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WATER COLUMN PRODUCTIVITY, CALCITE PRECIPITATION, AND PHOSPHORUS DYNAMICS IN FRESHWATER MARSHES

DISSERTATION

Presented in Partial Fulfillment of the Requirements for

the Degree Doctor of Philosophy in the Graduate

School of The Ohio State University

By Michael A. Liptak, B.S.

*****

The Ohio State Umversity 2000

Dissertation Committee: Approved by Professor William J. Mitsch, Adviser

Professor David Culver

Professor Samuel Traina / Adviser Environmental Science Graduate Program UMI Number: 9994897

UMI*

UMI Microform 9994897 Copyright 2001 by Bell & Howell Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code.

Bell & Howell Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 ABSTRACT

Algal and respiration can cause significant diurnal changes in water chemistry', and can increase pH enough to cause precipitation of minerals. During the precipitation of calcite (CaCOp other chemical species such as phosphorus (P) can sorb onto the newly forming crystals and thus be removed from the water column. While calcite precipitation and subsequent P removal have been studied extensively in lakes, rivers, and streams, they have not been studied in temperate wetlands.

Calcite precipitation and associated P removal were examined in two full-scale I -ha created experimental fi-eshwater marshes and in twenty 1 -m’ experimental mesocosms in central

Ohio. Water, algae, and sediment samples were taken from July 1998 to May 1999 at sites from the inflow to the outflow of the marshes. Diurnal dissolved oxygen data taken every half-hour firom July 1996 through December 1998 at the experimental marshes were used to estimate gross primary production (GPP), respiration (R), and net primary production

(NPP). NPP, GPP and R showed strong seasonal changes, with maxima in the summer

(3.43 to 6.23 g O, m'^ d ') and minima (0.36 to 2.10 g O, m‘‘ d ') in the winter. Summer

GPP values were similar to values for eutrophic hardwater lakes, indicating that the shallow euphotic zone of wetlands can be as productive on an areal basis as deeper euphotic zones in lakes. Summer GPP values in the middle subbasins were not significantly different between the planted and unplanted wetland in 1996 or 1998, but were significantly higher in the planted wetland in 1997. Conductivity and temperature data were used in conjunction with hydrologie data to develop budgets for total dissolved

solids (TDS). Retention of total dissolved solids ranged from -0.7 to 12.7 Mg ha ' yr‘‘ (-0.4 to 13.5 percent retention, respectively) and averaged 7.9 Mg ha ' yr ' (6.3 percent retention). The two wetlands were not significantly different in total or percent retention fi'om 1996 to 1998; however, Wetland 2 had higher total and percent retention in 1996 and

1997, while Wetland 1 had higher total and percent retention in 1998.

The total dissolved solids budget showed that the wetland acted as sinks for dissolved materials, consistent with calcite precipitation. Calcite saturation indices were positive for all water samples, indicating that calcite precipitation is thermodynamically favored. Ca and P concentrations decreased fi'om inflow to outflow, and calcite and dolomite were found in the algal biomass, as well as in the wetland sediments, while suspended sediment samples fi’om the river inflow did not contain significant amounts of calcite, indicating that the calcite precipitated in the wetlands and was not imported as suspended riverine sediments. Dolomite may have been imported via the river inflow. Total calcite in both basin sediments increased by an estimated 4.5 metric tons ha ' yr ' and and dolomite by over 1.4 metric tons ha ' yr ' fiom 1994 to 1999. Scanning electron microscopy showed calcareous material encrusting algal filaments. The total amount of P associated with calcite was up to 47 percent of the total P contained in the algal mat, suggesting that P coprecipitation essentially doubled the P removal capability of the algal mat.

Calcite precipitation was also investigated in twenty 380-L shallow-water (30 cm) mesocosms to determine whether calcite precipitation/dissolution occurred on a diurnal time-scale in wetlands, and whether sorption with calcite was a significant sink for P. Ten mesocosms were covered with black cloth to inhibit photosynthesis, while ten mesocosms were left uncovered and stocked with filamentous algae fiom the experimental marshes

(major spp. Cladophora, Rhizoclonium, Hydrodictyon). Water, algal biomass and sediment samples were taken fiom June 1998 to May 1999. Saturation index values were always positive, showing that calcite precipitation was thermodynamically favored for both treatments on all sampling dates. Dissolved oxygen, temperature, pH, and saturation index

iii showed strong diurnal patterns in the uncovered mesocosms, and less so in the covered mesocosms. Calcium, soluble reactive P, and total P showed no diumal changes in either treatment, but were significantly lower in the water column of the uncovered mesocosms.

Calcite precipitation occurred in the algal mats of the uncovered mesocosms, and calcite in the algal mats increased by 6.55 ± 1.05 g-eq CaCO^ in the uncovered mesocosms over one growing season. There were no algal mats present in the covered mesocosms, and calcite and dolomite in all mesocosm sediments were not significantly different fi'om the initial soil samples.

IV Dedicated to my wife, Heather ACKNOWLEDGMENTS

There are a great number of people I wish to thank for their help, friendship and encouragement along my educational path. I would like to thank Dr. William Mitsch, my advisor, for his encouragement, patience, and intellectual support. 1 would like to thank my committee for their help, especially Dr. David Culver, for his comments on my manuscript. I would like to thank all the people who encouraged me as an undergraduate biology student, including Dr. Johan Gottgens, Dr. Bob Sinsabaugh, Dr. Bill Bischoff,

Dr. Charles Creutz, and Dr. Phil Yeager. 1 would also like to thank Mr. Frank DeMarco, my high school biology teacher, and Mrs. Parker, the advisor of the Green Eco-team for encouraging my early interest in ecology.

I would like to thank all the people who have helped me gather and analyze my samples and data over the past four years; without you my research would not have been possible.

Sharon Johnson, Heather Liptak, Doug Spieles, Mike Brady, Greg Sablak, Kevin Mohler,

Holly Montgomery, Melanie Ford, and Virginie Bouchard all provided invaluable assistance. Special recognition goes to Sharon Johnson, Heather Liptak, and Greg Sablak for assistance imtil the wee hours of the morning.

Doug Beak and Dedra Woner are thanked for their invaluable assistance in sample analysis, particularly organic carbon analysis. Thanks to Billy Lindsey for training me on the proper use of the flame atomic absorption spectrophotometer. Thanks to Sandy Jones and Dr. Neil Smeck for help with the calcite and dolomite analyses, and to John Mitchell

and Wietse van Gerven for their expert help with scanning electron microscopy and

elemental analysis.

VI The wetlanders of Kottman Hall are thanked for their assistance and for their cameraderie and friendship. Naiming Wang, Lisa Svengsouk, Sharon Johnson, Virginie

Bouchard, Sarah Harter, Molly Bean, Terry LeMaster, Bill Acton, Randy Bruins, Doug

Spieles, Changwoo Ahn, Erica Filippi, Janice Gilbert, John Gutrich, Dan Fink, Eric

Lohan, Greg Sablak, Amie Gifford, Holly Montgomery, Melanie Ford, Megan Hunter,

Mike Brady, Matt Cochran and Rikke Broennum. Thanks to Bob Naim, wetlander emeritus, for taking the soil samples in 1993 and 1995 and for answering my questions about his procedures and results patiently.

A special thanks to Doug Spieles, for making 378 Kottman Hall a fun place to be.

Thanks to my family, who has supported me in all of my dreams and endeavors. Finally, and most importantly, thanks to my wife. Heather, whose love and understanding have kept me sane and happy throughout grad school.

The first three years of my graduate studies were funded through a fellowship from the

USDA Water Needs Program.

vu VTTA

November 17, 1972 ...... Bom - Akron, Ohio

199 5...... B.S. Biology, The University of Toledo

1995-199 6...... Lab technician. The University of Toledo

199 6...... SCA/ AmeriCorps volunteer, Everglades National Park, FL, USA

1996-199 9...... SDA Water Needs Fellow, The Ohio State University

1999-2000...... Graduate Teaching and Research Associate, The Ohio State University

2000...... Ecologist, ASC Group, Inc., Columbus, OH

PUBLICATIONS

Peer-reviewed journal articles

Gottgens, J.F., and M.A. Liptak. 1998. Longterm assimilation of agricultural runoff in a Lake Erie marsh. Verh. Internat. Verein. Limnol. 26:1337-1342.

Sinsabaugh, R. L., R.K. Antibus, C.R. Jackson, S. Karpanty, M. Robinson, M. Liptak, P. Franchini. 1997. A beta-sitosterol assay for fine-root mass in soil. Soil Biology & Biochemistry 29:39-44

Book chapters/proceedings

Sinsabaugh, R.L., and M.A. Liptak. 1997. Enzymatic conversion of plant biomass. In: The Mycota, vol. IV. pp. 347-358. Esser, K. and Lemke, P.A., eds. Springer- Verlag, Berlin. viii Liptak, M. 1995. Long-term nutrient assimilation by a diked Lake Erie coastal marsh. Proceedings of the National Conference on Undergraduate Research, volume 111. pp. 890-894. Robert D. Yearout, editor.

Other publications

Liptak, M.A., and W.J. Mitsch. 1999. Algal-induced calcite and phosphorus coprecipitation. Pages 183-190. In: Olentangy River Wetlands Research Park Annual Report 1998, W.J. Mitsch and V. Bouchard, eds. School of Natural Resources, The Ohio State University, Columbus, OH.

Bouchard, V., M. Liptak and W.J. Mitsch. 1999. Vegetation establishment in the mitigation billabong at the Olentangy River Wetland Research Park in 1998. Pages 161-166. In: Olentangy River Wetlands Research Park Annual Report 1998, W.J. Mitsch and V. Bouchard, eds. School of Natural Resources, The Ohio State University, Columbus, OH.

Liptak, M.A., and W.J. Mitsch. 1998. Algal production and calcite precipitation in the Olentangy River Wetlands. Pages 155-162. In: Olentangy River Wetlands Research Park Annual Report 1997, W.J. Mitsch and V. Bouchard, eds. School of Natural Resources, The Ohio State University, Columbus, OH.

Liptak, M.A., and W.J. Mitsch. 1998. Algal production and calcite precipitation in wetland mesocosms. Pages 251-262. In: Olentangy River Wetlands Research Park Annual Report 1997, W.J. Mitsch and V. Bouchard, eds. School of Natural Resources, The Ohio State University, Columbus, OH.

Mitsch, W.J, S.M. Johnson, and M.A. Liptak. 1998. Planting and planting success of the new mitigation wetland at the Olentangy River Wetland Research Park in 1997. Pages 205-210. In: Olentangy River Wetlands Research Park Annual Report 1997, W.J. Mitsch and V. Bouchard, eds. School of Natural Resources, The Ohio State University, Columbus, OH.

Liptak, M.A., L. Svengsouk, S.M. Johnson, and W.J. Mitsch. 1997. Wetland macrophyte development in the experimental wetlands at the Olentangy River Wetland Research Park during the third growing season 1996. Pages 159-172. In: Olentangy River Wetlands Research Park Annual Report 1996, W.J. Mitsch, ed. School o f Natural Resources, The Ohio State University, Columbus, OH.

FIELDS OF STUDY

Major Field: Environmental Science

IX TABLE OF CONTENTS

Page

Abstract ...... ii

Dedication ...... v

Acknowledgments ...... vi

Vita...... viii

List of Tables ...... xiii

List of Figures...... xvi

List of Abbreviations ...... xix

Chapters.

1. Introduction ...... 1

1.1 Goals and objectives ...... 2

2. Aquatic metabolism and water chemistry in freshwater ecosystems ...... 5

2.1 Aquatic metabolism and water chemistry ...... 5 2.2 Carbonate-bicarbonate solution chemistry and p H ...... 6 2.3 Calcite precipitation ...... 8 2.3.1 Abiotic causes of calcite precipitation ...... 9 2.3.2 Mechanisms of algal-induced precipitation ...... 10 2.3.2.1 Direct incorporation ...... 10 2.3.2.2 Indirect extracellular precipitation ...... 11 2.4 Influence of calcite precipitation on other chemical species ...... 12 2.4.1 Phosphorus ...... 15 2.4.2 Other nutrients ...... 16 2.4.3 Organic carbon ...... 16 2.4.4 M dals...... 18 2.5 Calcite precipitation in hardwater lakes ...... 18 2.5.1 Seasonal studies ...... 18 2.5.2 Short-time interval studies ...... 19 2.6 Calcite precipitation in streams and rivers ...... 20 2.7 Calcite precipitation in wetlands ...... 21 3. Methods ...... 23

3.1 Site description ...... 23 3.1.1 Mesocosm description ...... 28 3.2 Hypotheses ...... 31 3.2.1 Full-scale wetland hypotheses ...... 31 3.2.2 Mesocosm experiment hypotheses ...... 32 3.3 Full-scale wetlands ...... 32 3.3.1 Aquatic metabolism ...... 32 3.3.2 Total dissolved solids budget ...... 37 3.3.3 Spatially detailed diumal water quality ...... 42 3.3.3.1 Field sampling ...... 42 3.3.3.2 Laboratory analyses ...... 45 3.3.4 Metaphyton analyses ...... 46 3.3.4.1 Field sampling ...... 46 3.3.4.2 Laboratory analyses ...... 46 3.3.5 Sediment analyses ...... 48 3.3.5.1 Field sampling ...... 48 3.3.5.2 Laboratory analyses ...... 49 3.3.6 Statistical analyses ...... 50 3.4 Mesocosms ...... 51 3.4.1 Field sampling ...... 51 3.4.2 Laboratory analyses ...... 52 3.4.3 Statistical analyses ...... 53

4. Results...... 55

4.1 Full-scale wetlands ...... 55 4.1.1 Aquatic metabolism ...... 55 4.1.2 Temperature ...... 59 4.1.3 p H ...... 59 4.1.4 Conductivity ...... 63 4.1.5 Total dissolved solids budget ...... 63 4.1.6 Spatially detailed water quality data ...... 69 4.1.6.1 Diumal changes ...... 69 4.1.6.2 Wetland comparisons ...... 73 4.1.6.3 Inflow vs. outflow ...... 73 4.1.6.4 Shallow vs. deep water ...... 76 4.1.7 Metaphyton ...... 76 4.1.8 Sediments ...... 79 4.1.8.1 Sediment analyses ...... 84 4.1.8.2 Chemical analyses ...... 90 4.2 Mesocosm experiment ...... 94 4.2.1 Water column biogeochemistry ...... 94 4.2.1.1 Dissolved oxygen and GPP ...... 96 4.2.1.2 pH ...... 96 4.2.1.3 Conductivity ...... 99 4.2.1.4 Temperature ...... 99 4.2.1.5 Oxidation-reduction potential ...... 101 4.2.1.6 Saturation index ...... 101 4.2.1.7 Dissolved calcium ...... 101 4.2.1.8 Phosphoms ...... 102 xi 4.2.1.9 Carbon ...... 102 4.2.2 Metaphyton biomass and elemental analyses ...... 103 4.2.3 Sediments ...... 103

5. Discussion ...... 107

5.1 Gross primary productivity and algal biomass of shallow wetlands ...... 107 5.2 Influence of aquatic primary productivity on aquatic biogeochemistry in wetlands ...... 113 5.3 Calcite precipitation ...... 114 5.4 Phosphorus sorption with calcite ...... 116 5.5 Ca and P flow through the experimental wetlands ...... 116

6. Conclusions and Recommendations ...... 121

6.1 Conclusions ...... 121 6.2 Recommendations ...... 122

Bibliography ...... 124

Appendices:

Appendix A - Wetland water quality data ...... 137 Appendix B - Additional wetland water quality data ...... 141 Appendix C - Wetland aquatic metabolism ...... 145 Appendix D - Carbonates in metaphyton biomass ...... 147 Appendix E - Metaphyton elemental analysis ...... 148 Appendix F - Total metaphyton carbonates ...... 151 Appendix G - Physical properties of wetland sediments ...... 153 Appendix H - Soil color of wetland sediments ...... 154 Appendix I - Soil chemistry of wetland sediments ...... 155 Appendix J - Scanning electron microanalysis ...... 157 Appendix K - Calcium carbonates in wetland sediments ...... 159 Appendix L - Mesocosm water quality data ...... 163 Appendix M - Additional mesocosm water quality data ...... 169 Appendix N - Mesocosm aquatic metabolism ...... 175 Appendix O - Calcium carbonates in mesocosms ...... 177 Appendix P - Mesocosm metaphyton biomass ...... 179 Appendix Q - Elemental analyses of mesocosm metaphyton ...... 181 Appendix R - Elemental analyses of mesocosm sediments ...... 184 Appendix S - Mesocosm sediment chemistry ...... 185

xu LIST OF TABLES

Table Page

Chemical substances and properties which interact with calcium carbonate in aquatic systems ...... 13

4.1 Gross primary production (GPP) and respiration (R) in research wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998. GPP and R were calculated using data t^ e n every half-hour from four YSl 6000 data sondes (YSl, Inc., Yellow Springs, Ohio). W1 = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing) ...... 56

4.2 Results of general linear models for GPP, R, and NPP in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998 ...... 58

4.3 Average values for temperature, pH, and conductivity in the research wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998 ...... 60

4.4 General linear model results for water temperature in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998 ...... 61

4.5 General linear model results for pH in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998 ...... 64

4.6 General linear model results for conductivity at 25 “C in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998 ...... 66

4.7 Total dissolved solids budget in megagrams (Mg) per year for the 1 -ha experimental wetland basins at the Olentangy River Wetland Research Park, 1996-98 68

4.8. Summary of diumal trends in water quality parameters in the experimental wetland basins at The Olentangy River Wetland Research Park, 1998-99. The first symbol represents change from dawn to dusk, and the second represents the change from dusk to the following dawn. A plus (-i-) symbol indicates a significant (a = 0.05) increase, while a minus (-) symbol indicates a significant (a = 0.05) decrease. A zero (0) indicates that the change is not significant (a = 0.05) ...... 70

xni 4.9 Statistical differences between inflow, middle, and outflow subbasins of the experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. Different letters signify a significant difference (a =0.05) between sites within a sampling date. Comparisons between sampling dates are not shown ...... 75

4.10 Algal biomass and percent cover in deepwater areas of experimental wetlands at the Olentangy River Wetland Research Park, 1998-99. C= Cladophora, R=Rhizoclonium, H=Hydrodictyon, S=Spirogyra, NP= no macroalgae present. W1 = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing) ...... 77

4.11 P associated with algal biomass and with calcium carbonate in deepwater areas of experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. W l= Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing) 80

4.12 Bulk density and percent organic matter of sediments in the experimental wetlands at the Olentangy River Wetland Research Park. Different letters indicate significant difference (a=0.05) between years. * indicates significant difference (a=0.05) between upper (0-8 cm) and lower (8-16 cm) sediment layer in the same year. Data from 1993 and 1995 were taken from a previous study of the experimental wetland basins (Naim 1996) ...... 85

4.13 Accumulation rates for calcium carbonate minerals (calcite, dolomite, and calcium carbonate equivalent (CCE)) precipitated in the experimental wetland basins at the Olentangy River Wetland Research Park, 1994-1999. * denotes accumulation rates significantly different from zero (a = 0.05) ...... 88

4.14 Diumal trends in water chemistry in wetland mesocosms, 1998. The first symbol represents the difference between dawn and the following dusk. The second symbol represents the difference between dusk and the following dawn. + denotes a statistically significant increase, and - indicates a statistically significant decrease (a = 0.05). A zero represents no significant statistical difference (a = 0.05) ...... 95

4.15 Biomass in algal mesocosms and important chemical components in the early and late growing season. Chemical constituents are expressed as average ± standard error(ii). Different letters indicate a significant difference between the June and September sampling dates (a=0.05). CCE = calcium carbonate equivalent ...... 104

4.16 Total amount of chemical constituents contained in the algal mats in the algal mesocosms, 1998 ( ave. ± std. error (n)). Different letters indicate a significant difference between the June and September sampling dates (a=0.05) ...... 104

4.17 Chemical characteristics of sediment in mesocosms prior to flooding (Initial), and in the treatment (Algae) and control mesocosms after 1 yr continuous flooding. Ave ± std. error (n). Different letters denote significant difference between samples(o=0.05). * denotes that the value is not significantly different from zero ...... 106

XIV 5 .1 Growing season gross primary productivity (GPP) in wetlands and hardwater lakes ...... 108

5.2 Algal biomass in wetlands and lakes. * denotes a reference taken from Vymazal 1995a...... 111

5.3 Calcite precipitation and deposition rates in wetlands and hardwater lakes ...... 115

5.4 Ratio of P to Ca in calcite precipitated in wetlands and hardwater lakes ...... 117

XV LIST OF FIGURES

Figure Page

1.1 Conceptual diagram of the flows of calcium and phosphorus in the experimental wetland basins ...... 3

3 .1 Plan view of the Olentangy River Wetlands Research Park at The Ohio State University, Columbus OH, during the study period. Water is pumped from the Olentangy River into the two experimental marshes (1 and 2) and flows through each basin into a combined swale/stream system and back into the Olentangy River. The mesocosm compound (3) used in the study is located northwest of the basins ...... 24

3.2 Locations of soil (•) and water (* ) samples and YSl datasondes locations (x) in the two experimental marshes for this study (1996-99) with a permanent 10 m X 10 m grid system established in 1993. Prior to flooding (1993), soil samples were collected at grid intersections within the wetland basins (Naim, 1996). In 1995, soil samples were collected at every other intersection (the intersection of dark lines within the basins)(Naim 1996) ...... 25

3.3 Example of typical growing-season diumal changes in water quality parameters in the middle subbasin of Wetland 1 experimental marsh at the Olentangy River Wetland Research Park, July 17-18, 1997: a) dissolved oxygen and temperature, and b) conductivity and pH ...... 27

3.4 Wetland basin during drawdown on August 3, 1994. The white substance in the foreground is dried metaphyton, whose color is an indicator that the metaphyton mat may contain calcium carbonate. (Photograph by William J. Mitsch) ...... 29

3.5 Experimental wetland mesocosms as a) elevation view and b) plan view. A represents algae treatment and C represents control treatment. Numbers refer to mesocosm identification numbers ...... 30

3.6 Illustration of the method used to estimate gross primary productivity (GPP) and respiration (R) (Odum 1956). Dissolved oxygen (DO) readings are used to determine the rate of change for DO during the day, while both photosynthesis (?) and respiration(R) are occurring, and at night, when it is assumed that only R is occurring. The nighttime data points are used to determine the rate of R, shown in b) by a dotted line. The rate of R is added to the rate of change for DO and integrated over daylight hours to calculate GPP in gO ; m'^ d '. This number is multipled by the average depth to determine areal GPP (c) in g O, m'M‘‘ ...... 34 xvi 3.7 Regression plots for the temperature-dependent empirical relationship between conductivity and total dissoved solids, a) a linear regression for the entire temperature range. This model was discarded in favor of b) a second-order equation ...... 39

4.1 Summer gross primary production (GPP) in the middle subbasins of the experimental wetlands, 1996-98, expressed as a) annual averages for 3 years and b) individually by year. W1 =Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). W1 had significantly higher GPP in summer 1997 (paired t-test). Error bars indicate standard error, n = number of paired data points. Asterisks (*) indicate significant differences bet'.veen W1 and W2 ...... 57

4.2 Winter temperature, summer temperature, pH and conductivity in the middle subbasins of the experimental wetland basins, 1996-1998. No data are available for conductivity in the middle subbasin of W2 summer 1997. Error bars show std. error, numbers above bars are number of data points. Wl=Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). Asterisks (*) indicate significant differences between W1 and W2 (paired t-test) ...... 62

4.3 Diumal variations in water quality in the experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. Error bars show standard errors ...... 71

4.4 Dissolved and total carbon species in the middle and outflow subbasins of the experimental wetland basins, summer 1998. TDC = total dissolved carbon, DIG = dissolved inorganic carbon, DOC = dissolved organic carbon, TC = total carbon, TIC = , and TOC = total organic carbon. Error bars show standard error; numbers show number of data points ...... 74

4.5 Average metaphyton biomass (g m ‘) vs. summer nutrient levels (mg L ‘) in the middle and outflow subbasin of flie experimental wetlands, 1998-99. Error bars show standard errors ...... 78

4.6 Scanning electron micrograph of Cladophora filament encrusted with calcium carbonate. Sample was taken in mesocosm 46 on September 8, 1998 ...... 81

4.7 Detail of Cladophora filament encrusted with calcium carbonate. Sample was taken in mesocosm 46 on September 8, 1998 ...... 82

