631)









Phosphorus Addition (15 ug L1)

Water column SRP concentrations. The initial SRP concentrations ranged from

0.017 mg L-1 in Lake Kissimmee to a high of 0.026 mg L-1 in Lake Hatchineha (Table 3-

8). The mean water column SRP concentrations at day 2 ranged from a low in Lake

Kissimmee (0.010+0.001 mg L1) to a high in Cypress Lake (0.0230.003 mg L-1).

Concentrations decreased in all lakes, except, Lake Tohopekaliga, in which

concentrations increased at a rate of 8% and declined in all other lakes at a rate between

6% in Cypress Lake to 41% in Lake Kissimmee. These results suggest P retention by

sediments in all lakes, except Lake Tohopekaliga.

The mean SRP concentration ranged from a high in Lake Istokpoga (0.024 0.008

mg L-) to a low concentration in Lake Kissimmee (0.015 0.002 mg L-) at day 7 (Table

3-8). Water column SRP concentrations increased in Lake Tohopekaliga and Istokpoga

over a 7 day period, even after the initial spike, suggesting P release from the sediments

at a rate of 5 and 33%, respectively. In Lake Kissimmee, Cypress Lake and Lake

Hatchineha water column SRP concentrations decreased at a rate less than 45%,

suggesting P retention by the sediments.

After 7 days, the water column SRP concentrations continued to increase over the

course of the experiment for all lakes at a rate between 0% in Lake Kissimmee to 75% in

Lake Tohopekaliga. The mean water column SRP concentrations at day 25 ranged from

a low in Lake Kissimmee (0.0170.002 mg L-) to a high in Lake Tohopekaliga

(0.035+0.019 mg L1) (Table 3-8). These results suggest that all the lakes all releasing P

from the sediments at this P addition (15 ug L-1).














Table 3-8. Percent change in SRP mg L-1 at 15 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%)
indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP concentrations.
n=6 for all lakes except Cypress in which n=5.


Initial -------------SRP (mg L)--------------- -----Percent Change (%)----
Cone.
Lake (mg L1) 2 d 7 d 25 d 2 d 7 d 25 d
Tohopekaliga 0.020 0.022 0.002 0.021+0.010 0.035+0.019 8 5 75
Cypress 0.024 0.0230.003 0.0180.005 0.0320.020 -6 -25 33
Hatchineha 0.026 0.0220.002 0.0180.004 0.030+0.026 -15 -31 15
Kissimmee 0.017 0.010+0.001 0.0150.002 0.0170.002 -41 -12 0
Istokpoga 0.018 0.0130.003 0.0240.008 0.0290.016 -28 33 61









P Flux rates. At 2 days, the mean SRP flux ranged from a rate of -0.64 1.094

(mg m-2 d-1) in Lake Tohopekaliga to a rate of -2.32 0.237 (mg m-2 d-1) in Lake

Istokpoga (Table 3-9). The negative P flux rates of all the lakes suggest that the

sediments are retaining phosphorus. Phosphorus flux rates were significantly higher for

Lake Kissimmee with Lake Tohopekaliga and Cypress at day 2 (P<0.001). The

dissimilarities may be due to differences in sediment type and physical and chemical

properties of the sediment. For example, Lake Tohopekaliga is a sandier lake with lower

total C, N, and P (16.3 18.8, 1.37 1.38, and 138 127 mg kg-1 compared to Lake

Kissimmee C, N, P (124 121, 11.7 + 11.3, and 703 685 mg kg-1 (see chapter 2, Table

2-1).

The mean 7 day SRP flux rates ranged from -0.061 0.270 mg m-2 d-1 in Lake

Kissimmee to 0.367 0.228 mg m-2 d-1 in Lake Istokpoga. The positive P flux rates of

Lake Istokpoga suggest P release from the sediments, while the negative P flux rate of all

the other lakes indicate P retention by the sediments. This data suggests that Lake

Istokpoga may be the only lake functioning as a source of P to the overlying water

column at this water column P level (15 ug L-1). Phosphorus flux rates were significantly

lower for Lake Istokpoga compared with Kissimmee, Tohopekaliga, Cypress, and

Hatchineha (P<0.05). Phosphorus flux was not significantly correlated with any of the

sediments characteristic, however, TP was significantly and positively correlated with

LOI, Ca, Mg, Fe, and Al.