4.8 Calcium carbonate in algal sample taken in mesocosm 46 on September 8, 1998. This calcite formed aroimd an algal filament, which afterwards decayed, leaving only the calcite ...... 82

4.9 Calcite in sediment samples taken in the experimental wetland basins at the Olentangy River Wetland Research Park in 1998. Both the well-defined crystals and the finer-grained precipitate are calcium carbonate. Algal filaments were found to be associated with only the fine-grained form, not the larger crystals ...... 83

xvii 4.10 Calcite, dolomite, and calcium carbonate equivalent in the sediments of the experimental basins at the Olentangy River Wetland Research Park in 1993, 1995 and 1999. Archived samples from a previous study (Naim 1996) were used for the calcium carbonate analysis of 1993 and 1995 samples ...... 86

4.11 Calculated totals of calcite and dolomite contained in the sediments of the experimental wetland basins at the Olentangy River Wetland Research Park in 1993, 1995 and 1999...... 89

4.12 Calculated totals of calcium carbonate minerals in the sediments of the Olentangy River Wetland Research Park prior to flooding (1993), 17 months post-flooding (1995), and 5 years post-flooding (1999). Wl = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). In=inflow subbasin, Mid=middle subbasin, Out=outflow subbasin ...... 91

4.13 Chemistry of the sediments in the experimental wetland subbasins at the Olentangy River Wetland Research Park, 1993-9. Data from 1993 and 1995 are taken from a previous study (Naim, 1996) ...... 92

4.14 Available and total P in the sediments of the experimental wetland subbasins at the Olentangy River wetland Research Park, 1993-9. Data from 1993 and 1995 were taken from a previous study of the basins (Naim, 1996). Total P analysis was not performed on the lower sediment layer (8-16 cm) in 1993 or 1995 ...... 93

4.15 Diumal trends in water quality in wetland mesocosms, 1998. Error bars show standard errors ...... 97

4.16 Gross primary production in wetland mesocosms at the Olentangy River Wetland Research Park, 1998. Different letters indicate a significant difference between treatments (a = 0.05) ...... 98

4.17 Chemical constituents in the water column of wetland mesocosms at the Olentangy River Wetland Research Park, 1998. Different letters indicate significant differences between treatments (a = 0.05) ...... 100

5.1 Diagram of the flows of calcium and phosphoms in an average experimental wetland basin in 1998. Flows are in g m yr ', and storages are in g m " ...... 118

xvm LIST OF ABBREVIATIONS

A - algae treatment alk- total alkalinity avg - average C - carbon, control treatment, Celsius Ca - calcium d - day d^- water depth D ie - dissolved inorganic carbon dm - decimeter DO - dissolved oxygen DOC - dissolved organic carbon g - gram GPP - gross primary productivity, g O, m d' GPP^„i - gross primary productivity, g O, m'^ d"' GPPinj, - gross primary productivity, g O*, m'^ h ' h - hour ha - hectare ICP - inductively coupled plasma km - kilometer L - liter m - meter max - maximum min - minute, minimum mL - milliliter |iL - microliter mg - milligram Mg - megagram |ig - microgram n - number of data points NPP - net primary production, g O, m'^ d ' ORWRP - Olentangy River Wetland Research Park P - phosphorus PAR - photosynthetically active radiation R - respiration rate, g 0, m'^ d ‘ R„o, - respiration rate, g O, m'^ d ' Rj„g - average nighttime respiration rate, g O; m‘^ h ‘ SC - specific conductance SD - standard deviation SE - standard error sec - second SRP - soluble reactive phosphorus T - temperature, °C TC - total carbon xix TDC - total dissolved carbon TDS - total dissolved solids TIC - total inorganic carbon TOC - total organic carbon TP - total phosphorus 81 - saturation index STAR - Service Testing and Research y r-y ear

XX CHAPTER 1

INTRODUCTION

Primary production and respiration, collectively referred to as metabolism, are functions which are particularly important as indicators of the general state of an ecosystem. These biological processes, in turn, influence a number of physical and chemical characteristics in aquatic ecosystems (Buffle and DeVitre 1994). The influence of aquatic metabolism is particularly pronoimced in shallow-water ecosystems such as wetlands, where the euphotic zone is often restricted to a few cm depth (Cronk and Mitsch

1994a,b, Mitsch and Gosselink 1993). Water column metabolism in wetlands is associated with many important characteristics of the water column including species composition and diversity, turbidity, dissolved oxygen, nutrient biogeochemistry, pH, carbon dioxide, conductivity by stimulating precipitation, and temperature by shading and turbidity effects

(Mitsch and Gosselink 1993). As an ecosystem matures, it often ameliorates the harsher effects of its physical environment such as temperature and solar radiation, and biological feedback becomes a very important regulator of the ecosystem’s biological, physical, and geochemical processes (Odum 1969).

One of the most important functions of wetlands is their role as nutrient sinks

(Mitsch and Gosselink 1993). Their high productivity, low flow, and coupled anoxic and oxidized zones make them ideal for removal of nutrients such as nitrogen and phosphorus.

Phosphorus (?) is a particularly important nutrient in freshwater ecosystems. It is often the limiting nutrient in freshwater ecosystems, and when present in excess can cause

1 eutrophication of water bodies (Wetzel 1983). Wetlands can act as sinks for phosphorus, thus reducing the nutrient loading of downstream water bodies. Constructed wetlands use the capability of these ecosystems to remove nutrients as a final polishing step in wastewater treatment (Kadlec and Knight 1996).

Wetlands remove phosphorus from the water column through a variety of processes

(Fig. 1.1): sedimentation of particulate matter, which often contains phosphorus, direct uptake fi'om the water column by plankton, periphyton, submersed aquatics and metaphyton, and in some cases, sorption with minerals precipitating in the water column

(Scinto 1997). Ecosystem metabolism is central to the direct uptake and sorption processes. In productive wetlands, aquatic primary production increases pH levels during the day, which may be enough to cause calcium carbonate, or calcite, to precipitate in wetlands fed by hardwater sources. While sedimentation and direct uptake of phosphorus have been studied in detail in wetlands, sorption with calcite remains a relatively unstudied mechanism for phosphorus immobilization.

1.1 Goals and objectives

The goal of this dissertation is to examine the influence of seasonal and diumal aquatic metabolism on the water and sediment chemistry of two shallow-water created fireshwater wetlands, investigating in particular how photosynthesis causes precipitation of calcium carbonates and associated sorption of phosphorus.

To determine this, the dissertation has five major objectives:

1) Determine the rates of aquatic metabolism in two flow-through experimental wetland

basins, and compare these with rates for highly productive lakes.

2) Determine the changes in aquatic chemistry as surface water passes through the

experimental wetland basins to determine the effects of aquatic metabohsm and physical

processes on water column chemistry. Legend Energy Ca Solar CO2

Air Water column

HgCOg'^HCOgWCOs:

inflow ►

Dissolved R Ca2+ Primary p ro d u c t

p-

CaCO.

Turbulenci Sorbed P

Fig. 1.1 - Conceptualr ^ dia^am of the flows of calcium and phosphorus in the experimental wetland basins, 3) Calculate a budget for total dissolved solids in the experimental wetland basins.

4) Determine whether calcite precipitation occurs in the wetland basins, and its causes.

5) Determine the significance of phosphorus sorption with calcite as a removal mechanism

for dissolved phosphorus in the water column. CHAPTER 2

AQUATIC METABOLISM AND WATER CHEMISTRY IN FRESHWATER

ECOSYSTEMS

2.1 Aquatic metabolism and water chemistry

Photosynthesis and respiration affect the chemistry of natural waters in many ways.

The photosynthetic process can be expressed as the following chemical equation:

6C0, + 6H,0 —► CgH.zOg + 6 0, (2-1)

This process adds O, to the water column while simultaneously removing CO,.

Aerobic respiration is the reverse reaction to photosynthesis:

6 0 , + CgHi^O, ► 6 CO, + 6H, (2-2)

and removes O, from the water while adding CO,. In productive aquatic ecosystems, dissolved oxygen increases during the day due to the dominance of photosynthesis over respiration, and decreases at night due to respiration. Carbon dioxide shows the opposite pattern, decreasing during the day and increasing at night. Carbon dioxide is part of the carbonate-bicarbonate buffering system, which is a major influence on the pH of natural waters. Removing CO; from the water column acts to increase pH, and adding CO, to the water column causes pH to decrease.

2.2 Carbonate-bicarbonate solution chemistry and pH

In order to understand the influence of aquatic metabolism on pH and mineral precipitation, it is first necessary to understand the chemistry of dissolved carbon dioxide

species. Many complete treatments of the subject are available (Wetzel 1983, Drever 1988,

Cole 1994, Stumm and Morgan 1996). Dissolved inorganic carbon in aquatic systems originates from two major sources; CO, in the atmosphere and mineral dissolution. CO,

from the atmosphere can diffuse into water, or can be incorporated through wind mixing. Its equilibrium concentration in water depends upon the partial pressure of CO, in the air

above the water column, according to Henry's law. After CO,(g) becomes hydrated to

CO,(aq), it can form the weak acid H,COy

CO,(g) CO,(aq) (2-3)

H,0 + CO,(aq) H,CO^ (2-4)

Under normal conditions, CO,(aq) is present in far greater concentrations than

HjCOj. These two species (CO,(aq) and H,CO^) are generally combined into one

composite term, H,CO V *. Therefore, the combined equation would be:

C0,(g) + H , 0 . ^ H ,C O / pK.= l.46 (2-5) Spéciation of CO, depends on the pH of the solution. At pH < pK,, the dominant form is

H,COj*. At pH values above pK, (6.35), HCG^* becomes the most abundant species through the reaction

H ,C O / ^4— H^ + HCOj' pK, = 6.35 (2-6)

At pH values above 10.33, CO ' becomes the most abundant species in the reaction

H C O j--^= ^ H+ + C O / pK,= 10.33 (2-7)

At high pH values, calcium carbonate, or calcite, can precipitate through the following reactions:

C a'' + C O / CaCOj (2-8)

Ca' + 2 HCOj CaCOj + H,0 + CO, (2-9)

Photosynthesis removes inorganic C from the water column in the general reaction expressed in Equation 2-1 :

6 CO^ + 6H,0 — C^H,jO^ + 6 0 , (2-1)

Removing CO^(aq) from the water column would change the equilibrium between

HCOj and H^CO^*, shifting equation 2-6 to the left. This would remove H"*" ions from the water column, thus increasing pH. Adding CO,(aq) to the water column would shift the equilibrium in the opposite direction, thus decreasing pH. However, at pH values > 6.35, CO^(aq) is not the most abundant form of inorganic C, and CO? concentrations become extremely small at higher pH values common in hardwater lakes and streams. Some aquatic species have adapted to using HCO^ as a carbon source when CO,(aq) is not available. Precipitation of calcite through reaction 2-9 utilizes bicarbonate and produces CO,, which can be used for photosynthesis. Most calcification occurs in aquatic systems with alkaline pH values, so most of the inorganic C would be in the form of H C O ,. Many of the calcifying algae species show carbonic anhydrase activity, which converts bicarbonate to carbon dioxide (Vymazal 1995a). As these species remove HCO, from the water column, they cause the surrounding water volume to become more alkaline.

Although the exact mechanism is not known, it may involve transport of H* ions into the cell with the HCO/ or transport of OH' ions out of the cell.

2.3 Calcite précipitation

Calcite precipitates in both freshwater and marine systems. Although both biotic and abiotic factors can cause calcite precipitation (Effler 1984), algal production has been recognized as a significant cause of carbonate precipitation in marine systems since the nineteenth century (Wallich 1877) and in freshwater systems since the early twentieth century (Minder 1922). The formation and sedimentation of calcite crystals in these systems can affect the cycling of carbon, phosphorus, and other chemical species, primarily by providing a large surface area upon which ions can sorb or become incorporated into the crystals themselves, thus removing the ions from solution.

Calcium carbonate exists in two crystal forms, the rhombohedral crystal calcite and the orthorhombic crystal aragonite. Calcite is the form found in most freshwater systems, while the marine algae generally form aragonite, with the notable exception of the coccolithophorids, planktonic algae which form outer shells of calcite. Although most

8 species are only able to form either calcite or aragonite, some corallinacean algae are able to deposit a mixture of magnesium calcite, aragonite and calcite (Medakovic et al. 1995).

Calcification has been documented in the following algae families: Cyanophyceaea,

Chlorophyceaea, Charophyceaea, Prymnesiophyceaea, Chrysophyceaea, Dinophyceaea,

Phaeophyceaea, and Rhodophyceaea (Vymazal 1995a). Charophyceaea is the major family of calcifying fi-eshwater algae, and Prymnesiophyceaea is the major family of marine calcifying algae. Important calcifying algal species are Emiliania hiixleyi in marine systems, and Phacotus spp., Chara andspp., Synechococcus spp. in freshwater systems.

Calcite precipitation associated with algal primary production has been documented in coral reefs (Small and Adey, in press), open ocean systems (Bramlette 1958, Westbroek et al. 1993), estuaries (Boers et al. 1998), the Everglades (Yates 1996, Scinto 1997), streams (Stewart 1988, House et al. 1989), rivers (Green et al. 1978, Green and Smeck

1979, House and Denison 1997, 1998, House and Warwick 1998), temperate hardwater lakes throughout the world (Otsuki and Wetzel 1974, Effler 1984, Stabel 1988, Thompson et al. 1997, Danen-Louwerse et al. 1995, Friebertshauser et al. 1992), fish ponds

(Eiseltova and Pokomy 1994), and permanently ice-covered Antarctic lakes (Hawes and

Schwarz 1999, Neumarm 1999).

2.3.1 Abiotic causes of calcite precipitation

Calcite precipitation can be caused by physical factors which reduce the solubility of calcium and carbonate ions in water. Some factors which cause calcite precipitation are increased water temperature (Strong and Eadie 1978, Stewart 1988, Rosen et al. 1996), which decreases the solubility of CO^, influx of high amoimts of dissolved Ca ions firom natural weathering of parent material or industrial processing wastes (Womble et al. 1996), and removal o f CO^ firom the water, which causes an increase in pH. When water fi-om underground sources emerges, it can undergo outgassing of CO, and temperature changes which can cause calcite precipitation (Cole 1975, Abdelouas et al. 1998). In some aquatic systems, both biotic and abiotic factors play an important role in calcite precipitation

(Freibertshauser et a/. 1992, Effler 1984)

2.3.2 Mechanisms of algal-induced precipitation

2.3.2.1 Direct incorporation

Algal photosynthesis can influence the formation of calcium carbonate in two ways; through direct incorporation into a well-structured exoskeleton or through extracellular precipitation of randomly arranged crystals. Algae can directly incorporate calcium carbonate into an outer shell (lorica or coccolith); this process is fotmd in both planktonic and sessile species in fresh (Krienitz et al. 1993, Thompson et al. 1997) and salt water

(Medakovic et al. 1995). The sessile corallinacean algae can produce more than 50% of the calcareous material in coral reefs (Aharon 1991, in Medakovic et al. 1995). The interaction between sessile coral and free-living algal species is synergistic; Small and Adey

(in press) found that the presence of free-living algae with stony corals increased coral calcification by 60 to 120 percent in a coral reef mesocosm. The stony coral species removed HCO^, with little pH or CO^ ion elevation, while free algae removed CO,, and raise pH and CO^, but did not cause calcification.

The most important calcite-precipitating marine plankton are the coccolithophorids.

These algae form plates of calcite outside their cell membrane called coccoliths, which are periodically shed and subsequently settle to the ocean floor, forming large carbonate deposits. Marine algae have been associated with carbonate production since very early in the earth's history, at least since the Lower Jurassic (Bramlette 1958). One species of coccolithophorid, Emiliania huxleyi , occurs in large blooms in the ocean worldwide

(average annual area 1.4 x 10^ km') and is thought to be responsible for the majority of the

10 modem calcium carbonate deposits on the ocean floor (Westbroek et al. 1993). Some sources estimate that as much as 90% of the carbon in recent marine sediments may be calcite (Aiken et al. 1992, in Fagerbakke et al. 1994).

Phacotus spp. and Synechococcus spp. are freshwater planktonic algae which form outer shells of calcite known as loricae and play major roles in carbon and phosphoms cycling in some freshwater lakes (Krienitz et al. 1993, Thompson et al.

1997). The mechanism of lorica formation in Phacotus is thought to take place in cellular organelles and transported to the surface after mineralization (Hepperle and Krienitz 1996).

2.3.2.2 Indirect extracellular precipitation

Other freshwater algae do not form loricae, intracellular crystals or coccoliths, but instead cause extracellular precipitation of calcite. This occurs because CO, or HCO^ uptake from the surrounding water due to photosynthesis causes alkalization of the water immediately surrounding the cell (Shiraiwa et al. 1993)). At neutral or slightly acidic pH, the photosynthetic reaction depletes carbon dioxide in the water column. The removal of

CO] causes the carbonate-bicarbonate equilibria to shift to the left (indicated by the larger arrows in the below equations), removing hydrogen ions from the water column and thus increasing the pH.

C0^(g) + H , 0 .^ : d L . H ^ c o / pK ,= 1.46 (2-5)

H ,C O / ► K + U C O ^' pK, = 6.35 (2*6)

H+ + C O /' pK ,= 10.33 (2-7)

11 At typical pH values for hardwater lakes (7-9), free CO, concentrations are usually very low, and many algae utilize the more abundant bicarbonate ion as a carbon source. By a mechanism which is not fully understood, HCO^ ions are taken up by the cell from the water column and replaced by OH ions, which increase the pH of the solution (Shiraiwa et al. 1993) and thus increase the likelihood of calcite precipitation. When the solution becomes supersaturated and a suitable triggering event occurs, calcium ions can precipitate with carbonate in the following reaction:

Ca" + 2 HCO; ^ CaCO/s) + H,0 + CO, (2-9)

The formation of calcium carbonate releases CO, into the water, and it is speculated that algal species use this CO, in photosynthesis (Nimer and Merrett 1992, in Westbroek et al. 1993, Nielsen 1995). Thus, calcite precipitation may confer a competitive advantage on algae in waters with low dissolved inorganic carbon concentrations, although the increase in sinking rate of the algae due to the increased mass of calcite may negate the effects of increased CO, availability.

2.4 Influence of calcite precipitation on other chemical species

The production of numerous small calcite crystals can influence the chemical composition of the water column by providing a large surface area upon which other elements can adsorb or coprecipitate. Chemical species affected by calcite precipitation include phosphorus, metals, organic acids, and organic carbon species (Table 2.1). Since many of these constituents sorb onto the active growth sites of calcite crystals or become incorporated into the crystal matrix, they influence the rate of precipitation, often acting as inhibitors of further crystal growth.

12 Substance/Property Location Reference Phosphorus lakes, estuaries Boers etal 1998 Lake Veluwe Danen-Louwerse er a/. 1995 Onandoga Lake, NY Effler and Driscoll 1985 laboratory Giannimaras and Koutsoukos 1987 Lakes Stechlin, Haussée; Germany Gonsioczyk et a/. 1998 Maumee River, OH Green et al. 1978 laboratory House 1987 Great Ouse River, UK House and Denison 1997 River Wey, UK House and Denison 1998 laboratory House and Donaldson 1986 River Swale, UK House and Warwick 1998 laboratory House et al. 1986a,b experimental stream House et a/. 1989 Lake Balaton, Hungary Istvanovicset al. 1989 Wallensee Jager and Rohrs 1990 laboratory Kastelan-Macan and Petrovic 1995 laboratory Kitano et al. 1978 Lake Constance, Germany Kleiner 1988 Feldberger Haussée, Germany Krienitz et al. 1996 Black Lake, BC Murphy era/. 1983 Lawrence Lake, MI Otsuki and Wetzel 1972 Figure Eight Lake Prepas et al. 1990 Lake Constance, Germany Rossknecht 1980, Krienitz et al. 1996 Lake Michigan, US Shafer and Armstrong 1994 sediment biofilm Woodruff et al. 1999

Organic carbon (biomass) Lake Breiter Lucin Koschel et fl/. 1983 Lake Constance, Germany Kuchler-Krischun & Kleiner 1990 Lakes Zurich, Sempach; Weilenmann et al. 1989 Switzerland

Transparency Gwasco Lake, NY Effler era/. 1987 Great Lakes, US Strong and Eadie 1978 Otisco Lake, NY Weidemann er a/. 1985

Continued on next page

Table 2.1 - (Chemical substances and properties which interact with calcium carbonate in aquatic systems.

13 Table 2.1, continued

Substance/Property L ocation R eference M etal ions U Arizona Abdelouas ef a/. 1998 Pb, Cd laboratory Bilinski ef a/. 1995 Cd Tennesssee Cicerone er a/. 1999 K, Fe, Pb, Zn, Cr, Cd Lachine Canal, Canada Galvez-Cloutier and Dube I998a,b Mg, Fe laboratory House era/. 1986a Pu, u. Am, Tu, Pb laboratory Mcecc and Bcnninger 1993 Pb, Cd KS, MO, OK O'Day et al. 1998, Carroll et al. 1998 Pb, Zn, Cu laboratory Petrovic er a/. 1999 B, Se fly ash waste Reardon era/. 1993 Mg Lake La Cruz, Spain Rodrigo era/. 1993 Sr Lake Constance, Germany Stabel 1988, 1989 Cd laboratory van der Weidjen er a/. 1994, 1997 Pb Lake Michigan, US Van hoof and Andren 1989 Mn, Fe, Cd River Glatt, Switzerland von Gunten eral. 1994 Cd, Co, Cr, Cu, Ni, Pb, Zn laboratory Vymazal 1995b Fe laboratory Wetzel and White 1985

Organic substances organic substances laboratory Chave 1965 dissolved organic C Chave and Suess 1970 dissolved organic C Chascomus Pond, Argentina Conzonno and Cirelli 1995 dissolved organic C Onandoga Lake, NY Effler and Driscoll 1985 humic acids laboratory Fiskus and Manning 1998 polyphosphonates laboratory Hamza era/. 1993 marine organic acids laboratory Kastelan-Macan and Petrovic 1996 pyrene, anthracene, laboratory Onken and Traina 1997 and humic acid yellow organic acids Lawrence Lake, MI Otsuki and Wetzel 1973, 1974, Wetzel etal. 1974, Wetzel and White 1985 humic acids laboratory Petrovic er al. 1999 polyphenols Lake Powell Reynolds 1978 dissolved humic acids Lawrence Lake, MI Stewart and Wezel 1981 vitamin B,, Lawrence Lake, MI White and Wetzel 1985

14 An important distinction must be made between the terms sorption and coprecipitation. Coprecipitation is the incorporation of chemical impurities directly into the crystal matrix of a growing crystal. Sorption is a general term that includes adsorption, the association of molecules with the surface of a solid, absorption, the incorporation of molecules within a solid, and coprecipitation processes. Since distinguishing between adsorption, absorption and coprecipitation is not possible using the methods used in this dissertation, the general term sorption will be used for the results of this study. However, the terminology used in previous studies is maintained in the following section.

2.4.1 Phosphorus

Since initial studies by Otsuki and Wetzel (1972), the effect of calcite precipitation on freshwater phosphorus dynamics has been widely studied in the field (Green et al.

1978, Murphy et al. 1983, Effler and Dricoll 1985, Shafer and Armstrong 1994, Krienitz et al. 1996), in laboratory and mesocosm studies (House and Donaldson 1986, House

1987, House etal. 1986a,b, 1989, Kasetelan-Macan and Petrovic 1996), and in computer simulations (Koschel et al. 1983). Calcite precipitation affects the cycling of P in freshwater aquatic systems in two major ways: through sorption reactions and through flocculation of entire algal cells. P can be incorporated into the crystal structure of calcite as crystals grow or can adsorb onto the surface of newly formed crystals. The incorporation of P at crystal growth sites slows the formation of calcite crystals and at higher concentrations may stop precipitation entirely, or delay precipitation until much higher levels of calcium carbonate saturation are reached. For this reason, P is often referred to as an inhibitor of calcite precipitation.

Phosphate coprecipitation with calcite is of particular interest because of its possibility as a natural method of regulating the trophic status of a lake (Otsuki and Wetzel

1972, Koschel et al. 1983, House etal. 1989, Hartley et al. 1995, 1997). Otsuki and

15 Wetzel (1972) showed that phosphate coprecipitated with calcite in filtered lake water when pH was increased using NaOH and Na^CO^, and found that at pH 9.5 and 10.0, over 74% of the phosphate precipitated with the carbonates. The rate of coprecipitation was particularly rapid at 24 C, with approximately 74% of the phosphate precipitating within 5 minutes. They then suggested that calcite precipitation acts as an indirect population control mechanism for algae and macrophytes by reducing available phosphate in the water column, and that the process of eutrophication would be slower in hardwater lakes than in softwater lakes because of this phosphate removal mechanism.

The second major method of P removal during precipitation events is through the flocculation of entire algal cells. Since calcite precipitation usually occurs very near the surface of algal cells, the calcite crystals can bind to algal cells during formation. When the calcite crystals sink to the bottom of the lake, the attached algal cells sink as well, thus removing the P which is present inside their cells. This process can be an important method of P removal in some lakes (Koschel et al. 1983, Kiichler-Krischun and Kleiner

1990).

2.4.2 Other nutrients

Although P has been the most-studied nutrient associated with calcite precipitation, calcite can remove other nutrients firom the water column (Table 2.1). Calcite has been shown to sorb nitrate (Jurinak and Griffin 1972), potassium (Galvez-Cloutier and Dube, 1998a,b), silica (Kitano et al. 1979) and vitamin (White and Wetzel 1985) in the water column.

2.4.3 Organic carbon

Calcite precipitation strongly affects the cycling of inorganic carbon in aquatic ecosystems through its impact on dissolved carbonic acid species, but it can also affect the

16 cycling of organic carbon such as humic acids, which can sorb onto the crystal surfaces

(Table 2.1). The incorporation of entire algal cells into the matrix of growing calcite crystals and their subsequent settling out of the water column can also be an important mechanism for organic carbon removal in lakes (Kiichler-Krischun and Kleiner 1990).

Humic acids act to inhibit calcite precipitation (Chave and Suess 1970, Stewart and

Wetzel 1981, Wetzel and White 1985). Stewart and Wetzel (1981) found that flilvic acids were significant inhibitors of calcite precipitation, completely blocking crystal growth at concentrations > 2 mg/L. However, calcite can remove significant quantities of organic acids during precipitation events. In a shallow eutrophic lake, Conzonno and Cirelli ( 1995) found that dissolved organic matter decreased concurrently with a large increase in calcite saturation index in spring and summer, and concluded that humic acids were associated with newly forming calcite crystals. This association removed the humic acids firom the water column, but prevented crystal growth, resulting in the high saturation index values.

Humic acids on the surfaces of calcite crystals affect the way the crystals interact with other dissolved chemical species. Some organic acids have been found to inhibit calcite dissolution as well as precipitation (Compton et al. 1989). The formation of a humic acid complex acts to stabilize calcite crystals (Chave 1965), which can prevent or enhance their interactions with other ions present in solution (Chave 1965, Petrovic et al.

1999). The presence of humic acids affects the sorption of metals onto calcite minerals

(Petrovic et al. 1999). At acidic pH values, the increasing humic acid concentrations caused increased sorption of Cu'\ but decreased sorption of Zn".

Humic acid complexes on calcite minerals affect sorption of non-organic solutes

(Onken and Traina 1997). Increasing humic acid concentrations caused increased sorption of both pyrene and anthracene to geologic and reagent calcite.

17 2.4.4 Metals

Calcite crystals can sorb metal ions onto newly forming crystal surfaces (Cicerone et al. 1999, Petrovic et al. 1999). Many different metals can adsorb or coprecipitate with calcite, including Am, B, Cd, Cr, Cu, Fe, Mg, Mn, Se, Sr, Pb, Th, U, and Zn (Table

2.1). As stated earlier, humic acids can increase metal sorption onto calcite crystals.

Magnesium acts to inhibit calcite formation (Chave and Suess 1970)

2.5 Calcite precipitation in hardwater lakes

2.5.1 Seasonal studies

Stabel (1986) studied seasonal shifts in calcite solution equilibria and their relationship to sedimentation in Lake Constance. Over three years, seasonal peaks in calcite precipitation and sedimentation occurred from late May to early October. These peaks were concurrent with blooms of six algal species, and many crystals contained attached or occluded algal cells. Therefore, algal production was the most probable cause of calcite precipitation in Lake Constance.

When Krienitz et al. (1993) examined uptake of available calcium in northeastern

German hardwater lakes by Phacotus spp., they found that in two eutrophic lakes,

Phacotus accounted for 95 to 100 percent of the total calcite formed. Phacotus was found to precipitate 5 to 20 percent of the calcium carbonate under normal circumstances in the growing season.

Calcite precipitation in Fayetteville Green Lake was found to be caused by a unicellular lorica-forming , Synechococcus (Thompson et al. 1997). The whiting event in the lake occurred at the same time as the exponential growth phase of

Synechococcus, and the highest concentrations of calcite were found at a depth which corresponded to the subsurface maximum of Synechococcus.

18 Murphy et al. (1983) found that soluble reactive P concentrations in Black Lake,

British Columbia decreased in the summer, coinciding with a bloom of Aphanizomenon flos-aquae. The role of calcite precipitation in phosphorus removal was inferred from the

fact that SR? concentrations decreased dramatically in blooms in which calcite precipitation

occurred, and decreased little in blooms without calcite precipitation.

Koschel et al. (1983) used a dynamic ecosystem model to investigate the causes of

the trophic state of Lake Breiter Lucin. The results of the model showed that self-

flocculation of algal with calcite ciystals and their subsequent settling provided the best

explanation for the observed decrease in phosphate concentrations in the summer.

2.5.2 Short-time interval studies

Given the diurnal increases in pH and saturation of calcite in the water column,

some researchers have studied calcite precipitation and dissolution on shorter time-scales

than seasonal. Kiichler-Krischun and Kleiner (1990) studied calcite precipitation at daily

intervals in Lake Constance. They found that the time lag between maximum algal biomass

and the start of calcite precipitation was within 1 day, which was much shorter than that

found by earlier studies. The longer induction period found in previous studies was

concluded to be an artifact of their longer sampling intervals. Calcite crystals formed more

than 90% of inorganic dry weight and 40% of total dry weight in the suspended sediment.

The crystals were associated with Chlorella spp. and Stephanodiscus hantzschii , as well

as other algae, and contributed to their settling out of the photic zone.

Phosphorus concentrations were less than 10 |ig/l when calcite first precipitated due

to prior uptake by algae. Thus, Kuchler-Krischun and Kleiner (1990) concluded that

phosphorus coprecipitation would not significantly affect the rate of phosphorus removal

fix»m Lake Constance, although calcite crystal formation did affect the amount of

phosphorus in the photic zone by forming aggregates with algal cells. When these

19 aggregates sank out of the epilimnion, the phosphorus which had been taken up by the cells was removed from the water column into the sediments.

House et al. (1989) modeled the precipitation of calcite, carbon dioxide and oxygen transfer, and coprecipitation of phosphate in a recirculating experimental stream during a 24-hour experiment. Total calcium concentration, pCO„ and total alkalinity increased during the night and decreased to minima at 1600 to 1800 hours, while conductivity and pH showed the inverse pattern, increasing during the day and decreasing at night. There was a loss of calcium from the water, which was associated with calcite precipitation. In the model, the predicted coprecipitation of phosphorus was small, with a maximum of 6% removal.

Hartley et al. (1997) demonstrated that extracellular calcite precipitation and phosphate coprecipitation occur at similar rates to abiotic calcite precipitation through experiments with algal cultures of Chlorococcum sp. The rate of decrease in soluble reactive phosphorus concentrations was found to be similar to rates in abiotic experiments, indicating that the mechanism of phosphate coprecipitation is the same for algal induction as for abiotic calcite precipitation.

Cicerone et al. (1999) found that dissolved Ca concentrations in a lake in

Tennessee varied on a diel cycle which was strongly correlated with changes in dissolved oxygen and pH due to algal production. Calcite formed during daylight hours and dissolved at night, when pH dropped and CO^ concentrations rose. Cadmium sorption to calcite was shown to occur on a rapid time scale (<6 hr), indicating that Cd dynamics could be mediated by the diel precipitation and dissolution of calcite.

2.6 Calcite precipitation in streams and rivers

Green and Smeck (1979) found in-stream precipitation of calcite was associated with algal production in the Maumee River. However, the calcite did not contribute to the

20 sediments on the river bottom, but dissolved in the lower part of the water column. Green et al. (1978), studying the same river, found that P in the suspended sediments was positively correlated with calcite content of the sediments. Evidence of P removal due to calcite precipitation has been observed in rivers in England (House and Denison 1997,

1998, House and Warwick 1998). Calcite has also been found in sediments of freshwater canals (Galvez-Cloutier and Dube 1998a,b, Wall and Wilding 1976).

2.7 Calcite precipitation in wetlands

Wetlands have not been extensively studied as potential sites for calcite precipitation

(Reddy et al. 1993, Scinto 1997, Wu and Mitsch 1998, Naim and Mitsch 2000). There are many reasons for this lack of published studies on calcite precipitation. First, wetland ecology is a younger science than limnology. Second, the differences between most wetlands and lakes are profound. Emergent wetlands are generally shallow ecosystems, which do not undergo stratification as do lakes. The photic zone is very shallow and almost always extends to the bottom sediments. Many wetlands are flowthrough systems, and most are only seasonally flooded. Dissolved organic carbon is usually abundant in wetland surface water and may inhibit calcite formation.

Nonetheless, productive wetlands fed by hardwater sources could experience significant calcite precipitation. As water passes through a wetland, it is often warmed by solar radiation. High aquatic primary productivity causes increased pH during the day, especially in the volume of water directly surrounding the algal filaments. This volume of water does not experience turbulent mixing, but rather is dominated by diffusion processes, and thus can become highly alkaline. Increased temperature and pH decrease the solubility of calcite and can cause its precipitation from the water column. Calcite precipitation is found on a large scale in the Everglades (Scinto 1997) because of the limestone bedrock and the predominance of periphyton.

21 The occurrence of calcite precipitation in temperate wetlands and its importance in phosphorus dynamics is an important unanswered question, and is the major subject of this dissertation.

22 CHAPTER 3

METHODS

3.1 Site description

This study was carried out at the Olentangy River Wetland Research Park

(ORWRP), a 12-ha wetland research facility located on the campus of The Ohio State

University, Columbus, Ohio (Fig. 3.1); 83° T 81" W longitude, 40° 1' 59" N latitude.

Two 1-ha experimental wetland basins were constructed at the ORWRP in 1993-1994 on an abandoned agricultural field located on a fioodplain. They receive water pumped from the adjacent Olentangy River, a 4th order stream. The native soil under the wetland basins is a Ross Series, loamy mesic Cumulic Hapludoll, and no evidence of hydric soils or of excessive carbonates in the soil was found prior to construction (Naim 1996). The experimental marshes were constructed as mirror images of one another and with identical geomorphology; each wetland contains three deepwater (0.35-0.5 m) areas firom inflow to outflow, as well as shallower (0.0-0.35 m) areas between the deepwater areas and near the edges (Fig. 3.1, Fig. 3.2). The shallow areas are vegetated with emergent macrophytes such as Schoenoplectus tabernaemontani, Sparganium eurycarpum and Typha spp., while the deepwater areas do not have emergent macrophytes. Conversely, the deepwater areas have almost continuous cover by filamentous algal species {Cladophora,

Rhizoclonium, Hydrodictyon, and Spirogyra) during the summer, as well as occasional

23 linton Park Weir River Intake

Pumps Olentangy Intake Pipes 10 30 m

Mesocosm Compound

Bottomland Outflo HardwoofL illabon^ Forest Mltlgatldn i Sw^le ^\^A^tland\ & Strea

Dodrldge Street Weir

Wetland Dodrldoe Street Discharge to River

Figure 3.1- Plan view of the Olentangy River Wetlands Research Park at The Ohio State University, Columbus OH, during the study period. Water is pumped from the Olentangy River into the two experimental marshes (1 and 2) and flows through each basin into a combined swale/stream system and back into the Olentangy River. The mesocosm compound (3) used in the study is located northwest of the basins.

24 160 m N .î 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 À

\

200 m \

Figure 3.2 - Locations of soil (•) and water (* ) samples and YSI datasondes locations (x) in the two experimental marshes for this study (1996-99) with a permanent 10 m x 10 m grid system established in 1993. Prior to flooding (1993), soil samples were collected at grid intersections within the wetland basins (Naim 1996). In 1995, soil samples were collected at every other intersection (the intersection of dark lines within the basins) (Naim 1996).

25 cover by Lemna minor, Potamogeton pectinatus, Potamogeton and Najas natans minor

(Wu and Mitsch 1998, Kantz and Deal 1998, 1999) The shallow areas have almost no filamentous algae or submersed aquatic macrophytes present, and only a small amount of

Lemna. Wetland 1 was planted in May 1994, while Wetland 2 was left as an unplanted control. As a result. Wetland 1 had a higher percent cover of emergent vegetation in the first few years of the basins’ development. For the period of the study, both wetland basins were roughly equal in percent vegetative cover. During the years in which the water quality data were collected (1996-98), the wetlands were very similar in both structure and ecosystem fimction (Mitsch, pers. comm.) and were considered generally converged

(Mitsch et al. 1998, Bouchard and Mitsch 1999). By 1999, Wetland 2 had become dominated by Typha spp., while Wetland 1 remained a more diverse patchwork of plant species, such as Schoenoplectus tabernaemontani and Sparganium eurycarpum in addition to Typha spp.(Mitsch,pers.comm.).

Both the emergent macrophytes and the producers (macroalgae, plankton, floating­

leaved and submersed aquatic plants) in the wetlands are highly productive, and the wetland basins show large diurnal changes in water chemistry during the growing season

(Fig.3.3). Temperature can increase by several ° C during the day due to solar heating.

Dissolved oxygen concentrations and pH also increase during the day; dissolved oxygen

sometimes exceeds 30 mg/L and pH can exceed 10 during the day in summer.

Conductivity decreases by approximately 100 |iS/cm during the day, suggesting that ions

are being removed firom solution in significant amounts. Conductivity also decreases from

inflow to outflow. These diurnal changes in conductivity and pH, as well as decreases in

conductivity from inflow to outflow suggest that calcite precipitation may occur in the

wetlands.

26 DO mg/L Temp C 25

20 £ O) 3 2 0) Q. E

0:00 6:00 12:00 18:00 0:00 6:00

•Cond

500

9 ? 400

350

300 0:00 6:00 12:00 18:00 0:00 6:00 time, hr

Fig. 3.3 - Example of typical growing-season ditimal changes in water quality parameters in the middle subbasin of Wetland 1 experimental marsh at the Olentangy River Wetland Research Park, July 17-18,1997: a) dissolved oxygen and temperature, and b) conductivity and pH.

27 Other evidence suggests calcite precipitation is occurring in the wetlands. The dominant macroalgal species at the ORWRP {Cladophora) has been found to precipitate calcite (Kishler 1967, Taft and Kishler 1973, Wood 1975, Sikes 1978) and Hydrodictyon has shown the ability to alkalize external medium while taking up HCG^ when CO^ levels are low (Rybova et al. 1991). Extremely high levels of calcium (mean of 137 mg/g dry weight) were found in metaph}7on samples taken during an earlier study at the ORWTIP

(Wu and Mitsch 1998). During drawdown events early in the wetlands’ development, white crystals were observed on the sediment and algal surfaces (Mitsch, pers. comm..

Fig. 3.4). Because of these observations, calcite precipitation was strongly suspected to have occurred in the wetland basins.

3.1.1 Mesocosm description

In addition to the full-scale wetland studies, a replicated mesocosm experiment was designed to determine the role of algal production in calcite precipitation. Twenty l-m ’ mesocosms consisting of 380-L stock tanks set into the ground and filled with 25-30 cm of non-hydric soil and 30-35 cm of river water simulated unvegetated deepwater areas of the full-scale wetlands (Fig. 3.5). Ten of the twenty mesocosms, randomly selected, were stocked in June 1998 with 450 g wet weight (approximately 59 g dry weight) of filamentous algae that came firom the adjacent full-scale experimental wetlands (major genera Cladophora, Rhizoclonium, Hydrodictyon, and Spirogyra) and fi-om a stock tub of algae maintained on site. Algal samples were examined using a microscope and presence of major genera were confirmed. The other ten (control mesocosms) were covered with black cloth to prevent algal production.

Water temperature provides a possible confounding effect, because higher water temperature in the algae mesocosms would cause higher saturation of calcite. The uncovered algae mesocosms had significantly different water temperatures than the covered

28 Fig 3.4 - Wetland basin during drawdown on August 3, 1994. The white substance in the foreground is dried metaphyton, whose color is an indicator that the metaphyton mat may contain calcium carbonate. (Photograph by William J. Mitsch)

29 Control stand pipes Algal treatm ent

Fabric cover

soil soil

(G3

Fig. 3.5 - Experimental wetland mesocosms as a) elevation view and b) plan view. A represents algae treatment and C represents control treatment. Numbers refer to mesocosm identification numbers.

30 controls. However, the difference in temperature between the algae and control mesocosms was not enough to cause the observed difference in saturation index (SI) values between the treatments. When SI values were calculated using higher temperatures

(equivalent to algae mesocosms) in the control mesocosms, the difference between treatments remained significant.

3.2 Hypotheses

In these sections the hypotheses tested in the two scales studied (whole-ecosysem studies and mesocosm experiment) are presented.

3.2.1 Full-scale wetland hypotheses

Water quality data fi-om the full-scale (1-ha) experimental wetlands were analyzed to test the following hypotheses:

1) Water column GPP and R in the deepwater areas of the experimental wetlands show significant seasonal patterns, with high areal rates during the growing seasons comparable to extremely eutrophic lakes.

2) There is no significant difference in GPP and R between the two experimental wetland basins for the years of macrophyte cover convergence (1996-1998).

3) Water chemistry change is significant for all parameters fi-om inflow to outflow during the growing season: pH, DO and temperature will increase, and conductivity will decrease.

4) Calcite precipitation occurs at significant rates in the experimental wetland basins as a result of high aquatic productivity during the growing season.

31 5) Phosphorus is sorbed with the calcite and is thereby removed from the water column.

6) Calcite and sorbed phosphorus are deposited into the sediments, forming a P sink.

7) Calcite precipitation and phosphorus sorption occur on a diurnal time-scale.

3.2.2 Mesocosm experiment hypotheses

The mesocosm experiment was designed to test the following hypotheses:

1) Calcite precipitation occurs in the presence of algae (algal mesocosms), but not in their absence (control mesocosms).

2) Calcite precipitation/dissolution occurs on a diurnal schedule, with precipitation occurring during the day and dissolution at night.

3) Phosphorus sorption with calcite occurs in the algae mesocosms.

4) Phosphorus sorption and desorption occurs on the same time-scale as calcite precipitation and dissolution.

3.3 Full-scale wetlands

3.3.1 Aquatic metabolism

From July 1996 to December 1998, four YSI 6000 (YSI Inc., Yellow Springs,

Ohio) datasondes have been deployed in the two experimental wetland basins, one in each middle and outflow deepwater areas (Fig. 3.2). These sondes were hung under wetland

32 boardwalks so that the probes would be suspended in the middle of the water column. The sondes measured water temperature, pH, specific conductance, and dissolved oxygen at half-hour intervals. Sondes were removed fi'om the wetlands, downloaded, maintained and calibrated monthly according to the manufacturer’s instructions.

From the dissolved oxygen data, rates of gross primary productivity and respiration were determined using the diurnal oxygen curve method (Odum, 1956). The method is illustrated in Fig. 3.6. The rate of change in dissolved oxygen was calculated for each half- hour time interval according to the equation dPO = DO,-DO, (3-1) dt tj-t,

where

DO= dissolved oxygen, g m'^ t=time, hr

Average respiration (R^vg) was calculated from mean night respiration rates (for these calculations, 0:00 to 6:00 am was used, see Fig. 3.6) before (denoted 0:00-6:00am) and after (denoted 24:00 - 30:00 am) the day for each calculation, when it was clear that there was no residual effect of sunlight.

Kvg = -average dPO (3-2) dt 0:00-6:00, 24:00-30:00 where

R,„g = average respiration rate, g m'^ d '

33 dOO/dt g Op d* Ravg

dDO/dt g Ü 2 m’2 cT ' R

0.5

0:00 6:00 12:00 18:00 2400 3600

Fig. 3.6 - Illustration of the method used to estimate gross primary productivity (GPP) and respiration (R) (Odum, 1956). Dissolved oxygen (DO) readings are used to determine the rate of change for DO during the day, while both photosynthesis (P) and respiration(R) are occurring, and at night, when it is assumed that only R is occurring. The nighttime data points are used to determine the rate of R, shown in b) by a dotted line. The rate of R is added to the rate of change for DO and integrated over daylight hours to calculate GPP in g O; m'^ d'*. This number is multipled by the average depth to determine areal GPP (c) in g Oj m'^ d '.

34 Instantaneous gross primary productivity was calculated by adding average respiration to the instantaneous rate of dissolved oxygen increase in dissolved oxygen during the day.

GPPi.. = dPO + R,.ivg (3-3) dt V. where

GPP|^= instantaneous rate of gross primary productivity, g O, m'^ d '

The total gross primary production was then calculated by integrating these rates over time for the day.

dusk

GPP.., =J GPP,„ dt (3-4)

dawn where

GPP^g, = total daily gross primary productivity, g O, m'^ d '

Total daily respiration was calculated by multiplying the average hourly rate of respiration by 24 hours.

Ry., = 24 hr/d * (3-5) where

R„„,= total daily respiration, g O, m'^ d '

Equations 3-4 and 3-5 calculate GPP and R in terms of volume (g O, m'^ d '). To convert this to an area basis, GPP and R were multiplied by the average depth of the

35 deepwater basins (estimated from staff gage data measured twice daily) in order to express the results as g O, m'^ d '.

GPP = G P P ,/(L (3-6)

R = Rvc*d. (3-7) where

GPP = total daily gross primary production, g O, m ‘ d '

R = total daily respiration, g O, m * d ' d^ = daily average water depth, m.

Net primary production was calculated from GPP and R:

NPP = GPP - R (3-8)

where

NPP= net primary productivity, g O, m‘‘ d '

An oxygen diffusion correction was not considered in the estimation of metabolism,

for two reasons. First, the water column and surface in the wetland basins were

completely covered with filamentous algae or duckweed, which would act as physical

barriers to diflusive transport across the air-water interface (see e.g. Morris and Barker

1977), although it is recognized that some of the algae at the surface release oxygen directly

to the atmosphere. Other researchers have found diffusion rates to be negligible in similar

freshwater wetland ecosystems (Reeder 1990, Mitsch and Reeder 1991) because of the

relative lack of surface turbulence.

36 From the sonde data, daily averages, maxima, minima, and daily ranges were calculated for water temperature, pH, and conductivity as corrected to 25° C. These data and the GPP, NPP and R data were analyzed using a general linear model to determine which factors were statistically significant for each parameter measured. The main factors tested in the model were year, basin ( 1 or 2), season (spring, summer, fall, winter), and subbasin (middle, outflow). Interaction effects were also tested. For the purposes of the general linear model, spring was defined as March through May, summer as June through

August, fall as September through Nov, and winter as December through February.

3.3.2 Total dissolved solids budget

A budget for the inflow and outflow of total dissolved solids in the experimental wetland basins was developed for the years 1996-1998. Total dissolved solids concentrations (mg/L) can be calculated from conductivity measurements (|iS/cm) using an empirical factor which ranges from 0.5 to 0.9 (APHA 1989, Method 2510 A). However, this factor must be corrected for temperature effects, as conductivity increases with increasing temperature. Twenty-four 1-L water samples were taken in November 1999 from the inflow, middle, and outflow of the wetlands, and conductivity and temperature measurements were made concurrently using a YSI 610-D (YSI, Inc., Yellow Springs,

OH). Samples were taken back to the laboratory and 300-400 mL of each sample was immediately filtered through a 0.45 |jm cellulose filter. Two-himdred - mL subsamples of the filtrate were placed into preweighed erlenmeyer flasks, which were then dried at 105

°C. The flasks were cooled in a desiccator and reweighed. The remaining water samples were then placed in water baths to change their temperature and their conductivity and temperature were measured several more times to determine the effects of temperature on the empirical ratio mentioned above.

37 From these water samples, 48 data points were used to determine the empirical relationship among temperature, total dissolved solids and conductivity (Fig. 3.7). A single linear equation was calculated for 0-40 °C (Fig. 3.7a).

TDS = SC*(1.05069 -0.01583*T) (r2=0.9101, n=48) (3-9)

where

TDS = total dissolved solids, mg/L)

SC = specific conductance in |iS/cm)

T = temperature, “C

However, the data were better described by a second-order equation (Fig 3.7b).