At 25 days, the mean P flux ranged from a rate of 0.137 0.146 mg m-2 d-lin Lake

Istokpoga to a rate of 0.027 + 0.232 mg m-2 d-1 in Lake Hatchineha. The positive P flux









rates of all the lakes suggest that the lakes are releasing phosphorus to the water column.

There were no significant differences in P flux rates at day 25 at this P addition.



Table 3-9. Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 15 ug L-1 P additions at 2, 7, and 25
days. n=6 for all lakes except Lake Cypress n=5

--------------------------P flux mg m-2 d1-----------------
Lakes 2 day 7 day 25 day
Tohopekaliga -0.64 1.094 -0.081 0.0.285 0.112 + 0.208
Cypress -0.96 + 0.621 -0.235 + 0.164 0.024 + 0.139
Hatchineha -1.17 0.687 -0.237 + 0.160 0.027 + 0.232
Kissimmee -2.32 0.237 -0.061 0.270 0.028 0.030
Istokpoga -0.61 0.421 0.367 0.228 0.137 0.146


Phosphorus additions (30 ug L1)

Water column SRP concentrations. The site water ranged from 0.002-0.011 mg

L-1 plus the P addition which increased the concentration to 32, 33, 35, 39 and 41 ug L-1

for Lake Kissimmee, Istokpoga, Tohopekaliga, Cypress, and Hatchineha, respectively.

The mean water column SRP concentrations at day 2 ranged from a low in Lake

Kissimmee (0.0210.002 mg L1) to a high in Cypress Lake (0.0360.003 mg L1) and

Lake Tohopekaliga (0.0360.005 mg L1) (Table 3-10). Lake Tohopekaliga water

column SRP concentrations increased at a rate of 2% while all other lakes concentrations

declined in rates ranging from 8% in Cypress Lake to 30% in Lake Kissimmee at day 2.

The mean water column SRP concentrations ranged from (0.039 0.005 mg L1) in

Lake Tohopekaliga to (0.017 0.003 mg L1) Lake Kissimmee on day 7. Water column

SRP concentrations decreased in Lakes Cypress, Hatchineha, Kissimmee and Istokpoga

at day 7 at a rate between 15% in Lake Hatchineha and Istokpoga to 47% in Lake

Kissimmee, which suggests P retention by the sediments in these lakes. Lake









Tohopekaliga was the only lake to increase in water column SRP concentration at a rate

of 11%, which suggests P release from the sediments at day 7.

The mean water column SRP concentrations ranged from (0.0520.031 mg L1) in

Lake Tohopekaliga to (0.0140.003 mg L1) Lake Kissimmee on day 25. The SRP

concentrations increased in Lake Tohopekaliga, Cypress, Hatchineha, and Istokpoga over

the course of the experiment for all lakes at day 25 at a rate between 13% in Cypress

Lake to 63% in Lake Hatchineha. Water column SRP concentrations on day 25 for Lake

Tohopekaliga were much higher in one core at 0.106 mg L-1. This may be due to

heterogeneity of the sediment in the lake or biological release from organisms in the core.

Water column concentrations decreased in Lake Kissimmee at a rate of 56%, respectively

at this P addition (30 ug L-1).















Table 3-10. Percent change in SRP mg L-1 at 30 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%)
change indicate a decrease in SRP concentration while a positive (+) percent change indicate an increase in SRP
concentrations. n=6 .


Initial ------------------SRP (mg L1)------------ ---Percent Change (%)---
Cone.
Lake (mg L-1) 2 d 7 d 25 d 2 d 7 d 25 d
Tohopekaliga 0.035 0.0360.005 0.0390.023 0.0520.031 2 11 49
Cypress 0.039 0.036+0.003 0.0290.007 0.0440.0027 -7 -26 13
Hatchineha 0.041 0.0340.003 0.0350.013 0.0670.060 -17 -15 63
Kissimmee 0.032 0.0210.002 0.0170.003 0.0140.003 -34 -47 -56
Istokpoga 0.033 0.0240.003 0.0280.011 0.0400.027 -27 -15 21









P flux rates. At 2 days, the mean P flux ranged from a rate of -0.339 0.977 (mg

m-2 d-1) in Lake Tohopekaliga to a rate of -3.12 0.425 (mg m-2 d-1) in Lake Kissimmee

(Table 3-11). The negative P flux rates of all the lakes suggest that the sediments are

retaining phosphorus at day 2. Phosphorus flux rates were significantly higher in Lake

Hatchineha than Tohopekaliga. Flux rates were significantly higher in Lake Kissimmee

compare to Lakes Tohopekaliga, Cypress and Istokpoga (P<0.001). The differences may

be related to the different physical and chemical properties of the sediment.