Two data points were discarded as outliers, and the following equation was calculated:

TDS = SC*(0.0003655 *T^ - 0.03156*T + 1.17385) (r2=0.9814, n=46) (3-10)

Using equation 3-10, the TDS concentrations in the inflow and outflow of each basin were calculated firom specific conductance and temperature data taken twice daily at the inflow and outflow of the wetland basins from 1996 to 1998. The TDS concentrations in the middle subbasins were calculated firom specific conductance and temperature data taken by the YSI 6000 datasondes fi-om July 1996 through December 1998.

Calculating the TDS outflow firom the wetlands via groundwater required making some assumptions, as no conductivity data were available for groundwater outflow. The

TDS concentrations leaving each subbasin via groundwater were assumed to be equal to the concentrations in the surface water of each subbasin. When only inflow and outflow

38 1.2

1

ê 0.8 I 2 TJ ! O 0.6 §

0.2

0 10 20 30 40 50

Temperature,°C

1.2

1.0

I 0.8 ■o

0.6 iQ I- 0.4

0.2

0.0 0 10 20 30 40 50 Temperature, oC

Fig. 3.7 - Regression plots for the temperature-dependent empirical relationship between conductivity and total dissoved solids, a) a linear regression for the entire temperature range. This model was discarded in favor of b) a second-order equation.

39 data were available, it was assumed that the concentration of total dissolved solids in the groimdwater outflow was equal to the average of the TDS concentrations at the inflow and outflow of the wetlands.

[TDS]^ = ([TDSLM TDSW (3-1D where

[TDS]g^ = the concentration of total dissolved solids in the groundwater, g m '\

[TDS]j„ = concentration of TDS at the inflow of the wetland, g m'^

[TDSJou, = concentration of TDS at the surface outflow of the wetland, g

When only data from the middle subbasins were available, the groundwater leaving the wetlands was assumed to have the same concentration as the middle subbasins.

The amount of groundwater leaving the wetlands via each subbasin was calculated from the total groundwater outflow according to the area of each subbasin.

Qgw(subbasin) Qgw-^iubbasin (3 13) ^ to al where

Qgw(subbMin) ~ the total water flowing out a particular subbasin, m^ d ‘

= the total flow of groundwater leaving the wetland, m d 3 J-I

^subbasin ~ the area of a particular subbasin, m’

= the total area of the wetland basin, m’

Using this method, the inflow and outflow subbasins each accounted for approximately 25% of the total groimdwater flow, and the middle subbasin accounted for approximately 50 % of the total groundwater flow. The daily mean TDS concentrations

40 were multiplied by the daily volumes of surface water and groundwater flowing into and out of the wetlands, obtained firom yearly water budget calculations (Wang et al. 1997,

Wang et al. 1998, Wang and Mitsch 1999).

TDS^=[TDSL*Q^ (3-13)

TDS_ = [TDS]_*Q_ (3-14)

TDS^ . [TDS],„*Q^,„ + [TDS]^/Q^,„„ + [TDS1„*Q„„, (3-15)

where

TDSj„ = the daily sum of total dissolved solids entering the wetland, g d

Qin= the total flow of surface water entering the wetland, m^ d '

TDSgm = the daily sum of TDS leaving the wetland through surface water, g d .1

Qout= the total flow of surface water leaving the wetland, m^ d‘‘

TDSg,^ = the daily sum of TDS leaving the wetland through groundwater, g d'

Qgw(in)~ the total flow of groundwater leaving the inflow subbasin, m^ d '

Qgw(mid)“ the total flow of groundwater leaving the middle subbasin, m^ d '

Qgw(out) " the total flow of groundwater leaving the outflow subbasin, m^ d‘‘

These daily values were summed for each month.

TDS,„„ = ZTDS„ (3-16)

T D S ^ „ = ZTDS„ (3-17)

41 where

TDSjnfD = the raw monthly sum of TDS entering the wetland in surface water, g month '

= the raw monthly sum of TDS leaving the wetland in surface water, g month '

TDSg^(T) - the raw monthly sum of TDS leaving the wetlandin groundwater, g month '

To correct for missing data days, these monthly totals were multiplied by a correction factor, C^., for each type of flow (surface inflow, surface outflow, groundwater outflow)

C = - Q (3-19) where

Q = monthly total water flow, m^

Qcond - total water flow on days with available conductivity data, m^

These corrected monthly totals were summed for the entire year to determine the percent retention of total dissolved solids in the wetland basins.

3.3.3 Spatially detailed diurnal water quality

3.3.3.1 Field sampling

Water samples and measurements were taken in the wetland basins at dawn, dusk, and the following dawn on these dates: July 15-16, 1998; August 14-15, 1998; October

21-22, 1998; March 30-31, 1999; June 1-2, 1999. Samples were taken at seven points firom inflow to outflow within each of the two wetlands: one directly fi-om the inflow, and one in each of the deep and shallow areas in the inflow, middle, and outflow subbasins

(Fig 3.2). Temperature, dissolved oxygen, specific conductivity, and redox potential measurements were measured with a Hydrolab Surveyor 3 multiprobe (Hydrolab Corp.,

42 Austin, TX), and pH was measured using a Solomat 520c (Solomat, Norwalk, CT) with an Orion pH probe attached (Orion Research Inc., Beverly MA). Specific conductivity

(SC) values were corrected for temperature effects, and are presented normalized to 25° C.

Dawn-dusk-dawn dissolved oxygen data were used to estimate gross primary production

(GPP) using the method of Odum (1956).

Water samples were taken at each sampling point using 500-mL acid-washed plastic bottles. Total organic carbon samples were taken in the field in 30-mL amber glass bottles which had been acid-washed and baked at 250° C for 24 hr. All sample bottles were rinsed with site water before filling to remove any trace acidity which could affect the samples. Water samples were stored on ice and immediately taken to the laboratory, where they were analyzed for total alkalinity, dissolved calcium (Ca), soluble reactive phosphorus

(SRP), and total phosphorus (TP).

Temperature, pH, total alkalinity, dissolved calcium, and conductivity were used to calculate a saturation index (APHA 1989, Method 2330B), which showed whether calcite precipitation was thermodynamically favored in the wetlands.

SI = pH - pH, (3-20)

where

SI = saturation index pH = measured pH of water pH, = pH of the water if it were in equilibrium with calcite

pH, is calculated by the following equation

pH, = pKj - pK,+p[Ca^1 + p[HCO,] + 5 pf„ (3-21) 43 where

Ko = the second dissociation constant for carbonic acid at the water temperature

K, = the solubility product constant for calcite at the water temperature

[Ca**] = calcium ion concentration, g-moles/L

[HCOj'] = bicarbonate ion concentration, g-moles/L f^= activity coefBcient for monovalent species at the specified temperature

The parameters in equation 3-18 were calculated using the following equations

pK, = 107.8871 + 0.03252849*7 - 5151.79/T - 38.92561 logT+563713.9/7- (3-22) pK,= 171.9065+ 0.077993*7-2839.319/7-71.595 log T (3-23)

[HCO ■] = Aik. + lQ(Pfm-pH)_ iQ(pH-pfm-pKw) (3-24) 1+0.5*10'"""'^') pK^ = 4471/7+ 0.01706*7-6.0875 (3-25) pfm= A*m°/ ______-0.3 1 (3-26) 1+F

1 = 1.6*10'^ C (3-27)

A = 1.82* 10*(E7)-‘-^ (3-28)

E = 60954 - 68.937 (3-29) 7+116

where

7 = water temperature, K

Alkt = total alkalinity, g-eq/L

K^ = dissociation constant for water

E = dielectric constant

44 ^ = activity coefficient for monovalent species

C = conductivity, |imhos/cm

I = ionic strength

3.3.3.2 Laboratory analyses

Water samples were analyzed for total alkalinity by Gran titration (APHA 1989,

Method 2320). One hundred-mL samples were titrated with 200 pL aliquots of 0.1 M HCl to a pH of approximately 3. Gran titration was carried out within 6 hours of sampling.

Water samples were filtered through 0.45 pm cellulose filters for SRP analysis within 48 hr of sample collection, stored in glass test tubes at 4° C and analyzed within 30 d using a Lachat Quikchem 8000 automated ascorbic acid reduction method (APHA 1989

Method 4500-P F). Unfiltered total phosphorus samples were digested with ammonium persulfate and analyzed for total phosphorus using the same automated ascorbic acid reduction method.

Water samples were filtered through 0.2 pm polycarbonate membranes for dissolved Ca analysis. Samples were filtered within 48 h of sample collection, preserved with concentrated HNO 3 and stored at 4° C. Preserved samples were diluted 1:10 with distilled water and analyzed for Ca using flame atomic absorption spectroscopy (X=422.7 nm) (APHA 1989, Method 3111 B) . Due to equipment failure, some acidified samples were analyzed using a Ca ion-specific electrode (Orion Research, Inc., Beverly MA) without dilution.

Water samples were filtered through 0.2 pm glass fiber filters within 3 h of sampling for carbon analysis. Samples were then stored in 30-mL amber glass bottles until analysis. TOC samples taken at the site were also stored in 30-mL amber glass bottles. All samples were stored at 4° C and analyzed within 30 d using a Rosemount Dohrmann DC-

190 TOC analyzer (APHA 1989, Method 5310 B).

45 3.3.4 Metaphyton analyses

3.3.4.1 Field sampling

Algal biomass was sampled in the wetland basins at the height of the growing season (August 28, 1998) and early in the growing season (May 27, 1999). Sampling was done using a plastic 20-L bucket (inner diameter = 26.7 cm) with no bottom. The bucket was placed in an area with 100 percent algal cover and sunk into the sediment. All of the algae within the bucket was harvested by hand, placed into plastic bags, and transported on ice to the laboratory.

3.3.4.2 Laboratory analyses

Upon transport to the laboratory, samples were washed in distilled water to remove any sediment, then placed into aluminum weighing dishes and dried in a drying oven at

105° C. After drying, samples were weighed for estimation of total dry biomass. Samples were ground in a Wiley mill before any further analysis.

Ground algae samples were analyzed for calcite and dolomite using an acid reaction method (Dreimanis 1962). Dried sample was weighed into a reaction vessel, which was attached to a manometer, and 20 mL of 6M HCl with FeCl^ was added to the sample. The temperature, air pressure, and volume of CO, evolved were measured at 30 sec and at 40 min using the manometer to determine the amount of calcite and dolomite in the algae, respectively.

The dried biomass samples were so fine that after weighing, they had to be wetted with distilled water prior to the addition of the 6M HCl to prevent them fi-om floating on the acid and not all reacting at once. Since the time of reaction is the method of determining whether the carbonate is calcite or dolomite, results for the algae samples are presented in calcium carbonate equivalents. The carbonates associated with the algal samples reacted

46 immediately upon acidification, and so the major proportion of carbonates associated with the algal mat was assumed to be calcite and not dolomite, which has a much slower reaction time. Sample values were checked by adding known amounts of ground CaCO] to algal

samples, and these values were within 11% of calculated values. Subsamples were also

placed into weighing jars and dried at 105° C overnight to determine the moisture content

of the samples.

The remaining ground samples were then sent to the Service Testing and Research

(STAR) Lab at the agricultural experiment station of The Ohio State University in Wooster

for major elements analysis (P, K, Ca, Mg, Al, B, Cu, Fe, Mn, Mo, Na, S, Zn) using

inductively coupled plasma (IGF) emission spectroscopy (APHA 1989, Method 3120).

Microscopy and elemental analysis were conducted on algal samples at the Electron

Microscopy and Microanalysis Lab, The Ohio State University, using a JEOL 820

scanning electron microscope. Oven-dried algal samples were affixed to carbon stubs

using double-sided carbon tape. Copper tape was then affixed to the stub to prevent the

sample fi-om accumulating an electrical charge during examination. Samples were then

coated with elemental C and examined in the microscope. Unground algal filaments were

used for photomicrographs and elemental analysis, and ground samples were used for

elemental analysis when whole samples were not available.

X-ray diffraction analysis was performed on some of the ground algal samples to

verify the crystal form of the calcium carbonate found by scanning electron microscopy and

acidification. Powder mounts of samples were prepared by backloading into aluminum

holders. Samples were scanned in the range of 2 - 80 °20 with a Philips XRG-3100

generator and a Philips Electronics PW 1316/90 wide range goniometer equipped with a

curved graphite monochromator and theta compensating slit. Step-scan data were collected

with Databox Communication Software (Materials Data, Inc.) Instrumental settings for the

X-ray diffractometer were as follows:

47 Target = Cu

Radiation - CuK-alpha(unresolved)

Target voltage = 35 kV

Filament current = 20 mA

Detector = Scintillation

Counter voltage = 845.9 V

Step interval (°20) = 0.05

Count time = 4 s

3.3.5 Sediment analyses

3.3.5.1 Field sampling

Sediment cores were taken from the wetlands on May 5, 1999 to determine whether the wetland sediments had accumulated calcite or dolomite over the five years during which they had been flooded. Samples were taken at 12 locations in each basin (Fig. 3.2), giving two core samples each for the deep and shallow areas in the inflow, middle, and outflow subbasins of each wetland at specific locations on a permanent 10 m x 10 m. When possible, samples were taken at points corresponding to previous soil samples taken in

1995 and 1993 (Naim 1996), so that the current samples could be compared with the previous ones. Samples were taken 30.5 cm west of the selected grid locations whenever possible, using a 3.8 cm inner diameter PVC pipe, which was pushed into the sediment approximately 16 cm and then removed. The pipes were sealed with duct tape and transported back to the laboratory, where they were stored frozen until analysis.

To determine whether calcite or dolomite crystals were being imported into the wetlands through suspended sediment from the Olentangy River, water samples were collected from the river inflow pipe of Wetland 1 during the non-growing season

48 (November 1999- January 2000) and during the growing season (August 2000). On each sampling date, 60L of water was collected from the inflow pipe, flocculated with MgCb, the supernatant liquid poured off and the sample decanted into successively smaller containers until the suspended sediment could be dried at 105° C and analyzed for carbonates in the same method as the sediments cores.

3.3.5.2 Laboratory analyses

Core samples were extruded from the PVC pipe and split lengthwise into two halves. One half of each core was used for analysis; the other half was stored frozen until a later date, when it was dried at 105 °C, stored in a plastic bag, and placed in an archive for possible future use. The sediment at the wetlands consisted of two main layers: an upper layer of very soft muck, approximately 8 cm deep, and a lower clay layer. For the purposes of the analysis, the sample was split into these two layers.

The color of each sediment layer was determined using a Munsell Soil Color Chart

(Kollmorgen Instruments Corporation, Baltimore, MD). A 5-mL subsample was taken of each layer, placed into tared crucibles, and the wet weight was determined. Subsamples were dried at 105° C for five days, cooled in a desiccator, and weighed to determine the dry weight. Samples were then ashed in a muffle furnace for 24 h at 550° C, cooled in a desiccator, and weighed to determine the ash weight. From these measurements, the bulk density, percent water, and percent organic matter were estimated.

Dried sediment samples from 1999 (five years post-flooding), 1995 (one year post- flooding) and 1993 (pre-flooding) were ground to pass through a 1 mm sieve and analyzed for percent calcite and dolomite by acidification (Dreimanis 1962). Dried sample was weighed into a reaction vessel, which was attached to a manometer, and 20 mL of 6M HCl with FeClj was added to the sample. Temperature, air pressure, and volume of CO, evolved was measured at 30 sec and 40 min using the manometer to determine the amount

49 of calcite and dolomite in the sediment, respectively. Subsamples were also placed into weighing jars and dried at 105° C overnight to determine the moisture content of the samples.

Ground sediment samples were analyzed at the STAR Lab in Wooster for pH, exchangeable P, cation exchange capacity, exchangeable Ca, Mg, and K., and 13 major elements (P, K, Ca, Mg, Al, B, Cu, Fe, Mn, Mo, Na, S, Zn) using inductively coupled plasma (ICP) emission spectroscopy (APHA 1989, Method 3120).

Ground sediment samples from the inflow and outflow sites of the two basins were examined using scanning electron microscopy and microanalysis in the same manner as the algal samples. Sediment cores from the middle of the two basins were fixed in epoxy and then sliced lengthwise and coated with elemental C to provide 2 continuous core samples for examination along the depth profile. The form of calcium carbonate found in the sediment samples was confirmed using X-ray diffraction of ground sediment samples.

3.3.6 Statistical analyses

Because of the different methods used to collect the data, different statistical methods were used to analyze the data.

The water chemistry data was analyzed using SAS 6.12 statistical program (SAS

Institute). Because the data was taken over a 24-hour period during each sampling period, and because of the difficulty of assuming that water samples taken within each basin are independent, the data were analyzed using a repeated measures model. If parameters increased significantly from dawn to the following dusk, and then decreased from dusk to the following dawn, this was termed a significant diurnal increase. Likewise, if a parameter decreased from dawn to dusk, and then increased from dusk to the following dawn, this was termed a significant diurnal decrease.

50 Because the sediment samples were taken at the same locations over a period of time, but each location could be considered independent of the others, sediment data were compared using paired t-tests (a=0.05). Algae samples were compared using a general linear model, as the number of samples varied between sampling dates.

3.4 Mesocosms

3.4.1 Field sampling

Water samples and measurements were taken in each mesocosm at dawn, dusk, and dawn of the following day on four occasions during the growing season and one during the nongrowing season: July 8-9, 1998; July 28-29, 1998; August 20-21, 1998; September

22-23, 1998; December 3-4, 1998. Temperature, dissolved oxygen, specific conductance, redox potential, and pH were measured using the same instruments as in the basins. Dawn- dusk-dawn dissolved oxygen data were used to estimate gross primary production (GPP) and respiration using the method of Odum (1956).

Water samples were taken, stored, prepared, and analyzed using the same methods as were used for the basin water samples, unless otherwise noted.

Mesocosm algae were harvested on September 8 , 1998 by hand, separated into firee-floating and periphyton algae, placed into plastic bags, and stored on ice for immediate transport back to the laboratory. The wet weight of the entire algal mat was determined and 300-g (approximately 20% of total wet weight) subsamples were taken for analysis; the algal mats were then returned to their respective mesocosms.

Sediment cores were taken firom the center of each mesocosm the spring following the experiment (May 1999), when the sediments had been submersed for I yr. This allowed the sediment to undergo all seasons as submersed soil. Cores were taken using a

3.8 cm inner diameter PVC pipe, which was pushed into the sediment approximately 16 cm and then removed. The pipes were sealed with duct tape and transported back to the

51 laboratory, where they were stored frozen until they were extruded five days after sampling. Core samples were thawed slightly, extruded from the PVC pipe, and split lengthwise into two halves. One half was used for analysis; the other was placed in a plastic bag and stored frozen for future use.

3.4.2 Laboratory analyses

Water samples were analyzed for total alkalinity, dissolved Ca, soluble reactive phosphorus (SRP), TDC, DIC, DOC, TC, TIC, TOC, and total phosphorus using the same methods as for the basin samples. Calcium carbonate saturation index (SI) was calculated from temperature, pH, total alkalinity, dissolved calcium, and conductivity.

Samples were analyzed for total alkalinity by Gran titration except for December 3,

1998 samples, which were stored unfiltered in amber glass bottles and later analyzed on a

Lachat Quikchem 8000 using an automated methyl orange color reaction (Quikchem method 10-303-31-1-A).

Preserved filtered samples were diluted 1:10 with distilled water and analyzed for

Ca using the same methods as for the basin samples. Due to equipment failure of the flame atomic absorption spectrophotometer, samples taken on December 3, 1998 were analyzed

for Ca without dilution using a calcium ion-specific electrode (Orion model 97-20) attached

to a Solomat 520c.

Metaphyton biomass subsamples were weighed, washed in distilled water to

remove any sediment present, reweighed, and dried at 105° C. After drying and

cooling in a desiccator, subsamples were weighed to obtain a dry weight to estimate dry

weight/wet weight ratios. These subsamples were then ground in a Wiley mill before any

further analysis. Ground algae samples were analyzed for carbonate minerals using the

same method as for the sediment samples (Dreimanis 1962), and are presented as CCE.

52 Sample values were checked by known addition of ground CaCO] to algal samples, and these values were within 11% of calculated values.

Ground metaphyton samples were then sent to the STAR Lab for determination of major elements (P, K, Ca, Mg, Al, B, Cu, Fe, Mn, Mo, Na, S, Zn) by ICP analysis.

Moist soil color, bulk, density, percent organic matter, and calcium carbonates were determined for sediment samples using the same methods as in the basins. Ground sediment samples were analyzed at the STAR Lab in Wooster for pH, exchangeable P , cation exchange capacity, exchangeable Ca, Mg, and K, and 13 major elements (P, K, Ca,

Mg, Al, B, Cu, Fe, Mn, Mo, Na, S, Zn) using inductively coupled plasma (ICP) emission spectroscopy.

Ground sediment and algae samples were examined for the presence of calcite crystals and to determine the percentage of P in the calcite crystals using the same methods as for the basin algal and sediment samples.

3.4.3 Statistical analyses

Water quality data within each sampling date were compared using paired t-tests

(a=0.05) to determine whether there was a difference between dawn and the following dusk, and between dusk and the following dawn. If parameters increased significantly from dawn to the following dusk, and then decreased from dusk to the following dawn, this was termed a significant diumal increase. Likewise, if a parameter decreased from dawn to dusk, and then increased from dusk to the following dawn, this was termed a significant diumal decrease. Average dawn, average dusk, and average range (dusk- average dawn) were compared using a general linear model (date, treatment, date*treatment), and when the saturated model was appropriate, data were compared

53 between treatments and dates using the Tukey-BCramer multiple comparison procedure

(family error rate=0.05). Sediment and algal data were compared using 2-sample t-tests

(a=0.05).

54 CHAPTER4

RESULTS

4.1 Full-scale wetlands

4.1.1 Aquatic metabolism

GPP and R showed strong seasonal patterns, with maxima in the summer and minima in the winter (Table 4.1). Net primary production was not significantly different fi-om zero, except on two occasions (the middle subbasin of Wetland 1 in fall 1996 and winter 1996-7). The planted and unplanted wetlands were very similar in terms of aquatic metabolism. GPP and R were highest in the outflow subbasins; however, the middle subbasins occupy a much larger area and so have a greater impact in the system. GPP in the middle subbasins ranged from 0.36 g O, m ’ d'‘ in winter to 5.35 g O, m ' d ‘ in summer. Summer GPP values in the middle subbasins ranged fi’om 4.30 to 5.35 g O, m ’ d ' (Fig. 4.1a). Wetland 1 had significantly higher GPP in 1997, but the two wetlands were not significantly different in 1996 or 1998. A comparison of the three years of summer data as a whole also showed no significant difference between wetlands (Fig.

4.1b).

ANOVA tables for GPP, R, and NPP are shown in Table 4.2. For GPP and R, the following factors showed significant (a=0.05) main effects: year, season, and basin.

Interaction effects were significant for year*subbasin, season*basin, season*subbasin, and basin*subbasin. Net primary production was explained by a different general linear model.

The only significant main effects were for basin and subbasin, while five interaction terms

55 W1 Middle W1 Outflow GPP, g Oj d'* R, g O, m ‘ d ' GPP, g O, m * d ‘ R, g On m ‘ d" Summer 1996 4.30 ± 0.28(48) 4.28 ± 0.26(48) 5.70 ± 0.34(22) 5.41 ± 0.44(22) Fall 1996 1.92 ±0.29(52) 3.16 ±0.38(52) 2.94 ± 0.30(82) 2.88 ± 0.28(82) Winter 1996-7 0.36 ±0.10(13) 0.63 ±0.12(13) 0.99 ± 0.20(42) 0.95 ± 0.20(42)

Spring 1997 0.70 ±0.23(12) 0.60 ±0.23(12) 1.60 ±0.11(75) 1.64 ±0.12(75) Summer 1997 4.35 ± 0.43(77) 4.39 ± 0.42(77) 4.80 ± 0.53(50) 4.84 ± 0.52(50) Fall 1997 2.13 ±0.28(74) 2.12 ±0.27(74) 1.40 ±0.18(70) 1.49 ±0.19(70) Winter 1997-8 0.93 ± 0.08(80) 0.96 ± 0.06(80) 0.72 ± 0.08(75) 0.82 ± 0.07(75)

Spring 1998 3.57 ± 0.42(53) 3.57 ± 0.40(53) 4.82 ± 0.85(63) 4.75 ± 0.78(63) Summer 1998 4.93 ± 0.33(84) 4.90 ± 0.33(84) 6.11 ±0.50(75) 6.23 ±0.51(75) Fall 1998 1.47 ±0.14(67) 1.50 ±0.14(67) 2.90 ± 0.28(39) 2.95 ± 0.29(39) Average 2.29 2.42 3.00 3.00

W2 Middle W2 Outflow GPP, g 0, m ' d-‘ R, g 0 , m - d ' GPP, g 0 , m - d ' R, g 0 , m‘- d ' Summer 1996 5.35 ± 0.36(40) 5.29 ± 0.35(40) 5.95 ±0.42(22) 5.94 ± 0.42(22) Fall 1996 2.97 ± 0.27(54) 2.95 ± 0.25(54) 2.13 ±0.17(64) 2.07 ±0.17(64) Winter 1996-7 0.57 ±0.12(11) 0.52 ±0.13(11) 1.57 ±0.29(30) 1.68 ± 0.25(30)

Spring 1997 3.48 ± 0.39(63) 3.45 ± 0.39(63) 1.72 ±0.15(75) 1.67 ±0.14(75) Summer 1997 4.56 ± 0.50(48) 4.62 ± 0.48(48) 4.87 ± 0.64(50) 4.89 ± 0.63(50) Fall 1997 2.12 ±0.21(65) 2.13 ±0.20(65) 2.02 ±0.14(71) 1.96 ±0.16(71) Winter 1997-8 1.43 ±0.14(79) 1.46 ±0.13(79) 2.04 ±0.16(71) 2.05 ±0.16(71)

Spring 1998 5.15 ±0.44(86) 5.20 ± 0.43(86) 5.07 ±0.31(85) 5.15 ±0.31(85) Summer 1998 3.43 ± 0.69(55) 3.57 ± 0.72(55) 4.37 ± 0.33(82) 4.41 ± 0.32(82) Fall 1998 1.97 ±0.30(65) 2.00 ± 0.29(65) 2.08 ±0.17(58) 2.10 ±0.16(58) Average 3.03 3.04 3.08 3.10

Table 4.1 - Gross primary production (GPP) and respiration (R) in research wetland basins at the Olentangy Wver Wetland Research Park, July 1996 through December 1998. GPP and R were calculated using data taken every half-hour from four YSI 6000 data sondes (YSI, Inc., Yellow Springs, Ohio). W1 = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing).

56 n = 3 Id GPP !

W2

n = 48 n = 38 n = 48 n = 38 5 - ■a n = 55 n = 55 E o ' O) 3 - Q. CL 2 - (3

1 -

1996 1907 1998

Fig. 4.1 - Summer gross primary production (GPP) in the middle subbasins of the experimental wetlands, 1996-98, expressed as a) annual averages for 3 years and b) inàvidually by year. W1 =Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). W1 had significantly higher GPP in summer 1997 (paired t-test). Error bars indicate standard error, n = number of paired data points. Asterisks (*) indicate significant differences between W1 and W2.

57 GPP, g O, m-' d ' Source df Seq SS Adj SS Adj MS F P year 2 265.14 362.47 181.23 22.87 0.000 season 3 4282.17 4058.55 1352.85 170.73 0.000 basin 1 28.58 43.70 43.70 5.51 0.019 subbasin 1 18.57 8.24 8.24 1.04 0.308 year*subbasin 2 123.31 102.95 51.48 6.50 0.002 season*basin 3 163.76 175.41 58.47 7.38 0.000 season*subbasin 3 97.23 80.75 26.92 3.40 0.017 basin* sub basin 1 43.60 43.60 43.60 5.50 0.019 Error 2312 18320.03 18320.03 7.92 Total 2328 23342.38

R, g 0 , m"' d ' Source df Seq SS A JS S Adj MS F P year 2 307.24 402.98 201.49 26.18 0.000 season 3 4156.16 3900.22 1300.07 168.89 0.000 basin 1 16.38 30.54 30.54 3.97 0.047 subbasin 1 8.21 0.14 0.14 0.02 0.891 year*subbasin 2 123.31 109.79 54.90 7.13 0.001 season*basin 3 176.98 184.56 61.52 7.99 0.000 season* subbasin 3 113.75 98.44 32.81 4.26 0.005 basin* subbasin 1 32.68 32.68 32.68 4.25 0.039 Error 2312 17797.00 17797.00 7.70 Total 2328 22731.71

NPP, g O, m ' d ' Source df Seq SS Adj SS Adj MS year 2 2.597 1.347 0.674 1.04 0.355 season 3 1.337 2.675 0.892 1.37 0.250 basin 1 1.686 3.343 3.343 5.14 0.023 subbasin 1 2.086 7.428 7.428 11.43 0.001 year*basin 2 7.336 4.261 2.131 3.28 0.038 year* subbasin 2 13.843 12.790 6.395 9.84 0.000 season*basin 3 3.624 5.533 1.844 2.84 0.037 basin*subbasin 1 0.763 5.604 5.604 8.62 0.003 year*basin*subb 2 14.788 14.788 7.394 11.38 0.000 asin Error 2311 1502.092 1502.092 0.650 Total 2328 1550.151

Table 4.2 - Results of general linear models for GPP, R, and NPP in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998.

58 were significant (year*basin, year* subbasin, season*basin, basin*subbasin,

year*basin*subbasin). Analysis of the spatially detailed data showed that GPP and R were

significantly higher in the deepwater areas of both wetlands than in the shallow areas.

4.1.2 Temperature

Temperature showed a strong seasonal pattern as well, with maxima in the

summers and minima in the v.inters (Table 4.3). .\MOVA tables for average temperature, maximum and minimum temperatures, and daily range (maximum temperature - minimum temperature) are shown in Table 4.4. Average temperature showed significant main effects

for year, season, and basin, and a significant interaction term, season*basin.

In the middle subbasins, temperature was not significantly different between basins in any season except summer (Fig 4.2a, b). In the summers of 1996 and 1997, average water temperature (Fig 4.2a) in the middle subbasin of Wetland 1 was significantly higher than in Wetland 2 (1.08 °C in 1996 and 0.56 °C in 1997). In 1998, average water temperature was not significantly different in the middle subbasins of the two wetlands.

When data firom all three years were analyzed together, summer and winter temperatures in

Wetland 1 were higher overall (by 0.12 and 0.46 ° C, respectively), while the basins were not significantly different in average water temperature for spring and fall.

4.1.3 pH

Average pH values were high in the summer of 1996, and steadily decreased to more neutral values in 1997 and 1998 (Table 4.3). Average pH values in the middle subbasins ranged firom 7.01 in the fall to 8.26 in the summer. Comparison of summer pH values in the middle subbasins (Fig 4.2c) showed that Wetland 1 had significantly higher average pH values in 1996 and 1997, while Wetland 2 had significantly higher average pH

59 Temperature, °C W1 Middle W1 Outflow W2 Middle W2 Outflow Summer 1996 26.06 + 0.23(51) 26.60 + 0.42(22) 24.95 + 0.22(47) 25.92 + 0.43(22) Fall 1996 13.22 + 0.69(86) 13.09 ±0.73(83) 13.26 + 0.68(85) 13.18 + 0.69(87) Winter 1996-7 4.69 + 0.23(31) 4.24 + 0.15(45) 4.64 + 0.26(30) 4.19 + 0.17(50)

Spring 1997 9.61 + 1.17(11) 12.52 + 0.51(84) 10.70 + 0.45(66) 12.09 + 0.49(81) Summer 1997 24.90 + 0.32(78) 25.51 + 0.33(50) 24.82 + 0.31(50) 25.04 + 0.32(50) Fall 1997 12.64 + 0.75(73) 12.34 + 0.78(73) 12.57 + 0.74(74) 12.35 + 0.75(73) Winter 1997-8 4.71 +0.22(81) 4.54 + 0.25(76) 4.65 + 0.21(80) 4.69 r 0.19(78)

Spring 1998 14.31 + 1.09(53) 15.67 + 0.81(65) 13.00 + 0.66(74) 11.52 + 0.59(64) Summer 1998 24.38 + 0.24(85) 24.83 + 0.26(80) 24.74 + 0.18(67) 25.11 r 0.26(81) Fall 1998 15.35 + 0.79(65) 15.64 + 1.01(54) 14.94 + 0.82(61) 14.92 r 0.91(58)

pH W1 Middle W1 Outflow W2 Middle W2 Outflow Summer 1996 8.26 + 0.04 (51) 8.30 ± 0 .0 6 (22) 8.05 ± 0.05 (47) 8.47 ± 0.07 (22) Fall 1996 8.15 + 0.03 (86) 8.23 ± 0 .0 3 (83) 7.80 4 - 0.04 (84) 8.20 - 0.03 (85) Winter 1996-7 7.79 + 0.03 (31) 7.85 ± 0 .0 3 (45) 7.57 0.03 (30) 7.82 0.02 (50)

Spring 1997 8.17 ±0.09 (11) 8.13 ± 0 .0 4 (84) 8.07 0.02 (64) 8.14 - r 0.05 (81) Summer 1997 7.83 ±0.02 (25) 7.98 ± 0 .0 6 (50) 7.30 ±0.03 (50) 7.48 0.03 (50) Fall 1997 7.67 ±0.02 (72) 7.56 ± 0 .0 3 (66) 7.39 -f- 0.04 (74) 7.54 0.02 (73) Winter 1997-8 7.51 ±0.02 (80) 7.17 ± 0.03 (76) 7.01 0.03 (80) 7.25 - 0.03 (78)

Spring 1998 7.53 ±0.02 (53) 7.51 ± 0 .0 4 (70) 7.48 ± 0.04 (74) 7,57 0.04 (64) Summer 1998 7.23 ±0.03 (84) 7.56 ± 0 .0 4 (78) 7.56 ± 0.03 (67) 7.00 + 0.03 (81) Fall 1998 7.03 ±0.03 (65) 7.58 ± 0 .0 5 (52) 7.04 ± 0.02 (61) 7.52 O.IO (58)

Conductivity at 25 °C Wl Middle W1 Outflow W2 Middle W2 Outflow Summer 1996 471 ± 11.9 (51) 440 ± 14.5 (22) 471 ± 15.0 (47) 450 ± 18.9 (22) Fall 1996 612 ±8.0 (86) 590 ± 10.8 (83) 641 ± 8 .5 (84) 626 ±10.4 (85) Winter 1996-7 472 ± 13.4 (31) 678 ± 33.7 (45) 739 ± 27.3 (30) 648 ±31.6 (50)

Spring 1997 692 ±33.5(11) 604 ± 12.3 (80) 626 ± 15.7 (65) 589 ± 11.4 (72) Summer 1997 459 ± 16.8 (26) 347 ± 9.7 (28) ------656 ± 12.0 (50) Fall 1997 739 ± 9.5 (48) 958 ± 37.4 (66) ■ - 816 r 9.5 (72) Winter 1997-8 767 ± 12.1 (80) 564 ± 22.3 (76) 785 ± 13.2 (80) 778 ± 11.3 (78)

Spring 1998 849 ± 32.5 (53) 1196 ± 74.4 (70) 642 ± 22.6 (74) 578 ± 16.2 (63) Summer 1998 797 ±31.5 (85) 703 ± 23.8 (78) 1002 ± 18.4 (66) 732 ±31.3 (80) Fall 1998 1109 ±44.7 (63) 785 ±41.6 (50) 697 ±15.4 (60) 738 ± 18.5 (55)

Table 4.3 - Average values for temperature, pH, and conductivity in the research wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998. 60 Average temperature, C Source df Seq SS Adj SS Adj MS F P Year 2 2719 608 304 13.44 0.000 Season 3 122941 122236 40745 1802.51 0.000 Basin 1 119 159 159 7.03 0.008 Season*basin 3 293 293 98 4.32 0.005 Error 2514 56828 56828 23 Total 2523 182900

Maximum temperature, C Source df Seq SS Adj SS Adj MS F P Year 2 865 926 463 15.09 0.000 Season 3 159948 159948 53316 1738.73 0.000 Error 2524 77395 77395 31 Total 2529 238208

Minimum temperature, C Source df Seq SS AdjSS Adj MS F p Year 2 5207 1270 635 31.75 0.000 Season 3 97659 96977 32326 1616.15 0.000 Basin 1 86 128 128 6.39 0.012 season*basin 3 289 289 96 4.81 0.002 Error 2520 50404 50404 20 Total 2529 153645

Daily temperature range (maximum-minimum), C Source df Seq SS Adj SS Adj MS F P year 2 2080.87 2385.03 1192.51 173.36 0.000 season 3 8759.00 8771.73 2923.91 425.05 0.000 basin 1 2.51 0.09 0.09 0.01 0.911 subbasin 1 13.86 3.57 3.57 0.52 0.471 year*basin 2 110.88 62.54 31.27 4.55 0.011 year*subbasin 2 134.01 140.16 70.08 10.19 0.000 season*basin 3 72.01 72.01 24.00 3.49 0.015 Error 2515 17300.66 17300.66 6.88 Total 2529 28473.79

Table 4.4 - General linear model results for water temperature in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998.

61 t 27 ♦ o 47 □ W l T 50 i § 2 6 □ W2 47 T 50 (D 2 81 81 h ■ 1 ^ 1 ^ F g.25 T T 3 E 0) mm ~ 2 4 1996 1997 1998

29 □ W l 29 OW 2

30 30 80 80 1 SI ■ i 1996-7 1997-8 1998-9

^ 8.5 47 □ W l 47 E1W2 Q) 8 E 67 I 7 . 5 67 *

1996 1997 1998

1200 66 □ W l 66 BW2 800 47 47 26 i I ~ 400 1 8 1996 1997 1998

Fig, 4.2 - Winter temperature, summer temperature, pH and conductivity in the middle subbasins of the experimental wetland basins, 1996-1998. No data are available for conductivity in the middle subbasin of W2 summer 1997. Error bars show std. error, numbers above bars are number of data points. Wl=Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). Asterisks (*) indicate significant differences between Wl and W2 (paired t-test). 62 values in 1998. When data from all three years were analyzed together. Wetland I had significantly higher average pH values in all seasons. Year, season, basin, and subbasin were all significant main effects for average, maximum, minimum, and daily range of pH

(Table 4.5). Some interaction effects were also significant.

4.1.4 Conductivity

Seasonal averages tor conductivity (corrected tor temperature effects), are shown in

Table 4.3. Conductivity values ranged from 347 |iS/cm to 1002 |iS/cm. Conductivity tended to decrease in the summer, with one exception: the middle subbasin in Wetland 2 showed high average conductivity in summer 1998. Comparing between the middle subbasins in the summer. Wetland 1 showed significantly lower conductivities than did

Wetland 2 in 1998, but the two wetlands were not significantly different in 1996 (Fig.

4.2d). When seasonal data from 1996-98 were combined, summer was the only season in which the two middle basins were significantly different. In that case, Wetland 1 had lower conductivity than did Wetland 2. Conductivity had the most complex general linear model of all water quality parameters (Table 4.6). Average, maximum, minimum, and range of conductivity showed significant main and interaction effects for all parameters.

4.1.5 Total dissolved solids budget

The TDS budget shows that the ORWRP basins vary in their removal efficiency for dissolved solids from year to year (Table 4.7). In 1996 the two wetlands retained 7.4 and

13.5 percent of the total dissolved solids entering them. In 1997, Wetland 1 was approximately in steady state, with a very small calculated export of dissolved solids (0.4 percent), while Wetland 2 retained 4.8 percent of the TDS entering it. Both wetlands retained dissolved solids (7.1 and 5.5 percent, respectively) in 1998.

63 General linear model results for pH

Average pH Source df Seq SS Adj SS Adj MS F P year 2 235.865 245.056 122.528 1123.84 0.000 season 3 53.047 47.862 15.954 146.33 0.000 basin 1 12.144 9.061 9.061 83.1 0.000 subbasin 1 7.843 5.350 5.350 49.07 0.000 year*basin 2 0.721 1.107 0.554 5.08 0.006 season*basin 3 5.632 5.172 1.724 15.81 0.000 season* subbasin 3 5.240 5.240 1.747 16.02 0.000 Error 2441 266.134 266.134 0.109 Total 2456 586.626

Maximum pH Source df Seq SS Adj SS Adj MS F P year 2 92.283 66.152 33.076 111.65 0.000 season 3 274.216 269.777 89.926 303.55 0.000 basin 1 7.23 4.024 4.024 13.58 0.000 subbasin 1 23.935 21.699 21.699 73.25 0.000 season*basin 3 7.701 7.261 2.42 8.17 0.000 season*subbasin 3 3.128 3.128 1.043 3.52 0.014 Error 2446 724.615 724.615 0.296 Total 2459 1133.108

Continued on next page

Table 4.5 - General linear model results for pH in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 throu^ December 1998.

64 Table 4.5, continued

Minimum pH Source df Seq SS AdjSS Adj MS F P Year 2 281.652 307.837 153.918 1567.71 0.000 season 3 58.137 54.522 18.174 186.29 0.000 Basin 1 10.733 8.509 8.509 87.22 0.000 Subbasin 1 3.848 2.12 2.12 21.73 Ü.UÜÜ year*basin 2 0.299 0.704 0.352 3.61 0.027 season*basin 3 3.366 3.078 1.026 10.52 0.000 season*subbasin 3 6.278 6.278 2.093 21.45 0.000 Error 2442 238.432 238.432 0.098 Total 2459 602.747

Daily range of pH Source df Seq SS Adj SS Adj MS F P year 2 87.74 118.658 59.329 245.36 0.000 season 3 365.972 367.647 122.549 506.81 0.000 basin 1 0.345 1.411 1.411 5.84 0.016 subbasin 1 8.588 9.983 9.983 41.29 0.000 season*basin 3 6.472 6.354 2.118 8.76 0.000 season*subbasin 3 8.111 8.111 2.704 11.18 0.000 Error 2446 591.458 591.458 0.242 Total 2459 1068.687

65 Average conductivity at 25 “C Source df Seq SS Adj SS Adj MS F P year 2 16482174 29237061 1.5E+07 266.66 0.000 season 3 18405535 17463171 5821057 106.18 0.000 basin I 78661 641783 641783 11.71 0.001 subbasin 1 3400721 777913 777913 14.19 0.000 year*basin 2 6467059 11250305 5625152 102.61 0.000 year* subbasin 2 754553 1756670 878335 16.02 0.000 season*basin 3 15736088 12014117 4004706 73.05 0.000 season* subbasin 3 3787248 4326134 1442045 26.3 0.000 basin*subbasin 1 1905483 1043409 1043409 19.03 0.000 season*basin*subbasin 3 578941 791580 263860 4.81 0.002 year*basin*subbasin 2 4631893 4631893 2315947 42.25 0.000 Error 2343 128447271 128447271 54822 Total 2366 200675625

Maximum conductivity at 25 °C Source df Seq SS Adj SS Adj MS F p year 2 22802909 38035909 1.9E+07 273.56 0.000 season 3 19366774 18601759 6200586 89.19 0.000 basin I 1019 465651 465651 6.70 0.010 subbasin I 3680363 809489 809489 11.64 0.001 year*basin 2 8696560 14745925 7372962 106.05 0.000 year*subbasin 2 993830 2267451 1133726 16.31 0.000 season*basin 3 21289688 16071559 5357186 77.06 0.000 season*subbasin 3 5380617 6306900 2102300 30.24 0.000 basin*subbasin 1 2789307 1523769 1523769 21.92 0.000 season*basin*subbasin 3 992609 1127723 375908 5.41 0.001 year*basin*subbasin 2 4148742 4148742 2074371 29.84 0.000 Error 2343 162888142 162888142 69521 Total 2366 253030560 Continued on next page

Table 4.6 - General linear model results for conductivity at 25 °C in the experimental wetland basins at the Olentangy River Wetland Research Park, July 1996 through December 1998.

6 6 Table 4.6, continued

Minimum conductivity at 25 “C Source df Seq SS Adj SS Adj MS F P year 2 11052130 20462888 lE+07 218.30 0.000 season 3 18572361 17524424 5841475 124.63 0.000 basin 1 110412 634086 634086 13.53 0.000 subbasin 1 2476016 536529 536529 11.45 0.001 year*basin 2 4889894 8383240 4191620 89.43 0.000 year* subbasin 2 583115 1276402 638201 13.62 0.000 season*basin 3 11232617 8482106 2827369 60.33 0.000 season*subbasin 3 2647088 2953703 984568 21.01 0.000 basin*subbasin 1 1169677 649113 649113 13.85 0.000 season*basin*subbasin 3 401464 580895 193632 4.13 0.006 year*basin*subbasin 2 4403258 4403258 2201629 46.97 0.000 Error 2337 109532154 109532154 46869 Total 2360 167070186

Daily range of conductivity at 25 °C Source df Seq SS Adj SS Adj MS F p year 2 2444982 2897431 1448716 136.15 0.000 season 3 4606644 4412984 1470995 138.24 0.000 basin 1 111707 15954 15954 1.50 0.221 subbasin 1 152762 32407 32407 3.05 0.081 year*basin 2 570273 905183 452591 42.53 0.000 year* subbasin 2 98992 197806 98903 9.29 0.000 season*basin 3 1628044 1249100 416367 39.13 0.000 season*subbasin 3 581730 724482 241494 22.70 0.000 basin*subbasin 1 294840 172850 172850 16.24 0.000 season*basin* subbasin 3 356116 294804 98268 9.24 0.000 year*basin*subbasin 2 120694 120694 60347 5.67 0.003 Error 2339 24888688 24888688 10641 2362 35855474

67 Wetland 1

Surface inflow Surface outflow Groundwater outflow Retention Retention Year Mg/yr Mg/yr Mg/yr Mg/yr % 1996 90.6 62.8 21.1 6.7 7.4 1997 173.9 130.5 44.1 -0.7 -0.4 1998 159.4 141.1 6.9 11.3 7.1

Wetland 2 Surface inflow Surface outflow Groundwater outflow Retention Retention Year Mg/yr Mg/yr Mg/yr Mg/yr % 1996 94.6 63.8 18.1 12.7 13.5 1997 173.9 120.1 45.4 8.4 4.8 1998 158.9 124.5 25.6 8.8 5.5

Table 4.7 - Total dissolved solids budget in megagrams (Mg) per year for the 1-ha experimental wetland basins at the Olentangy River Wetland Research Park, 1996-98.

68 The variation in dissolved solids entering the wetlands is a function of two factors: natural variation in seasonal river flow (and thus pumping rate, which is regulated to mimic natural inputs from the river) from year to year, and mechanical failures of the pumps bring water from the Olentangy River into the wetlands. In 1996, due to mechanical problems, the pumps were not pumping for 146 days over the course of the year. Most of the non­ inflow time occurred in January, February, and May. In 1997 and 1998 the pumps were off for only 28 days each year. The highest percent retention of TDS occurred during

1996, the low-flow year.

4.1.6 Spatially detailed water quality data

4.1.6.1 Diurnal changes

Temperature, dissolved oxygen, and pH showed strong diumal changes in the wetland basins, increasing during the day and decreasing at night on all sampling dates

(Table 4.8, Fig 4.3). This pattern will be referred to as a diumal increase. A diumal decrease is the opposite pattern, decreasing during the day and increasing at night.

Conductivity showed diumal decreases for the July, October and March sampling dates, indicating that ions were being removed from solution during the day and added at night

(Table 4.8, Fig. 4.3c). Redox, SRP, and total P showed no consistent diumal trends.

Calcium showed a significant diumal decrease on the July 15-16 sampling date, and showed diumal changes on all sampling dates (Table 4.8). This is consistent with diumal removal of Ca from the water column during the day, possibly through precipitation, and replenishment at night through dissolution. TDC, DlC, TC, and TIC showed diumal decreases on four of the five sampling dates (Table 4.8), consistent with inorganic carbon uptake during the day due to photosynthesis and release at night due to respiration.

Dissolved organic carbon decreased during the day on three sampling dates (Table 4.8).

69 Parameter Jul 15-16 Aug 14-15 Oct 21-22 Mar 30-31 Jun 1-2 Dissolved oxygen +- 4"- 4*- 4-- 4*- pH +- 4*- 4"- 4“- 4“- Conductivity -4" 00 -4- -4- 0- Temperature -H- Redox 00 -0 -j—{. +0 00 Saturation indexi +- 4"- 4-- 4"- Ca -4* -0 0+ -0 4-4- SRP 00 +0 +0 00 +0 Total P 00 0- +0 00 00 TDC -4- -4- -4" -4* 0+ Die -4" -4" -4* 0+ DOC -0 -0 00 00 -0 TC -4" 0+ -4* -4- TIC -4* -4* 0+ -4- -4- TOC +0 -0 -4" 00 00 Total alkalinity -4" -4- 0+ 0+ -4 “

Table 4.8 - Summary of diumal trends in water quality parameters in the experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. The first symbol represents change firom dawn to dusk, and the second represents the change firom dusk to the following dawn. A plus (+) symbol indicates a significant (a = 0.05) increase, while a minus (-) symbol indicates a significant (a = 0.05) decrease. A zero (0) indicates that the change is not significant (a = 0.05).