The average P flux rate ranged from a negative rate of -0.381 + 0.174 (mg m-2 d-) in

Cypress Lake to a positive rate of 0.007 0.839 (mg m-2 d-1) in Lake Tohopekaliga at

day 7. The positive P flux values for Lake Tohopekaliga and Lake Istokpoga suggest that

the lakes are functioning as a P source to water column while the negative P flux rate of

the other lakes suggest P retention. There were no significant differences in P flux rates

between the lakes at day 7. This variability in P flux rates may be due to wide sediment

variability within the lakes, due to the presence of both sands and muds.

The mean P flux rate ranged from a negative rate of-0.117 0.202 mg m-2 d-1 in

Lake Istokpoga to a positive rate of 0.295 0.554 mg m-2 d-1 in Lake Hatchineha at day

25. The positive P flux values for Lake Hatchineha Tohopekaliga and Cypress suggest

that the lakes are functioning as a P source to water column while Lake Istokpoga and

Kissimmee negative P flux rates suggest P retention by the sediments. There were no

significant differences in P flux rates between lakes.









Table 3-11. Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 30 ug L-1 P additions at 2, 7, and 25
days.

--------------------P flux mg m-2 d-1---------------------
Lakes 2 day 7 day 25 day
Tohopekaliga -0.339 0.977 0.007 + 0.839 0.207 0.326
Cypress -1.04 0.920 -0.381 0.174 0.045 0.251
Hatchineha -1.80 + 1.064 -0.117 + 0.453 0.295 0.554
Kissimmee -3.12 + 0.425 -0.373 + 0.132 -0.109 0.041
Istokpoga -1.23 + 0.681 0.073 0.365 -0.117 0.202



Phosphorus additions (60 ug L-1)

Water column SRP concentrations. Water column SRP concentrations tended to

decrease in all the lakes over the course of the study, leading to P retention by the

sediments (Figure 3-6). At 2 days, the mean water column SRP concentrations ranged

from a low of 0.045 0.002 (mg L1) in Lake Kissimmee to a high of 0.061 0.005 (mg

L1) in Cypress Lake and 0.061 0.002 (mg L1) Lake Tohopkeliga, respectively (Table

3-12). Concentrations declined at a rate between 6 % in Lake Tohopekaliga to 38% in

Lake Kissimmee.

At day 7, the mean water column SRP concentration ranged between (0.046

0.007 mg L1) in Lake Tohopekaliga to (0.018 0.007 mg L1) in Lake Kissimmee. The

SRP concentrations in the water column declined at a rate between 29% in Lake

Tohopekaliga to 75% in Lake Kisimmee.

The mean water column SRP concentrations at day 25 ranged from a low in Lake

Kissimmee (0.011 0.004 mg L1) to a high in Lake Hatchineha (0.065 0.050 mg L-1).

The concentrations in the water column declined at a rate of 8% in Lake Hatchineha to a

rate of 85% in Lake Kissimmee at day 25.











0.08


0.06


S0.04


0.02


0.00
0 5 10 15 20 25
Time (days)


Figure 3-6. Phosphorus retention by sediments from station T2 of Lake Tohopekaliga at
60 ug L'1 P additions.












Table 3-12. Percent change in SRP mg L-1 at 60 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%)
change indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP
concentrations. n=6.

Initial ------------SRP (mg L1)---------------Percent Change %------
Conc.
Lake (mg L1) 2 d 7 d 25 d 2 d 7 d 25 d
Tohopekaliga 0.065 0.061+0.002 0.0460.007 0.0300.020 -6 -29 -54
Cypress 0.069 0.061+0.005 0.0450.012 0.061+0.033 -12 -35 -12
Hatchineha 0.071 0.0570.004 0.0370.011 0.0650.050 -19 -48 -8
Kissimmee 0.072 0.0450.002 0.0180.007 0.011+0.004 -38 -75 -85
Istokpoga 0.073 0.0470.008 0.0370.013 0.0370.022 -36 -49 -49









P flux rates. At 2 days, the mean P flux ranged from a rate low of -0.937 0.923

(mg m-2 d-1) in Lake Tohopekaliga to high rate of -3.615 0.518 (mg m-2 d-1) in Lake

Kissimmee (Table 3-13). The negative P flux rates of all the lakes suggest that the

sediments are retaining phosphorus at day 2 at P additions of 60 ug L-1. Phosphorus flux

rates were significantly higher in Lake Kissimmee compare to Lake Tohopekaliga

(P<0.05) at day 2.