70 18 River inflow 16 inflow c 14 o Middle 12 Outflow I, 10 1 e o s

Jul 16 Aug 15 Oct 21 Mar 30 Jun 1

10.00 • River inflow 9.50 ■ Inflow ■ Middle 9.00 ■ Outflow

^ 8.50

8.00

7.50

7.00

Jul 16 Aug 15 Oct 21 Mar 30 Jun 1

1200 • River inflow 1000 ■ Inflow •Middle ■Outflow 800

; 600

400 Jul 16 Aug 15 Oct 21 Mar 30 Jun 1 Continued on next page

Fig. 4.3 - Diumal variations in water quality in the experimental wetland basins at the Olentangy River Wetland Research Park, 1998-9. Error bars show standard errors.

71 Fig 4.3, continued

30

25

1 20 • River inflow 2 §. 15 ■inflow E Q) ■ Middle 10 ■Outflow

Jul 16 Aug 15 Oct 21 Mar 30 Jun 1

e 90 ■ River inflow ■ Inflow f 70 ■ Middle é 60 ■Outflow I 50 I 40 ° 30 20 Jul 16 Aug 15 Oct 21 Mar 30 Jun 1

5.8 5.6 S 5.4 1 5.2 1 ^ 2 4.8 « 4.6 River inflow Inflow ,®u 4.4 Middle « 4.2 Outflow

c CO c c c w cc c cc (0 c ■o *o*o Jul 16 Aug 15 Oct 21 Mar 30 Jun 1

72 Total alkalinity showed diumal changes on every sampling date, and showed a diumal decrease in July, August and June (Table 4.8). Saturation index showed diumal increases on every sampling date (Table 4.8).

4.1.6.2 Wetland comparisons

A major question in the study was the difference between the two wetland basins.

While Wetland 1 was planted and Wetland 2 was left to colonize naturally, in 1996-98, the two wetlands had converged in stmcture (biomass, percent macrophyte cover) and ftmction

(nutrient removal) (Mitsch et al. 1998). In the analysis of water quality data, the effect of basin was significant at least once for every parameter measured. It was significant on all five sampling dates for TDC (Fig. 4.4), and for only one of five dates for temperature, DO, conductivity, and total alkalinity. Wetland 1 had lower SRP than Wetland 2 on the July 15 and August 15 sampling dates, and lower total P on August 15, October 21, and March 30.

The differences in dissolved and total carbon species was statistically significant, but were within the stated error of the analysis method (1 ppm), so they were disregarded.

4.1.6.3 Inflow vs. outflow

As water flowed fi-om the inflow to the outflow of the wetland basins, many of its characteristics were significantly altered (Table 4.9). Conductivity, dissolved calcium, total carbon, and total inorganic carbon generally decreased from inflow to outflow.

Temperature increased from inflow to outflow in the day during the summer, but decreased from inflow to outflow at dawn. SRP decreased significantly on every sampling date, while total P decreased on four of the five sampling dates. The decreases in conductivity show removal of ions from the water column. The decrease in Ca and both forms of P shows that these ions are removed from solution though uptake or sorption.

73 60

B Middle 50 □Outflow

40 11 05 30 E

20

8 8 8 8 10

0 C TOC DOC TOC

Fig. 4.4 - Dissolved and total carbon species in the middle and outflow subbasins of the experimental wetland basins, summer 1998. TDC = total dissolved carbon, DIG = dissolved inorganic carbon, DOC = dissolved organic carbon, TC = total carbon, TIC = total inorganic carbon, and TOC = total organic carbon. Error bars show standard error; numbers show number of data points.

74 Date Site Temp DO Cond pH Redox Ca SRP TP TDC D ie DOC TC TIC TOC Aik July 14, 1994 Inflow ab a a a a a a a a a a a a a a Middle a a a a a ab b b a a a ab b a a Outflow b a b a a b b b a a a b b a a

August 13, 1994 Inflow a ab a a a ab a a a a a ab ab a a Middle b a ab a a a b b a a a a a a a Outflow ab b b a a b c c a a a b b a a

October 20, 1994 Inflow a a a a a a a a a a a a a a a Middle b ab b b b a b b a a a a a a a Outflow b b c b b a c c b b a b b a b

LA March 29, 1995 Inflow a a ab a a a a ab a a a a a a ab Middle b b a a a b a a a b b a b ab a Outflow ab a b a a c b b b c b b c b b

May 31, 1995 Inflow a a a a a a a a a ab a a ab a a Middle a b b b a ab b b a a b a a ab a Outflow a a c ab a b b b a b b a b b b

Table 4.9 - Statistical differences between inflow, middle, and outflow subbasins of the experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. Different letters signify a significant difference (a =0.05) between sites within a sampling date. Comparisons between sampling dates are not shown. 4.1.6.4 Shallow vs. deep water

The water depth of the samples was a significant factor for all samples on at least one sampling date. Water depth influences solution chemistry in two ways: the shallow sites had a water column in closer proximity to the sediments, and the shallow sites were shaded by emergent vegetation, while the deepwater sites were not. Water depth was most significant for temperature, dissolved oxygen, conductivity, TDC, DOC and saturation index. In general, deepwater areas had higher temperature, DO, pH, and saturation index values than shallow areas, and lower dissolved carbon. These differences can be explained by different conditions in the deepwater and shallow areas. Shallow areas are shaded by emergent macrophytes, decreasing solar heating. Deepwater areas have much more algal cover and production, which explains the higher DO, pH, and SI values. Lower dissolved carbon levels in the deepwater areas could be explained by algal uptake of inorganic C for photosynthesis. Higher DOC levels in the shallow waters could be due to decomposition of macrophyte detritus which is not present in the deepwater areas.

4.1.7 Metaphyton

Metaphyton biomass was highest in the middle subbasins for both sampling dates

(Table 4.10). Estimates of total biomass showed that the middle subbasins had higher total algal biomass than inflow and outflow sites. This is due to the larger area covered by metaphyton in the middle subbasins, as the middle subbasins usually did not have the highest biomass values per unit area. Wetland 1 had more total algal biomass than did

Wetland 2; this corresponds with field observations of the two wetlands. Nutrient levels in the middle subbasins are higher than in the outflow subbasins; however, nutrient levels are not significantly correlated with algal biomass (Fig. 4.5), indicating that another factor, perhaps light, may be limiting the growth of algae.

76 Dry Area covered Major algal biomass by algal mat Ibtal biomass Date Wetland Location algal spp. gm - m* kg Aug 28, 1998 1 Inflow NP 0 0 0 Aug 28, 1998 1 Middle C, R, H, S 62 ± 7 (5) 1130 69.6 Aug 28, 1998 1 Outflow C,R 70 ± 10(6) 580 40.6 Wl Total 1710 110.2

Aug 28, 1998 2 Inflow H 13±2(5) 120 1.6 Aug 28, 1998 2 Middle C, R,H 58 +11 (5) 890 51.9 Aug 28, 1998 2 Outflow R,C 19 ± 5 (5) 46 0.9 W2 Total 1056 54.4

May 27, 1999 1 Inflow H 70 + 18(2) 580 40.6 May 27, 1999 1 Middle H,C 78 ± 10(2) 1870 144.9 May 27, 1999 1 Outflow C 136+11(2) 48 6.6 Wl Total 2498 192.1

May 27, 1999 2 Inflow S,H 70(1) 370 25.8 May 27, 1999 2 Middle H 33 ± 3 (2) 1090 36.1 May 27, 1999 2 Outflow H,S 23 ± 3 (2) 550 12.5 W2 Total 2010 74.4

Table 4.10 - Algal biomass and percent cover in deepwater areas of experimental wetlands at the Olentangy River Wetland Research Park, 1998-99. C= Cladophora , R-Rhizoclonium , H=Hydrodictyon , S=Spirogyra , NP= no macroalgae present. Wl = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). 150

o> "O (0 O)

0.02 0.04 0.06 0.08 0.1 Total P, mg P L '

150 -

« . . 100 -

m S' 50 CO cn

0.01 0.02 0.03 0.05 I Soluble reactive P, mg P L

150 f

% 100 CO M II a t 50 CO O ) t

Nitrate+ nitrite, m gN L

Fig. 4.5 - Average metaphyton biomass (g m'^) vs. summer nutrient levels (mg L ‘) in the middle and outflow subbasins of the experimental wetlands, 1998-99. Error bars show standard errors.

78 Metaphyton showed significant amounts of calcium carbonates attached to their filaments, except for Spirogyra, which showed no evidence of any carbonates associated with its biomass. 1998 end-of-season samples showed a total calcium carbonate content of

30.5 kg in Wetland 1 and 16.1 kg in Wetland 2 (Table 4.11). Spring samples in 1999 showed higher amounts of calcium carbonates in Wetland 1 than in Wetland 2 (52.2 kg and

6.8 kg, respectively). This corresponds to observations that Wetland 2 developed algal cover at a slower rate than Wetland 1.

Scanning electron microscopy showed that the calcium carbonate materials associated with the algal mat were attached to and surrounding individual algal filaments

(Figs 4.6-9). The materials associated with the algal filaments did not show a defined crystal form (Fig. 4.9). X-ray diffi-action analysis confirmed the presence of crystalline calcite in the algal samples. Elemental analysis indicated the presence of small amounts of

P, at an approximate molar ratio of 10.2 ± 1.2 mmol P/mol Ca. This becomes a mass ratio of 3.15 ± 0.39 mg P/g CaCO]. Using these ratios, the carbonates in the metaphyton mat contained approximately 200 g P in the algae in summer 1998 and 185 g P in spring 1999

(Table 4.11). This is equivalent to 47 percent of the total P contained in the metaphyton mat in 1998 and 32 percent of the 1999 total. Therefore, P sorption with calcium carbonates is a significant a sink for P, in some subbasins immobilizing more P in carbonates than is present in the algal biomass itself (Table 4.11).

4.1.8 Sediments

Having shown that phosphorus is associated with calcium carbonate in the metaphyton mats, the sediments were then examined to see whether any carbonates firom the algal mat were deposited into the sediments for more long-term storage.

79 Total P in Pin Algal biomass CaCO, CaCO, Pin CaCO,' algal mat algal biomass % of total P Date Wetland Location kg g/g dry biomass kg g g g as CaCO,-P Aug 28, 1998 1 Inflow 0.0 0.00 0.0 0.0 0.0 0.0 Aug 28, 1998 1 Middle 69.6 0.25 17.6 75 190 115 40 Aug 28, 1998 1 Outflow 40.6 0.32 12.9 55 60 5 91 W1 Total 110.2 0.28 30.5 130 250 120 52

Aug 28, 1998 2 Inflow 1.6 0.00 0.0 0.1 12 12 1 Aug 28, 1998 2 Middle 51.9 0.31 15.9 68 158 90 43 Aug 28, 1998 2 Outflow 0.9 0.16 0.1 0.6 2.2 1.6 27 W2 Total 54.4 0.30 16.1 69 172 103 40 Both Wetlands 164.6 0.28 46.6 199 422 223 47 ooo May 27, 1999 1 Inflow 40.6 0.19 7.9 25 238 214 10 May 27, 1999 1 Middle 144.9 0.28 41.2 130 189 59 69 May 27, 1999 1 Outflow 6.6 0.47 3.1 10 5 0 W1 Total 192.1 0.27 52.2 164 432 268 38

May 27, 1999 2 Inflow 8.9 0.00 0 0 37 37 0 May 27, 1999 2 Middle 36.1 0.11 4.1 13 105 93 12 May 27, 1999 2 Outflow 12.5 0.22 2.7 9 13 4 66 W2 Total 57.5 0.12 6.8 21 155 134 14 Both Wetlands 249.6 0.24 59.0 185 588 402 47

a) average P/CaCOj ratio =3.15 + 0.39 mg P/g CaCO,

Table 4.11 - P associated with algal biomass and with calcium carbonate in deepwater areas of experimental wetland basins at the Olentangy River Wetland Research Park, 1998-99. W l= Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). > 3 .

"V ■ '

* 4 " k

" ' t ' ■■

- ^ V' ' S' ■'-■I'*’ f r,.- » ■.

200 ^im

Fig. 4.6 - Scanning electron micrograph of Cladophora filament encrusted with calcium carbonate. Sample was taken in mesocosm 46 on September 8 , 1998.

81 Fig. 4.7 - Detail of Cladophora filament encrusted with calcium carbonate. Sample was taken in mesocosm 46 on September 8 , 1998.

Fig. 4.8 - Calcium carbonate in algal sample taken in mesocosm 46 on September 8 , 1998. This calcite formed around an a l ^ filament, which afterwards decayed, leaving only the calcite.

82 Fig. 4.9 - Calcite in sediment samples taken in the experimental wetland basins at the Olentangy River Wetland Research Park in 1998. Both the well-defined crystals and the finer-grained precipitate are calcium carbonate. Algal filaments were found to be associated with only the fine-grained form, not the larger crystals.

83 4.1.8.1 Sediment analyses

Two layers of sediments in the experimental wetlands could be easily distinguished, and were treated separately in analyses. The upper layer (generally the first 8 cm) was visibly different than the underlying layer. It was very dark and gelatinous, while the lower layer appeared similar to the parent upland soils at the ORWRP. Because of this, more physical and chemical changes were expected to occur in the upper layer than the lower sediment layer. The upper layer's bulk density was significantly lower, and percent organic matter significantly higher, than the lower layer (Table 4.12). The relative isolation of the lower sediments is shown by the fact that percent organic matter in the lower sediments remained unchanged firom 1993 to 1999. The upper sediments were darker and had more variable soil color than did the lower sediments.

Calcite and calcium carbonate equivalent (CCE) concentrations in the sediments were not significantly different between basins for 1993, 1995, or 1999 samples; dolomite was significantly higher in Wetland 1 in 1995, but otherwise showed no significant differences between basins (Fig. 4.10). The upper and lower sediment layers were not significantly different in 1993 except for calcite in Wetland 1. In 1995, Wetland 1 showed significantly higher calcite, dolomite and CCE in the upper sediment layer than Wetland 1, while Wetland 2 showed significantly higher dolomite in the upper sediment layer. In

1999, calcite, dolomite and CCE were significantly higher in the upper sediment layer than the lower sediment layer (Fig. 4.10).

Comparing between years, calcite, dolomite and CCE in the sediments increased significantly firom 1993 to 1995 and fi"om 1995 to 1999 in the surface sediments at the inflow and middle subbasins. At the outflow, dolomite and CCE increased firom 1995 to

1999, but no other differences in the surface sediments were significant. The lower sediment layer showed significant increases in calcite and CCE at the inflow subbasin firom

1995 to 1999. The lower sediment layer at the middle subbasin showed a significant

84 Bulk density, g cm^ Organic matter, % Year 0-8 cm 8-16 cm 0-8 cm 8-16 cm 1993 1.31 ±0.037 (24)a* 1.19 ±0.020 (24)a 5.4±0.10(24)a 5.5 ±0.07 (24)a 1995 0.69 ±0.028 (24)b* 0.99 ± 0.033 (24)b 6.3 ±0.22 (24)b* 5.5 ±0.12 (24)a 1999 0.96 ±0.043 (24)c* 1.43 ± 0.016 (24)c 9.4 ± 0.62 (24)c* 5.5±0.11 (24)a

Table 4.12 - Bulk density and percent organic matter of sediments in the experimental wetlands at the Olentangy River Wetland Research Park. Different letters indicate significant difference (a=0.05) between years. indicates significant difference (a-0.05) between upper (0-8 cm) and lower (8-16 cm) sediment layer in the same year. Data from 1993 and 1995 were taken from a previous study of the experimental wetland basins (Naim 1996). 00 Ui 6 0 ■ 1993 50 CO □ 1995 40 □ 1999 T3 O) 30 'aâ o 20

10

0

30 ■ 1993 I □ 1995 0 5 20 □ 1999 a I o Q 10

0

□ 1995 □ 1999

co §• Ô) LU O ü H Inflow Middle Outflow Inflow Middle Outflow 0-8 cm 8-16 cm

Fig. 4.10 - Calcite, dolomite, and calcium carbonate equivalent in the sediments of the experimental basins at the Olentangy River Wetland Research Park in 1993, 1995 and 1999. Archived samples from a previous study (Naim 1996) were used for the calcium carbonate analysis of 1993 and 1995 samples. 86 increase in CCE from 1995 to 1999, and an increase in calcite and CCE from 1993 to

1995. The lower layer at the outflow showed no significant changes in carbonates (Fig.

4.10).

Calcite, dolomite, and total carbonate accumulation rates were calculated from the change in concentration of carbonates in the sediments from the initial samples in 1993 to the 1999 samples (Table 4.13). The amount of carbonates in the sediments was assumed to be constant from 1993 to initial flooding in March 1994. The inflow and middle subbasins had higher accumulation rates than the outflow subbasins. Carbonate accumulation was higher in the upper sediment layer than in the lower sediment layer.

The average calcite concentration in the suspended sediments entering the wetlands during the non-growing season was 0.013 + 0.069 percent by mass (n= 6), while dolomite averaged 10.4 ± 7.9 percent by mass (n= 6). During the growing season, calcite concentrations were 1.06 + 0.681 percent by mass (n=3), while dolomite averaged 2.32 +

0.576 percent by mass (n=3). Calcite concentrations were not significantly different from zero during the growing and non-growing seasons. Therefore, it is unlikely that the calcite found in the wetland sediments is imported from the river. However, dolomite concentrations were significantly different from zero in the growing season samples,

indicating that the dolomite in the sediment could be imported from the Olentangy River.

The total mass of calcite and dolomite in the sediment of each wetland basin was calculated for 1993, 1995, and 1999. While these calculated totals cannot be compared

statistically, both calcite and dolomite increased with time. From 1993 to 1999, over

16.000 kg of calcite was deposited into the surface sediments of Wetland 1, and over

18.000 into the surface sediments of Wetland 2 (Fig. 4.11). Calcite in the lower clay layer

of sediments increased as well, increasing by over 1800 kg in Wetland 1 and over 1400 kg

87 Calcite Dolomite CCE g m’’ yr ‘ g m ’ yr ‘ g-eq CaCOj m * yr ‘ 0-8 cm Inflow 76.2 ± 18.9 ( 6)* 48.2+ 10.0 (6)# 128.6+ 28.1 ( 6)* Middle 97.0± 25.9 ( 8 )* 24.7± 4.1 (8 )* 123.8± 29.4 ( 8 )* Outflow 30.4± 14.4 (8 ) 9.6± 5.0 (8 ) 40.8+ 18.5 ( 8 )

8-16 cm Inflow 17.0± 5.9 (7)* 12.2± 6.4 (7) 30.3+ 10.9(7)* Middle 6.4 + 3 ^ (9) 4.6± 2.0 (9) 11.4 ± 4.5 (9)* Outflow 2.8 + 4 3 (9) -4.9± 2.2 (9) -2.5± 5.1 (9)

Table 4.13 - Accumulation rates for calcium carbonate minerais (calcite, dolomite, and calcium carbonate equivalent (CCE)) precipitated in the experiment^ wetland basins at the Olentangy River Wetland Research Park, 1994-1999. * denotes accumulation rates significantly different fi"om zero (a = 0.05).

88 25.000 □Wetland 1 □W etland 2 20.000

5* 15,000 B o g 10,000

5,000 m

1993 1995 1999 1993 1995 1999 0-8 cm 8-16 cm

8,000

7.000 □ Wetland 1 □ Wetland 2 6.000

^ 5,000 B g 4,000 O O 3,000

2,000

1,000

0 1993 1995 1999 1993 1995 1999 0-8 cm 8-16 cm

Fig. 4.11 - Calculated totals of calcite and dolomite contained in the sediments of the experimental wetland basins at the Olentangy River Wetland Research Park in 1993, 1995 and 1999. 89 in Wetland 2. Dolomite showed similar patterns, increasing by over 5000 kg in the surface sediments in both basins. Dolomite in the lower clay layer of sediments increased by over

900 kg in Wetland 1 and over 300 kg in Wetland 2.

The spatial pattern of carbonate deposition shows that the inflow and middle subbasins deposit more calcite and dolomite than the outflow subbasins (Fig 4.12). The levels of calcite and dolomite in the inflow areas are puzzling, because there was very little macroalgal biomass and low GPP in the inflow subbasins during the years of the study.

This precipitation could be the result of decreased calcite solubility due to the warming of the water in the first subbasin or other physical factors, or to production of macrophytes such as Potamogeton natans , which are common in the inflow areas. Plants of the genus

Potamogeton have been shown to precipitate calcite on the surfaces of their leaves (Prins etal. 1980).

Scanning electron microscopy showed calcite inclusions in the upper sediments.

However, the concentrations of P in the calcite could not be determined due interference effects of the surrotmding sediment matrix. Assuming that the calcite in the sediment is completely due to algal-induced precipitation, and that the ratio of P to calcite remained similar, 57 kg of P were removed from 1993 to 1999 through sorption with calcite deposited into the sediments of Wetland 1, and 62 kg of P were retained in Wetland 2.

4.1.8.2 Chemical analyses

The sediments showed significant differences between wetlands in 1993 for pH, available P, Mg and Ca, and cation exchange capacity. However, no significant differences were found in 1995 and 1999 for either the upper or lower sediment layers.

Upper and lower sediment layers were different for all measured parameters on at least one of the three sampling dates (Figs 4.13 - 4.14). Therefore, upper and lower sediment layers were statistically analyzed separately.

90 a 12,000 ■ 1993 10,000 □ 1995

05 8,000 □ 1999

I 6,000 ca ^ 4,000

2,000

0 I

b 4,000 ■ 1993 □ 1995 3.000 □ 1999 S 03 I 2,000 o o Q 1.000

C 16,000 „ 14,000 ■ 1993 8 12,000 □ 1995 O 10,000 □ 1999 9 8,000 6,000 Ü 4,000 ^ 2,000

W1 In W1 Mid W1 Out W2 In W2Mid W2 Out

Fig. 4.12 - Calculated totals of calcium carbonate minerals in the sediments of the Olentangy River Wetland Research Park prior to flooding (1993), 17 months post-flooding (1995), and 5 years post-flooding (1999). W1 = Wetland 1 (planted), W2 = Wetland 2 (naturally colonizing). ln=inflow subbasin, Mid=middle subbasin, Out=outflow subbasin.

91 ■ 1993 E11995 0 1 9 9 9

5,500 1993 01995 01999 ^ 5,000

^ 4,500 CO m 4,000

I 3,500 O) I 3,000 u « 2,500 2,000

500 ■ 1993 0 1995 0 1999

CO o ^ 400

300 Inflow Middle Outflow Inflow Middle Outflow 0-8 cm 8-16 cm

Fig 4.13 - Chemistry of the sediments in the experimental wetland subbasins at the Olentangy River Wetland Research Park, 1993-99. Data from 1993 and 1995 are taken from a previous study (Naim 1996).

92 2 0 1993 G 1995 □1999

^ 15 t CL ® ^ 10 æ O) c co I a

■ 1993 01995 01999

CL 600

300 Inflow Middle Outflow Inflow Middle Outflow 0-8 cm 8-16 cm

Fig. 4.14 - Available and total P in the sediments of the experimental wetland subbasins at the Olentangy River Wetland Research Park, 1993-99. Data from 1993 and 1995 were taken from a previous study of the basins (Naim 1996). Total P analysis was not performed on the lower sediment layer (8-16 cm) in 1993 or 1995.

93 Soil pH increased as time of flooding increased, but was not significantly different firom inflow to outflow in any year (Fig 4.13a). Soil pH for the upper sediments was not significantly different from the lower sediments in 1993 or 1995, but was significantly higher in the upper sediments in 1999.

Exchangeable Ca increased significantly in the upper sediments from 1993 to 1995, and from 1993 to 1999 (Fig 4.13b). Data from 1995 and 1999 were not significantly different. The upper and lower sediments were not significantly different with respect to exchangeable Ca in 1993, but were significantly different in both 1995 and 1999.

Exchangeable Ca was not significantly different between inflow, middle, and outflow sites in 1995 and 1999, with the exception of the surface layer in the middle and outflow subbasins in 1995.

Exchangeable Mg did not show significant differences from inflow to outflow, but did increase significantly from 1993 to 1999 (Fig 4.13c).

Available P showed no significant difference between inflow, middle and outflow samples in 1993 (Fig 4.14a). In 1995, the inflow surface sediments were significantly different from the middle surface sediments. In 1999, the lower sediments were significantly different at the inflow from the outflow.

Total P increased in the upper sediments from 1993 to 1999 (Fig 4.14b). Since there were no data for the lower sediments in 1993 and 1995, no comparisons can be made

for the lower sediment layer.

4.2 Mesocosm experiment

4.2.1 Water column biochemistry

A summary of the diurnal pattems of 16 water column chemical parameters which were selected as indicators of ecosystem function in the mesocosms experiment is shown in

Table 4.14. Each of these parameters is discussed below.

94 Total Date Treatment DO pH Cond Temp Redox SI Ca SRP TP TDC D ie DOC TC TIC TOC alkalinity July 8 , 1998 Algae + - + - 00 + - +0 +- 00 00 00 0- 00 0+ 00 00 00 00 July 8 , 1998 Control 00 +0 +0 + - +0 + - 00 00 00 0- 00 0+ 00 0+ 00 00

July 28, 1998 Algae "h- + - 00 + - 0+ + - 00 00 00 -4- -+ 00 -4- -+ +0 00 July 28, 1998 Control 00 00 00 + - ++ - + 00 00 00 00 00 00 0- 0- 00 00

Aug 20, 1998 Algae + - 4"- 00 + - 0+ + - 00 00 00 -4" -4- 00 -+ -4- 00 00 Aug 20, 1998 Control 00 00 00 + - ++ 4-- 00 00 00 00 00 00 00 00 00 00

Sept 22, 1998 Algae +- + - 0+ 0- -+ 4"- 00 00 00 00 00 00 0+ -4- 00 0+ Sept 22, 1998 Control 00 00 0- 0- - + 4-- 00 00 00 +0 +0 00 0- 0- 00 00 o u« Dec 3, 1998 Algae 00 00 -0 +0 0+ 4-- 00 00 00 00 00 00 00 00 00 00 Dec 3, 1998 Control 00 00 -0 ++ +0 4-- 00 00 -0 00 00 00 00 00 00 00

Table 4.14 - Diumal trends in water chemistry in wetland mesocosms, 1998. The first symbol represents the difference between dawn and the following dusk. The second symbol represents the difference between dusk and the following dawn. + denotes a statistically significant increase, and - indicates a statistically significant decrease (a - 0.05). A zero represents no significant statistical difference(a = 0.05). 4.2.1.1 Dissolved oxygen and GPP

Dissolved oxygen increased significantly during the day and decreased significantly

at night in the algae mesocosms for every sampling date except December 3 (Table 4.14,

Fig 4.15a). Control mesocosms showed no significant diumal changes in dissolved oxygen on any sampling date (Table 4.14, Fig 4.15a).

GPP, calculated fi’om the diumal changes in dissolved oxygen, was significantly higher in the algal mesocosms than in control mesocosms for every sampling date (Fig.

4.16), and GPP in the control mesocosms was not significantly different from zero (except

on July 28, when the control mesocosms showed a negative GPP because dissolved

oxygen concentrations increased from dusk to dawn). Production in the algae mesocosms

was highest in July and August, decreased in September and further decreased in

December.

4.2.1.2 pH

pH in the algae mesocosms showed the same diumal pattems as dissolved oxygen,

significantly increasing during the day and decreasing at night, except in December (Table

4.14, Fig 4.15b). Average dusk pH values for the algae treatment exceeded 9.7 in the

summer, with some algae mesocosms having pH maxima exceeding 10. These pH values

are comparable to values found in the full-scale experimental wetlands, and are conducive

to calcite precipitation. The control mesocosms showed a significant diumal increase only

once, on the first sampling date in July.

96 'A— Algae ■o— Control

T3 O)

0--0 — — - I

o - - - Control

...o 7.5 7.0

A A -O---Control

d 30 Ü 25 - A — Algae -O— Control I 20 "A I- I

III IIIIIIIII Jul 8-9 Jul 28-29 Aug 20-21 Sept 22-23 Dec 3-4

Fig 4.15 - Diumal trends in water quality in wetland mesocosms, 1998. Error bars show standard errors. 97 6

I □ Algae | ■Control I

5

4 ■a E O 3 O) Û. Q. o 2

1

0 a . Jul 8-9 Jul 28-29 Aug 20-21 Sept 22-23 Dec 3-4

Fig. 4.16 - Gross primary production in wetland mesocosms at the Olentangy River wetland Research Park, 1998. Different letters indicate a significant difference between treatments (a = 0.05).

98 4.2.1.3 Conductivity

Conductivity (corrected to 25 ° C) rose throughout the sampling period, indicating that ions were being added to the water column, probably from the sediment or from the river water used to stock the mesocosms (Fig. 4.17a). Half of the mesocosms’ water was removed each time before the addition of river water, but evaporation after filling may have concentrated the ions in the mesocosms. Conductivity in the algae mesocosms was significantly lower than in the control mesocosms for all sampling dates (Fig. 4.17a), indicating that some ions were being removed from solution in the algae mesocosms but not in the control mesocosms. This is an indicator that calcite precipitation may be occurring; however, it is also consistent with algal uptake of nutrients.

4.2.1.4 Temperature

Temperature showed significant diumal changes for all mesocosms on every sampling date, generally increasing during the day and decreasing at night (Table 4.14,

Fig. 4.15d). The temperature increase would decrease the solubility of CO, in water and thus favor calcite precipitation. As expected, water temperatures were generally lower in the control mesocosms than in the algae mesocosms. This anomaly of the shading effect of the black cloth did not significantly affect the difference in saturation index between the treatments. The maximum difference in water temperatures between algal and control mesocosms was 2.5 “ C, which occurred at dusk in July. By the Arrhenius equation, cooler water temperatures in the control mesocosms would be expected to slow biological processes by a maximum of 16% as compared to the algal mesocosms. However, the limiting factor regulating GPP in the control mesocosms was the lack of light. In an unshaded mesocosm with no metaphyton, water temperatures would be expected to be higher due to the lack of shading from the metaphyton mat. However, these increased temperatures should not be enough to cause calcite precipitation alone.

99 a 1200 □Control I l 000 BAIgae ^ 800

■èu 600 I 400 U 200 b 80 □Control , 60 □Algae _l O) E 40 -■ (0 O 20 -■

0 -■ d m m

c Tj 70 a □Control g 60 a tL 50 BAIgae S 40 a a 1 30 2 20 b b a I 10 b b m , a ' I 0 d 100 I □ Control . 80 iHAIgae CT 60 a-' 40 2 g 20

Jul 8-9 Jul 28-29 Aug 20-21 Sep 22-23 Dec 3-4

Fig. 4.17 - Chemical constituents in the water column of wetland mesocosms at the Olentangy River Wetland Research Park, 1998. Different letters indicate significant differences between treatments (a = 0.05).

100 4.2.1.5 Oxidation-reduction potential

Redox potential showed a diumal decrease once, in fall. Otherwise, redox tended

to increase, but showed no distinct pattern.

4.2.1.6 Saturation index

Calcite saturation index (SI) values showed significant diumal changes for all

treatments and sampling dates (Table 4.14, Fig. 4.15c). The values of SI were always

positive, indicating that calcite precipitation was favored in all mesocosms both during the

day and at night. The presence of high SI values is not sufficient to conclude that

precipitation occurs, and further evidence was needed to conclude that precipitation

occurred. Algal mesocosms showed saturation indices increasing during the day and

decreasing at night for all sampling dates except in the winter, when SI increased both

during the day and at night. This diumal change indicates that the likelihood of calcite to

precipitate increased during the day in the algal mesocosms. Control mesocosms showed

SI values increasing significantly during the day and decreasing at night for all sampling

dates except on July 8 and July 28; however, the increases and decreases were significantly

smaller than those in the algal mesocosms. These smaller diumal changes could be due to

diumal temperature variation and smaller changes in pH.

4.2.1.7 Dissolved calcium

Dissolved Ca concentrations in the algae mesocosms were significantly lower than

in the control mesocosms for every sampling date (Fig 4.17b). This indicates that these

ions were being removed fi’om solution, supporting the hypothesis of calcite precipitation.

If calcite precipitation did occur, the crystals would be expected to appear in the metaphyton

biomass or in the sediment (see metaphyton section below).

101 4.2.1.8 Phosphorus

As expected, algal mesocosms had significantly lower SRP levels than control mesocosms on every sampling date except during winter (Fig. 4.17c). The removal of P firom solution could be due to algal uptake, sorption to sediment, or sorption with calcite.

Scanning electron microscopy results show that phosphorus was associated with the calcite crystals, and will be discussed in a later section. Total phosphorus in the algae mesocosms was lower than in control mesocosms for every sampling date except the winter sampling date (4.17d).

4.2.1.9 Carbon

TDC, TC and DIC showed significant diumal decreases in midsummer (July 28 and August 20), while TIC showed significant diumal decreases in midsummer and fall

(July 28, August 20, and September 22). The decrease in inorganic carbon is most likely due to uptake of inorganic C by algae or perhaps precipitation. DOC, and TOC parameters showed no consistent diumal pattems in any treatment on any date (Table 4.14).

Algae mesocosms showed significantly higher values of DOC and TOC than the control mesocosms on the July 28, August 20, and September 22 sampling dates. Algae mesocosms had significantly lower DIC and TIC on all sampling dates except July 8 , where no significant difference was found. Diumal changes in inorganic carbon were expected, because photosynthesizing algae use inorganic carbon in the water column for photosynthesis and replace it through respiration. Total carbon and total dissolved carbon were significantly lower in the algal mesocosms than the control mesocosms for every sampling date except July 8 .

102 4.2.2 Metaphyton biomass and elemental analyses

Although calcium carbonate equivalence (CCE) decreased as a percentage of the total algal mass from June to August, total CCE significantly increased with the growing algal mat from an average of 12.8 g-eq CaCOj m'^ at initial stocking to an average of 19.3 g-eq CaCOj m'^ at fall sampling (Tables 4.14, 4.15). All algae samples contained calcium carbonates. Since reaction times were uncertain due to the fine nature of the ground algal samples, the amount of carbonates in the algal samples is reported only as calcium carbonate equivalent (CCE), and not as calcite and dolomite. However, most of the CO? which evolved during the laboratory analysis for carbonates evolved immediately upon acidification. Since calcite reacts much more quickly than dolomite upon acidification, it is reasonable to conclude that most if not all of the carbonates found in the algal samples was calcite.

As with the samples from the full-scale wetland basins, scanning electron microscopy showed algal filaments encrusted with calcite (Fig 4.6 - 4.8). The average

P/Ca ratio was calculated as 1.05 ± 0.04 mg P/g CaCOj (mean ± standard error, n=22).

Although the per-gram and total amount of P associated with the metaphyton mat decreased from summer to fall, perhaps due to P limitation in the non-flowthrough mesocosms, the amount of P associated with calcite increased (Table 4.16). P associated with calcite accounted for up to 31% of the total P in the metaphyton mat, a lower percentage than found in the basin algae samples, where calcite-P accounted for up to 91% of the total P in the metaphyton mat.

4.2.3 Sediments

Mesocosm sediments were examined to see whether any increase in carbonates

could be detected. The comparison of soil physical characteristics shows that the sediment

in the two treatments was very similar, only differing significantly in bulk density. The

103 Algal biomass Date g/m' P, mg/g Ca, mg/g Mg, mg/g CCE, % of dry mass Jun 22, 1998 58.9±4.i9(20)a 1.66 ±0.013(6)a 120.5 ± 1.0(6)a 3.8±0.02(6)a 21.7 ±0.32(2) Sep 8,1998 104.7 ± 6.9 l(10)b 0.63 ±0.031(10)6 82.7 ±4.48(10)6 5.4 ±0.26(10)6 18.4 ± 1.45(10)

Table 4.15 - Biomass in algal mesocosms and important chemical components in the early and late growing season. Chemical constituents are expressed as average ± standard error (n). Different letters indicate a significant difference between the June and September sampling dates (a=0.05). CCE = calcium carbonate equivalent.

s

% of mat P Date P, mg Ca, g Mg, mg CCE, g-eq CaC03 P in calcite, mg in calcite Jun 22,1998 97.4 ± 0.74(6)a 7.09±0.06(6)a 225 ± l(6)a 12.8 ± 0.19 (2)a 13.4 ± 1.24(2) 13.8 Sep 8,1998 65.5 ±4.53(10)6 8.45 ±0.44(10)6 562 ±46(10)6 19.3 ± 1.1 (10)6 20 3 ± 1.10(10) 31.0

Table 4.16 - Total amount of chemical constituents in the algal mats in the algal mesocosms, 1998 (ave. ± std. error (n)). Different letters indicate a significant difference between the June and September sampling dates (a=0.05). sediment in the algae mesocosms had a lower bulk density than in the control mesocosms and the initial soil, perhaps due to algal biomass in the soil.

Chemical analysis of the sediment samples showed no significant differences between algal and control treatments after flooding for total P, Ca, K, or Mg (Table 4.17).

However, soil exchangeable F was significantly lower in the algae treatment versus the control treatment, and both were significantly lower than in the initial samples. This indicates that some of the P in the sediments had solubilized, entering the water column upon submergence. The lower amount in the algae sediments could be due to the low levels of P in the water column, which would caused increased desorption from the sediments into the water coliunn.

Calcite and dolomite analysis of the sediments showed no significant increase in soil carbonates for either treatment when compared to the initial soil. Carbonate concentrations were all significantly different from zero, except for dolomite in the initial samples (Table 4.17). All values were very low (calcium carbonate equivalent <1.5%), and no evidence of carbonates (i.e., visible CO? evolution upon acidification) was observed during the sample analysis.

105 total P total Ca total Mg % Calcite % Dolomite % CCE Treatment mg/g mg/g mg/g by mass by mass by mass Initial 541 ±10.3(3) 5.20 + 0.09 (3) 4.48 ± 0.08 (3)b 0.802 ±0.161 (10) 0.486 ±0.090(10) 1.331 ±0.153(10) Algae 567 ± 10.4(10) 5.78 + 0.33(10) 4.80±0.10(10)a 0.913 ±0.193(3) 0.132 ±0.140(3)* 1.057 ±0.163(3) Control 572 ± 11.5(10) 5.55 ±0.25(10) 4.75 ± 0.09 (10)a 0.883 ±0.137(10) 0.508 ±0.153 (10) 1.435 ±0.182(10)

exch. P exch. Ca exch. Mg CEC Treatment Hg/g M8/g Itg/g meg/ 100 g pH Initial 13.0±0.00(3)a 2.91+0.02 (3) 451 ±4.7(3) 18.51 ±0.139(3) 7.65 ± 0.038(3):. Algae 6.6±0.91(10)b 2.88 ±0.05 (10) 447 ± 10.8(10) 18.34 ±0.223(10) 7.35±0.040(10)b Control 9.7±0.56(10)c 2.78 + 0.05(10) 433 ±6.6(10) 17.74 ±0.286(10) 7.48±0.030(10)c

§ Table 4.17 - Chemical characteristics of sediment in mesocosms prior to flooding (Initial), and in the treatment (Algae) and control mesocosms after 1 yr continuous flooding. Ave. + std. error(n). Different letters denote significant difference between samples (a=0.05). * denotes that the value is not significantly different from zero. CHAPTER 5

DISCUSSION

5.1 Gross primary productivity and algal biomass of shallow wetlands

The summer gross primary productivity in the full-scale wetlands (3.4 - 6.0 g 0 , m * d‘‘) was comparable to other productive temperate wetlands and hardwater lakes

(Reeder 1990, Vymazal 1995a, Table 5.1). The GPP compared well with the range of 4.3 -

8.4 g 0 , m'^ d ' observed in a coastal Lake Erie freshwater marsh (Reeder 1990) and to seasonal averages of 2.2 - 6.4 g O, m * d‘‘ obtained from constructed riparian wetlands in

Illinois (Cronk and Mitsch 1994b). When compared to eutrophic lakes, the areal gross primary productivity was very similar, indicating that even though the study wetlands are much shallower ecosystems, on an areal basis their productivity is equivalent to eutrophic lakes. The Fox Chain of Lakes in northeastern Illinois had areal GPP values of 1.0 - 9.6 g

O; m'^ d‘‘, with an average value of 4.2 g 0, m'^ d'‘ (Mitsch and Kaltenbom 1980). GPP values for the wetlands were higher than those found for Lake Constance, Germany (0 -

1.2 g Oj m'^ d ', Stabel 1988), even though the euphotic zone in that lake is 20 m deep.

The large extent of primary production in a shallow water column leads to larger changes in water chemistry than would occur if the primary production were dispersed over a euphotic zone several meters deep. Hence, aquatic primary producers have a large influence on the chemistry of the shallow wetland water column.

107 Study site Ecosystem GPP, g O, m 'd ' Author experimental wetlands, OH freshwater marsh 3.45 - 5.95 this study wetland mesocosms freshwater marsh 2.23 - 4.75 this study Old Woman Creek, OH freshwater coastal Lake Erie marsh 4.3 - 8.4 Reeder 1990 Des Plaines River, IL freshwater marsh 2.2 - 6.4 Cronk and Mitsch 1994b Lawrence Lake, Ml oligotrophic hardwater lake 5.3U Wetzel e/a/. 1972* Fox Chain of Lakes, IN eutrophic lakes 1.0-9.6 Mitsch and Kaltenbom 1980 Lake Constance, Germany lake 0-10.7# Stabel 1988 Delta Marsh, Lake Manitoba, Canada freshwater marsh 6.0# Robinson et al. 1997b Black Lake, EC, Canada hypereutrophic hardwater lake 5.0#& Muiphy et al. 1983 Fayetteville Green Lake, NY lake 0.6 - 7.7# Culver and Brunskill 1969

#converted from g C to g O,, 0.375 g C = 1 g O, & assumed i m depth of euphotic zone o 00 * cited in Vymazal 1995a

Table 5.1 - Growing season gross primary productivity (GPP) in wetlands and hardwater lakes. Aquatic gross primary productivity in wetlands is influenced greatly by available light and nutrients. Emergent macrophytes and woody species can significantly affect gross primary production by decreasing the amount of photosynthetically active radiation

(PAR) which reaches the water. The density and species of macrophytes often determines the amount of shading. Grimshaw et al. (1997) found that in dense Typha stands, PAR reaching the water surface decreased over 85% over open-water sites, and net primary production decreased by 80%. Rose and Crumpton (1996) found that in a prairie pothole wetland in Iowa, open water areas showed diurnal fluctuations of dissolved oxygen, while the water within Typha stands had very low levels of dissolved oxygen due to decreased production in the water column and increased oxygen demand due to the decomposition of the litter mat within the stand.

Nutrient levels are also important factors regulating algal productivity and total biomass. Cronk and Mitsch (1994a) found that in constructed Illinois wetlands, periphyton biomass was highest in the high-flow wetland cells and near the inflow sites, and attributed this fact to higher nutrient concentrations at these sites. Wu and Mitsch

(1998) found that metaphyton biomass per unit area in the experimental wetlands was highest at the inflow, and generally decreased fi-om inflow to outflow. The current study

found that metaphyton had the lowest biomass in the inflow subbasins, a complete reversal of the previous study. This could be due to increased turbidity at the inflow sites and higher turbulence, as well as shading effects by floating Lemna spp., which covered almost the entire inflow subbasins during the study period. Increased nutrient levels can

cause shifts in algal species assemblages (McCormick et al. 1998) and periphyton

communities have been suggested as indicators of early eutrophication in the Florida

Everglades (McCormick and Stevenson 1998).

109 Although wetlands are primarily noted for high macrophyte biomass production, wetlands can also produce large amounts of algal biomass due to their often high-nutrient status and high light availability in open water areas (Table 5.2). The fact that the euphotic zone in most wetlands includes the entire water column is conducive to mats of filamentous metaphyton which may not be found in deeper aquatic systems, where sunlight does not reach the sediments. In many wetlands, account for a small percentage of the total biomass production in the water column. Robinson et al. (1997a) found that phytoplankton accounted for only 1% of the algal biomass in a Canadian marsh; the other

99% of the biomass consisted of metaphyton (87%), followed by epiphyton (11%) and epipelon (1%). In total, the algal biomass in the Canadian study wetland was 244 g m '\

At the Columbus study site, Yu er al. (1997) measured phytoplankton primary productivity in the experimental wetlands by the light-dark bottle method and community metabolism by the diurnal oxygen method, and found that phytoplankton primary productivity accounted for only 17% of the total aquatic primary production. Although algae in wetlands have not been as well-studied as have higher plants, algal biomass can exceed the water-column biomass of submersed macrophytes in a wetland (McDougal et ai 1997). The influence of primary producers on the chemistry of productive wetlands is immense. Algal production can be especially important for nutrient removal in the early years of constructed wetlands. Algal populations establish very quickly in nutrient-rich aquatic systems, and their location in the water column and rapid growth rates can lead to significant removal of dissolved nutrients early in the development of a constructed wetland. Submersed and emergent macrophytes often take several years to establish in sufficient densities to affect nutrient uptake. Algal uptake and coprecipitation would be a mechanism to remove newly solubilized nutrients from the water column and prevent the wetlands from exporting dissolved P. Robinson et ai (1997a) observed that metaphyton were the dominant primary producers in newly-flooded marshes, and hypothesized that

110 Dty algal biomass Study site Ecosystem type Major genera gm - Author Columbus OH freshwater marsh Cladophora, Rhizoclimium, 13-136 this study Hydradicytun, Spirogyra wetland mesocosms freshwater marsh Cladophora, Rhizocloninm, 105 this study Spirog)'ra Delta Marsh, Lake Manitoba, Canada freshwater marsh Enteromoipha, Chaetophora 244 Robinson et n/. 1997a Delta Marsh, Lake Manitoba, Canada freshwater marsh Cladophora. Enteromorpha 150-350 McDougalet al. 1997 Des Plaines River, IL freshwater marsh Cladophora 0.05 - 6 Cronk and Mitsch 1994 England, fertilizer experiments Cladophora 1.7-18.2 Daldorph and Thomas 1991* ponds in Czech Republic ponds Cladophora, Hydrodictyon 33-83 Bohonkova1977* Colorado River, AZ Cladophora 17-144 Usher and Blinn 1990* Lake Krageholmssjon, Sweden Cladophora 30-272 Muller 1983* Nesyt Pond, Czech Republic Spirogyra, Oedogonium, 25-891 Lhotsky and Marvan 1975* Cladophora, Enteromorpha Everglades National Park, FL freshwater marsh Johanneshaptistia, 161-1180 Vymazal and Richardson 1995 Phonnidium, Tolypolhrix

Table 5.2- Algal biomass in wetlands and lakes. * denotes a reference taken from Vymazal 1995a. algal uptake was the reason that no increases in dissolved P were detected, despite the resolubilization of P from the newly-flooded sediments. At the experimental wetlands used in the present study, significant algal cover (up to 86 % of the surface) was evident in the first year of flooding (Wu and Mitsch 1998), when it was hypothesized that massive algal productivity was due to the release of nutrients from the sediments, previously used as heavily fertilized agricultural fields.

Wetland aquatic communities show definite seasonal trends in temperate climates, as aquatic producers and decomposers are more active at higher summer temperatures and higher light levels. Algal succession typically follows a seasonal rather than a multi-year pattern, because the life-span of algae is much shorter than aquatic plants, and because the large metaphyton mats generally do not overwinter. The algal mat senesces and decomposes each fall, and must recolonize in the spring, unlike many macrophytes, whose root structures remain over the winter. The increased cover of submersed and emergent aquatic macrophytes as constructed wetlands develop will affect the algal community as they compete for space, nutrients, and light.

The planted and unplanted experimental wetlands did not show significant changes in GPP and R during the study period. This is not surprising, as earlier studies had concluded that the wetland had converged in structure and function during the time period of the study. Wu and Mitsch (1998) found that aquatic metabolism was not significantly different between wetland basins during the first growing season after initial flooding. Any differences in aquatic metabolism could have taken place between 1994 and 1996, when the planted wetland had significantly higher macrophyte cover than the unplanted wetland.

However, the majority of the aquatic metabolism occurs in the deeper, unvegetated areas of the wetlands, which reduces the influence that macrophytes could have upon aquatic metabolism. The wetlands may diverge in aquatic metabolism in the future, as the wetland basins diverge in macrophyte cover.