The average P flux rate at day 7 ranged from a low of -0.543 0.420 (mg m-2 d-1)

in Lake Istokpoga to a high of -1.31 0.227 (mg m-2 d-1) in Lake Kissimmee. These

negative P flux rates suggest P retention by sediments for all five lakes. Phosphorus flux

rates were significantly higher in Lake Kissimmee with Lakes Tohopekaliga and

Istokpoga at day 7.

At day 25, the mean P flux ranged from a rate low of -0.081 0.471 (mg m-2 d-1) in

Lake Istokpoga to high rate of -0.399 0.269 (mg m-2 d-1) in Lake Tohopekaliga. The

negative P flux rates of all the lakes suggest that the sediments are retaining phosphorus

at day 25. There were no significant differences in P flux rates at day 25 at this P

addition.

Phosphorus additions (120 ug L1)

Water column SRP concentration. Water column SRP concentrations decreased

in all the lakes over the course of the study, suggesting P retention by the sediments

(Figure 3-7). At 2 days, the mean water column SRP concentration ranged from a low of

0.0880.001 (mg L-) in Lake Kissimmee to a high of 0.1230.023 (mg L-) in Lake

Hatchineha (Table 3-14). Concentrations declined at a rate between 7% in Lake

Hatchineha to 89% in Lake Kissimmee at day 2.









Table 3-13. Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 60 ug L-1 P additions at 2, 7, and 25
days.

----------------------P flux mg m-2 d-1---------------------

Lakes 2 day 7 day 25 day
Tohopekaliga -0.937 + 0.923 -0.675 + 0.281 -0.399 + 0.269
Cypress -1.969 + 1.429 -0.771 0.371 -0.354 + 0.048
Hatchineha -2.669 0.749 -1.00 + 0.384 -0.346 + 0.286
Kissimmee -3.615 0.518 -1.31 +0.227 -0.116 0.220
Istokpoga -2.648 + 1.854 -0.543 + 0.420 -0.081 + 0.471


At day 7, the mean water column SRP concentration ranged between (0.0130.014

mg L1) in Lake Kissimmee to (0.120 + 0.040 mg L1) in Lake Hatchineha. The SRP

concentrations in the water column declined at a rate between 8% in Lake Hatchineha to

94% in Lake Kissimmee at day 7.

The mean water column SRP concentrations at day 25 ranged from a low in Lake

Kissimmee (0.0070.010 mg L1) to a high in Lake Hatchineha (0.1290.065 mg L-1).

The concentrations in the water column declined at a rate of 2% in Lake Hatchineha to a

rate of 94% in Lake Kissimmee at day 25.

Phosphorus additions (120 ug L1)

P flux rates. At 2 days, the mean P flux ranged from a rate low of -2.443 1.149

(mg m-2 d-1) in Cypress Lake to high rate of-6.821 1.032 (mg m-2 d-1) in Lake

Kissimmee (Table 3-15). The negative P flux rates of all the lakes suggest that the

sediments are retaining phosphorus at day 2. The P flux rate for Cypress Lake was

significantly lower than Lakes Istokpoga and Kissimmee (P<0.001). Phosphorus flux

rates were also significantly higher in Lakes Kissimmee compared to Lake Hatchineha

and Lake Tohopekaliga (P<0.001) at day 2.










0.12

S0.09

E 0.06

0.03

0.00
0 6 12 18 24

Time (days)


Figure 3-7. Phosphorus retention by sediments from station 110007 of Lake Istokpoga at
120 ug L1 P additions.

The mean P flux rate at day 7 ranged from -0.87 0.419 (mg m-2 d-1) in Lake

Cypress to -2.91 0.494 (mg m-2 d-1) in Lake Kissimmee (Table 3-13). All lakes appear

to be retaining P (negative flux rates) at this P addition (120 ug L-1). These results imply

that none of the sediments in the lakes are net releasers of P to the water column at this P

addition.

However, even though sediments are taking up P, they still may not be taking out

enough P to lower the P concentrations in the water column. Flux rates were

significantly lower in Cypress Lake compared to Lakes Istokpoga (P<0.05). Lake

Kissimmee P flux rates were significantly higher than Cypress Lake, Lake Hatchineha,

and Lake Tohopekaliga (p<0.05).

At day 25, the mean P flux ranged from a rate low of -0.006 0.656 (mg m-2 d-1) in

Lake Hatchineha to high rate of -0.808 0.069 (mg m-2 d-1) in Lake Istokpoga (Table 3-

11). The negative P flux rates of all the lakes suggest that the sediments are retaining












Table 3-14. Percent change in SRP mg L-1 at 120 ug L-1 P additions, for all lakes, at day 2, 7, and 25. A negative (-) percent (%)
change indicates a decrease in SRP concentration while a positive (+) percent change indicates an increase in SRP
concentrations. n=6.

Initial -------------SRP (mg L-1)------------- ------Percent Change %-----
Conc.
Lake (mg L1) 2 d 7 d 25 d 2 d 7 d 25 d
Tohopekaliga 0.125 0.113 + 0.002 0.081 + 0.015 0.062 + 0.014 -9.3 -35.2 -50.4
Cypress 0.129 0.115 0.006 0.097 0.012 0.097 0.074 -11.0 -24.8 -24.8
Hatchineha 0.131 0.123 + 0.023 0.120 + 0.040 0.129 + 0.065 -6.5 -8.4 -1.5
Kissimmee 0.122 0.088 0.001 0.013 0.014 0.007 + 0.010 -27.9 -89.3 -94.3
Istokpoga 0.123 0.090 + 0.005 0.043 0.026 0.028 0.033 -26.8 -65.0 -77.2









phosphorus at day 25. Phosphorus flux rates were significantly lower in Lake Hatchineha

compared to Lakes Istokpoga, Tohopekaliga, and Kissimmee (P<0.01).

Table 3-15. Mean phosphorus flux rate (mg m-2 d-) for Lakes Tohopekaliga, Kissimmee,
Istokpoga, Cypress, and Hatchineha at 120 ug L-1 P additions at 2, 7, and 25
days.

-------------------P flux mg m-2 d-1------------------
Lakes 2 day 7 day 25 day
Tohopekaliga -3.364 + 2.145 -1.54 + 0.499 -0.700 + 0.207
Cypress -2.443 + 1.149 -0.87 + 0.419 -0.527 + 0.262
Hatchineha -2.896 + 0.257 -1.05 + 1.07 -0.006 + 0.656
Kissimmee -6.821 + 1.032 -2.91 0.494 -0.817 + 0.077
Istokpoga -5.055 + 1.380 -2.20 + 0.884 -0.808 + 0.069


Discussion

In general, the water column SRP concentration increased over time at no P

additions, showing P release from the sediment and decreased at high P additions (60 and

120 ug L-1), showing P retention by the sediment for all the lakes. Despite, retention by

the sediments at high P additions, water column SRP levels remained high (Figure 3-9).

This trend was observed for all lakes at day 2, 7, and 25, except on day 7 and 25 for

Kissimmee.

For Lake Kissimmee, the water column SRP concentration was much lower at high

P additions (120 ug L1) than at no P additions, which may be due to the trapping of P at

the aerobic sediment surface to which P adsorption by iron occurs under oxidized

conditions (Gachter and Meyer 1993, Keizer and Sinke 1992, Patrick and Khalid 1974).

For example, Lake Kissimmee has a great concentration of Fe and Al in the sediment

compared to any other metals (refer to chapter 2; Table 2-2). This is important because

Fe can either trap P at the aerobic sediment surface, preventing diffusive P release or bind

P at the anaerobic sediment surface, resulting in P release from the sediments. In Lake








84



Kissimmee, at P additions of 120 ug L1, the mean water column SRP concentrations was


lower at 0.013 + 0.014 (mg L') compared to 0.015+ 0.002 mg L-1 at no P additions at day


7.



0.18 Day 2
0.18


S0.12 Tohopekaliga
--Cypress

S-A- Hatchineha
U 0.06
o0.06 --- Kissirrmee
Istokpoga
060 120
0 60 120


Spike (ug L1)


Day 7


-- Tohopekaliga
--Cypress
-- Hatchineha
-- Kissimmee
-- Istokpoga


60 120

Spike ( ug L1)



Day 25


-- Tohopekaliga
---Cypress
-- Hatchineha
- Kissimree
- Istokpoga


60 120


Spike (ug L')


Figure 3-8. Water Column SRP (mg L') versus spike concentration ug L-1 for each lake.
at day 2, 7, and 25.


0.16

0.12

0.08

0.04

0


0.16

0.12

0.08

0.04