112 5.2 Influence of aquatic primary productivity on aquatic biogeochemistry in wetlands

Diurnal changes in dissolved oxygen and pH show that the primary producers in wetlands can drastically change the water chemistry on a diurnal time-scale. Increases in dissolved oxygen up to 30 mg L'% such as those found in the experimental wetlands in summer, have also been recorded in the Florida Everglades (Rader and Richardson 1992).

Increased pH affects the spéciation and sorption of many chemical species, particularly P and metals. Algae can sorb metals to their surfaces, and this process increases with increasing pH (Vymazal 1995b). Daily increases in temperature and pH cause calcite precipitation to become even more thermodynamically favored in wetlands and shallow lakes. However, calcite precipitation events in wetlands have not been recorded alone in the water column as a "whiting event" such as occurs in lakes, but have only been found associated with algal cells. Photosynthesis by algae and submersed aquatic macrophytes in the wetland water column thus seems to be the primary cause of calcite precipitation in wetlands, although physical conditions may increase the likelihood of such events. This is further supported by the results of the mesocosm experiment, in which no calcite precipitation occurred in the control mesocosms, despite the fact that they were continually supersaturated for calcite. The low levels of phosphorus in the algae mesocosms despite the release of P from the sediments indicate that algae may play an important role during the early development of created wetlands, where high-nutrient soils release their nutrients after

flooding. As the algae and submersed macrophytes decay, calcite is deposited into the sediments and can be a significant sink for P. In fact, calcified algal remains have been tested as substrates for constructed wetlands (Gray et al. 2000), where it removed 98% of the total phosphorus entering the system.

113 The central role of aquatic metabolism in calcite precipitation implies that changes in community structure and ecosystem processes which affect primary productivity can also affect the saturation and precipitation of calcite. Andersson et al. (1978) suggested that planktivory by fish caused significant increases in pH and calcite precipitation in the eutrophic Lake Bysjon, Sweden. Hanson et ai (1990) found that calcite saturation and precipitation decreased after a lakewide fish removal in Lake Christina, Minnesota. This was attributed to increased grazing of phytoplankton by Daphnia spp., whose populations increased in the lake due to decreased fish planktivory. In addition to influencing wetland water chemistry, aquatic primary producers can cause changes in the physical characteristics of the water column, influencing water temperature and the depth of the euphotic zone though self-shading. McDougal et al.

(1997) showed that floating mats of Cladophora in a Canadian marsh decreased surface irradiance by over 90% in the upper 10 cm of the water column.

5.3 Calcite precipitation

A comparison of the rate of calcite deposition into the sediments of the ftill-scale wetlands to those for eutrophic hardwater lakes shows a remarkable similarity in deposition rates (Table 5.3). The study site’s estimated calcite deposition rate of 1.2 g CaCO, m'^ d ' is similar to rates reported by Stabel (1989) and Otsuki and Wetzel (1974) for eutrophic hardwater lakes (1.24 and 1.22 g CaCOj m'^ d ' , respectively), although precipitation rates as high as 14 g CaCOj m’“ d ' have been reported in an Austrian eutrophic hardwater lake

(Weilenmann et al. 1989). The similarity in calcite precipitation rates between hardwater wetlands and eutrophic hardwater lakes suggests that even though different algal genera are involved, the calcite precipitation process is similar in both these ecosystems. Calcite precipitation may be a more widespread result of photosynthesis in productive hardwater

114 CaCO; deposition rate Study site g CaCO: m - d' Author experimental wetlands, OH 1.2 this study Lake La Cruz, Spain 2.23 Rodrigo et al. 1993 Pyramid Lake, NV 4.2 Galat and Jacobson 1985 Lake Constance, Germany 0.69- 1.04 Rossknecht 1980 Lawrence Lake, MI 1.22 Otsuki and Wetzel 1974 laboratory algal cultures avg = 1.05, max=1.63 Yates 1996 Lake Constance, Germany 1.24 Stabel 1989 Lake Wallensee, Germany 1.29-3.22 Jager and Rohrs 1990 Lake Sempach, Switzerland 1 - 14 Weilenmann et al. 1989 Lake Zurich, Switzerland 1 -6 Weilenmarm et al. 1989 Fayetteville Green Lake, bTY 1.45 Brunskill 1969 Green Lake,Jamesville NY 4.85 Efflerera/. 1981 Lake Attersee, Austria 0.68 Schroder e/a/. 1983

Table 5.3 - Calcite precipitation and deposition rates in wetlands and hardwater lakes.

115 wetlands than is currently known, and may play a significant role in P immobilization.

Calcite precipitation may play a role in immobilization of other chemical constituents in wetlands as well, such as dissolved organic carbon and metals.

5.4 Phosphorus sorption with calcite

Concentrations of P on the surface of tlie calcite crystals in the hardwater experimental wetlands were 7.88 mg P/g Ca, higher than those reported for eutrophic hardwater lakes (Table 5.4). This could be due to higher P concentrations in the water column of the research wetlands than in the lakes. Wu and Mitsch (1998) foimd average Ca concentrations of 137 mg Ca/ g dry weight in the study site, and P concentrations in the metaphyton mat of 0.5 - 4 mg P/ g dry weight. Assuming that 50% of the P found in the metaphyton mat was coprecipitated with calcite, calculated P/Ca ratios ranged fi’om to 1.8 -

14.6 mg P/g Ca. No seasonal difference was found in the P/Ca ratio for this study; however, other researchers have found seasonal differences in this ratio due to changes in water column P concentrations (Jager and Rohrs 1990, Rossknecht 1980). Kleiner (1988) found P concentrations of 3.44 mg P/g Ca in Lake Constance, Germany, while House and

Donaldson ( 1986) found a range of 0.4 - 4 mg P/g Ca, with P coprecipitation increasing as

P concentrations in the water column increased.

5.5 Ca and P flow through the experimental wetlands

An ecosystem diagram for the study site is shown in Fig. 5.1, detailing the flow of

Ca and P through the ecosystem, and the relative role of calcite precipitation upon P retention. The diagram is for a 1-m'^ area of an average wetland basin at the study site in

1998. An average wetland basin retains 4.5 g P m'^ yr, over 50% of the total P entering it.

This is consistent with the results of Mitsch et al. (1995), who found P retention rates in

116 P associated with calcite study site mg P/g Ca Author experimental wetlands 7.88 this study wetland mesocosms 2.63 this study Lake Wallensee, Germany 1.90 summer, 4.2 fall Jager and Rohrs 1990 Lake Constance, Germany 3.44 Kleiner 1988 artificial lake water 0.8 - 3.9 Hoevelaken * Lake Constance, Germany 1.0 spring, 0.6 summer Rossknecht 1980 2-3 Hieltjes and Lijklema 1979# 0.4-4 House and Donaldson 1986 Lake Michigan, USA 1.05 Shafer and Armstrong 1994 * pers. comm., in Danen-Louwerse et al. 1995 # cited in Danen-Louwerse et al. 1995

Table 5.4 - Ratio of P to Ca in calcite precipitated in wetlands and hardwater lakes.

117 Solar — Energy

Ca Air I W ater column

8.9 Water column 4.4

Inflow

2.770 2,290 Dissolved Ca2+ Macrophytes

4 1 1 4 0 kg dry wt. Metaphyton

3.38

13.3 kg dry wt Ca as CaCOo I

0.013 CO sorbed

100 ^ Sediment P ■ N 'j Sediment Ca

650 36.2 4610 Ca as CaCO' exchangeable Ca sorbed V

Fig. 5.1. Diagram of the flows o f calcium and phosphorus in an average experimental wetland basin in 1998. Flows are in g m"2 yr and storages are in g m"-.

118 constructed Illinois wetlands ranging from 0.4 - 2.9 g P m ’ yr, and higher than the sustainable P removal rate of 1 g P m‘‘ yr for natural wetlands found by Richardson and

Qian (1999).

Over 240 kg m'^ of calcium carbonates are deposited into the sediments of each basin yearly. Assuming that the carbonates in the sediment are entirely from algal-induced precipitation, 1.88 kg P m " are deposited to the sediments through coprecipitation and sedimentation. This is equal to 42% of the total P or 85% of the soluble reactive P retained in the wetlands, a significant percentage for a previously imstudied wetland pathway.

In lakes, sorption/coprecipitation with calcite is also significant as a mechanism for

P removal. Shafer and Armstrong (1994) found that deposition of calcite-P accounted for

12-15% of the annual flux of P to the sediments in Lake Michigan. Danen-Louwerse et al.

(1995) calculated that coprecipitation accounted for 50-85% of the total P removal over three years in the eutrophic Lake Veluwe. In the mesotrophic Lake Constance, 35% of the total P removal from the epilimnion occurred via coprecipitation (Kleiner 1988). Jager and

Rohrs (1990) found that 25% of the P removal from the water column in a eutrophic

German lake occurred by coprecipitation. These similar results show that when calcite precipitation occurs in productive aquatic systems, sorption with calcite can be a significant sink for phosphorus. Because productive wetlands often have high P concentrations in the water column, and because of their compressed eutrophic zone and high primary productivity which can cause the high pH values necessary for calcite precipitation, eutrophic hardwater wetlands could remove large quantities of phosphorus through sorption with calcite.

Algal systems show promise for nutrient removal (Craggs et al. 1996), and are being tested as a possible final polishing step for removing P to the low levels necessary for the Everglades Nutrient Removal Project (R.L. Knight, pers.comm.). The possibility

119 o f p removal through both direct uptake and sorption with calcite, as well as the short generation time and rapid growth of algal species makes algal removal of phosphorus an important emerging ecological engineering technique.

120 CHAPTER 6

CONCLUSIONS AND RECOMMENDATIONS

6.1 Conclusions

1. Gross primary productivity (GPP) in the water column of highly productive temperate wetlands is similar, on an areal basis, to GPP values reported for eutrophic hardwater lakes, showing that despite an extremely shallow water column, wetlands can be as productive as these deeper aquatic ecosystems.

2. Because of the shallow euphotic zone in wetlands, water column metabolism caused significant changes in dissolved oxygen, pH and conductivity in the experimental wetlands and algal mesocosms during the growing season (May-September).

3. Aquatic metabolism was not significantly different between the planted and unplanted wetlands overall during 1996-98, confirming earlier studies which concluded that the wetlands were converging in structure and function during this time period.

4. Aquatic metabolism in deepwater areas containing no emergent macrophytes was much higher than in shallow vegetated areas, due to shading effects and much shallower water in the latter areas.

5. Calcite precipitation occurred in the wetland basins and in the algal mesocosms as a result of algal photosynthesis, resulting in a decrease in conductivity of up to 12% on a diurnal time scale and a decrease in total dissolved solids of up to 13% on an annual time scale.

121 6. Algal-induced calcite precipitation was species-specific, occurring on certain macroalgal species {Cladophora and Hydrodictyon), but not on others {Spirogyra).

1. Significant amounts of P were associated with the calcite crystals through sorption, sometimes exceeding the amoimt removed fi-om the water column by algal uptake.

8. Calcite which precipitated on algal filaments in the water column was deposited into the sediments of the experimental wetlands.

9. Calcite precipitation occurred on a diurnal time-scale, as shown by decreases in calcium concentrations fi-om dawn to dusk in the experimental wetlands.

6.2 Recommendations

1. Further research is needed to determine the importance of calcite and phosphorus coprecipitation in other marshes fed by hardwater sources.

2. Because macroalgae obtain their nutrients directly fi-om the water column instead of the sediments, and because of the potential for phosphorus removal through

coprecipitation, constructed macroalgal treatment wetlands hold promise for removal of low

levels of phosphorus as a final polishing step in surface water treatment. If calcite

precipitation plays a significant role in phosphorus removal by constructed wetlands, many

questions must be answered to understand and optimize phosphorus removal though this

pathway.

3. Sequential extraction techniques or radioisotope experiments should be used to

determine the amoimt of phosphorus associated with calcite and dolomite in wetland

sediments.

122 4. The relative importance of biotic (i.e., pH-driven by primary production) and abiotic (i.e., driven by temperature changes or outgassing of CO, in groundwater-fed wetlands) calcite precipitation in P removal in wetlands must be addressed, as must the phosphorus removal rates o f algae by nutrient uptake.

5. One important question is whether phosphorus sorption with calcite in wetlands is a long-term phosphorus sink, or whether seasonal changes in water chemistry lead to desorption of calcite-immobilized phosphorus.

6. Investigations area needed to determine which species of algae and submerged aquatics precipitate the most calcite, and what conditions (water temperature, pH, and P and Ca loading/concentrations) lead to maximum sustainable phosphorus removal through sorption and/or coprecipitation with calcite.

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135 APPENDICES

136 APPENDIX A -WETLAND WATER QUALITY DATA

Water quality measurements in the water column in the experimental wetland basins. The key to the site code is: W l= Wetland 1, W2=Wetland 2, P=inflow pipe. I = inflow subbasin, M= middle subbasin, 0 = outflow subbasin. D=deepwater area, S=shallow area.

Temp DO Cond Cond at 25 C Redox Date Site Time C mg/L |iS/cm |iS/cm pH mV 7/15/98 WIP dawn 24.41 6.44 560 565 7.62 445 7/15/98 WIID dawn 23.6 5.68 566 579 7.68 439 7/15/98 WHS dawn 22.88 1.22 515 533 7.12 276 7/15/98 WIMD dawn 23.53 2.33 552 565 7.38 376 7/15/98 WIMS dawn 23.57 1.05 523 535 263 7/15/98 WIOD dawn 23.2 1.86 529 545 i~5 219 7/15/98 WIOS dawn 23.77 1.82 501 511 7.11 351 7/15/98 W2P dawn 24.37 6.41 562 568 7.77 378 7/15/98 W2ID dawn 23.64 6.06 566 579 7.93 381 7/15/98 W2IS dawn 23.51 1.55 554 568 7.4 215 7/15/98 W2MD dawn 23.31 6.95 548 563 7.67 178 7/15/98 W2MS dawn 23.46 1.24 550 564 7.33 370 7/15/98 W20D dawn 23.98 2.78 551 560 7.35 355 7/15/98 W20S dawn 23.68 1.11 513 524 7.33 308 7/15/98 WIP dusk 24.94 6.4 561 562 7.66 416 7/15/98 WIID dusk 24.37 6.69 565 571 7.82 290 7/15/98 WHS dusk 24.85 2.7 507 508 7.27 247 7/15/98 WIMD dusk 23.75 13.17 545 556 8.25 249 7/15/98 WIMS dusk 23.13 9.34 506 522 7.37 265 7/15/98 WIOD dusk 26.85 19.93 462 448 8.62 313 7/15/98 WIOS dusk 26.92 11.15 460 445 8.06 365 7/15/98 W2P dusk 24.92 6.64 561 562 7.75 401 7/15/98 W2ID dusk 24.76 6.68 556 558 7.88 394 7/15/98 W2IS dusk 24.33 2.35 545 551 7.23 215 7/15/98 W2MD dusk 26.15 14.9 513 503 8.42 306 7/15/98 W2MS dusk 23.55 8.62 510 522 7.84 221 7/15/98 W20D dusk 26.38 13.95 502 491 8.23 325 7/15/98 W 20S dusk 25.01 3.75 517 517 7.41 259 7/16/98 WIP dawn 25.37 6.94 575 572 7.71 460 7/16/98 WIID dawn 24.66 4.34 572 575 7.6 455 7/16/98 WHS dawn 22.93 0.46 540 558 7.14 144 7/16/98 WIMD dawn 23.58 1.05 568 581 7.25 267 7/16/98 WIMS dawn 23.51 1.04 546 559 7.31 273 7/16/98 WIOD dawn 24.33 1.37 519 525 7.37 285 7/16/98 WIOS dawn 23.93 0.76 488 497 7.14 278 7/16/98 W2P dawn 25.31 6.93 577 574 7.78 322 7/16/98 W2ID dawn 24.52 3.95 574 579 7.7 322 7/16/98 W2IS dawn 22.97 2.68 586 606 7.17 166 7/16/98 W2MD dawn 22.65 1.24 581 603 7.35 212 7/16/98 W2MS dawn 23.1 1.18 541 558 7.17 252 7/16/98 W 20D dawn 23.93 2.06 527 536 7.25 277 7/16/98 W 20S dawn 22.47 1.52 522 544 7.16 261 8/14/98 WIP dawn 23.82 4.84 613 625 7.37 618 8/14/98 WIID dawn 23.26 5.24 540 555 7.41 512 8/14/98 WHS dawn 22.56 3.28 551 573 7.34 315 8/14/98 WIMD dawn 21.77 3.94 544 573 7.38 407 8/14/98 WIMS dawn 20.44 2.06 538 578 7.27 446 8/14/98 WIOD dawn 22.02 4.8 528 554 7.57 412 8/14/98 WIOS dawn 21.61 4.41 501 529 7.44 418

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Temp DO Cond Cond at 25 C Redox Date Site Time C mg/L |lS/cm |iS/cm pH mV 8/14/98 W2P dawn 23.82 4.99 553 564 7.22 444 8/14/98 W2ID dawn 23.68 6.02 549 561 7.4 489 8/14/98 W2IS dawn 22.59 4.25 536 557 7.2 496 8/14/98 W2MD dawn 22.15 4.24 534 559 7.36 470 8/14/98 W2MS dawn 20.73 2.04 533 570 7.08 472 8/14/98 W20D dawn 22.06 4 539 565 7.2 491 8/14/98 W20S dawn 20.4 2.47 538 579 7.07 495 8/14/98 WIP dusk 25 7.42 574 574 7.69 471 8/14/98 WIID dusk 25.22 6.56 570 568 8.04 474 8/14/98 WHS dusk 23.98 4.34 592 602 7.52 501 8/14/98 WIMD dusk 21.92 17.36 588 618 8.54 404 8/14/98 WIMS dusk 24.22 3.4 566 573 7.39 338 8/14/98 WIOD dusk 27.33 26.25 410 394 9.49 371 8/14/98 WIOS dusk 22.06 18.31 487 511 8.58 333 8/14/98 W2P dusk 24.88 7.43 577 578 7.47 387 8/14/98 W2ID dusk 24.81 7.07 574 576 7.66 402 8/14/98 W2IS dusk 22.56 5.2 610 634 7.52 427 8/14/98 W2MD dusk 26.21 12.15 548 537 8.62 402 8/14/98 W2MS dusk 23.08 4.01 535 552 7.37 401 8/14/98 W20D dusk 25.53 11.79 540 535 8.16 415 8/14/98 W20S dusk 25.18 9.64 543 541 7.91 409 8/15/98 WIP dawn 24.19 5.54 570 578 7.52 522 8/15/98 WIID dawn 23.82 4.8 557 568 7.61 488 8/15/98 WHS dawn 23.19 2.99 561 578 7.06 450 8/15/98 WIMD dawn 22.74 0.63 560 581 7.3 466 8/15/98 WIMS dawn 22.16 1.95 560 586 7.44 461 8/15/98 WIOD dawn 23.04 4.22 503 519 7.51 366 8/15/98 WIOS dawn 21.84 3.02 481 506 7.32 368 8/15/98 W2P dawn 24.19 5.62 552 559 7.22 438 8/15/98 W2ID dawn 23.97 4.82 565 575 7.53 418 8/15/98 W2IS dawn 23.28 3.73 563 579 7.24 444 8/15/98 W2MD dawn 23.02 1.97 564 582 7.18 382 8/15/98 W2MS dawn 22.47 1.57 560 583 7.15 366 8/15/98 W20D dawn 23.02 1.8 557 575 7.24 377 8/15/98 W20S dawn 22.33 1.44 565 590 7.26 412 10/21/98 WIP dawn 14.03 6.54 767 928 7.56 539 10/21/98 WIID dawn 13.13 7.4 756 947 7.62 501 10/21/98 WHS dawn 11.32 7.26 742 993 7.79 484 10/21/98 WIMD dawn 10.45 6.45 716 988 8.01 435 10/21/98 WIMS dawn 7.71 3.89 690 1041 8.11 464 10/21/98 WIOD dawn 9.7 9.82 652 923 8.46 452 10/21/98 WIOS dawn 9.4 6.82 667 953 8.39 463 10/21/98 W2P dawn 14.04 6.39 765 925 7.49 523 10/21/98 W2ID dawn 12.97 8.62 751 947 7.67 501 10/21/98 W2IS dawn 12.75 6.52 742 943 7.75 492 10/21/98 W2MD dawn 10.88 6.94 723 983 7.93 478 10/21/98 W2MS dawn 8.31 6.59 715 1059 8.05 484 10/21/98 W20D dawn 9.78 8.86 683 964 8.23 467 10/21/98 W20S dawn 10.14 6.47 697 972 8.14 381 10/21/98 WIP dusk 13.71 6.38 723 886 7.06 512 10/21/98 WIID dusk 13.86 9.24 710 865 8 503 10/21/98 WHS dusk 13.12 7.03 699 876 8.14 507 10/21/98 WIMD dusk 14.44 18.64 666 793 8.88 496

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138 Appendix A, continued

Temp DO Cond Cond at 25 C Redox Date Site Time C mg/L pS/cm pS/cm __PH mV 10/21/98 WIMS dusk 10.68 7.75 650 890 9.04 502 10/21/98 WIOD dusk 12.54 13.81 617 790 9.48 503 10/21/98 WIOS dusk 12.05 7.97 614 801 9.24 504 10/21/98 W2P dusk 13.61 6.28 710 873 8.54 516 10/21/98 W2ID dusk 13.78 8.96 705 862 8.6 515 10/21/98 W2IS dusk 13.5 7.35 705 871 8.64 514 10/21/98 W2MD dusk 13.63 13.84 679 835 9.16 499 10/21/98 W2MS dusk 11.42 7.8 672 896 9 507 10/21/98 W 20D dusk 12.43 12.94 640 823 9.1 507 10/21/98 W 20S dusk 12.74 10.9 645 820 9.17 507 10/22/98 WIP dawn 12.54 6.91 706 904 7.08 624 10/22/98 WIID dawn 10.73 9.24 703 961 7.46 615 10/22/98 WHS dawn 9.08 6.13 693 1001 7.72 609 10/22/98 WIMD dawn 7.98 6.57 715 1070 7.91 611 10/22/98 WIMS dawn 6.08 6.86 692 1098 8.03 597 10/22/98 WIOD dawn 7.27 9.03 656 1004 7.47 573 10/22/98 WIOS dawn 6.76 8.42 629 978 8.36 577 10/22/98 W2P dawn 12.54 6.76 700 896 7.67 575 10/22/98 W2ID dawn 10.58 7.84 703 965 7.79 574 10/22/98 W2IS dawn 10.36 6.87 693 959 7.84 570 10/22/98 W2MD dawn 8.35 7.34 708 1047 8 565 10/22/98 W2MS dawn 6.45 6.62 693 1087 8.07 563 10/22/98 W 20D dawn 7.22 8.04 679 1040 8.21 551 10/22/98 W 20S dawn 7.83 6.91 689 1036 8.04 549 3/30/99 WIP dawn 10.58 9.18 600 824 8.02 480 3/30/99 WIID dawn 9.27 9.38 608 873 8.06 456 3/30/99 WHS dawn 8.05 8.26 608 908 8.03 457 3/30/99 WIMD dawn 6.64 9.21 601 937 7.91 447 3/30/99 WIMS dawn 5.74 6.11 582 933 7.94 444 3/30/99 WIOD dawn 8.14 10.5 568 846 8.3 437 3/30/99 WIOS dawn 6.68 6.04 562 876 7.9 424 3/30/99 W2P dawn 10.52 8.98 606 834 8.06 433 3/30/99 W2ID dawn 9.5 10.84 606 863 8.19 431 3/30/99 W2IS dawn 9.49 8.2 593 845 8.27 431 3/30/99 W2MD dawn 8.04 8.27 600 896 8.2 439 3/30/99 W2MS dawn 5.95 5.85 595 947 7.72 448 3/30/99 W 20D dawn 7.94 8.99 587 879 7.78 460 3/30/99 W 20S dawn 10.29 7.62 536 743 8 446 3/30/99 WIP dusk 11.19 9.41 599 805 7.97 474 3/30/99 WIID dusk 14.59 11.37 591 700 8.31 457 3/30/99 WHS dusk 14.48 8.97 583 693 8.25 458 3/30/99 WIMD dusk 16.97 13.58 567 642 8.62 445 3/30/99 WIMS dusk 13.7 9.18 562 689 8.38 454 3/30/99 WIOD dusk 17.17 18.63 544 614 9.07 452 3/30/99 WIOS dusk 15.79 12.43 522 588 8.92 440 3/30/99 W2P dusk 10.99 9.25 601 814 7.86 476 3/30/99 W2ID dusk 13.71 15.4 591 724 8.66 495 3/30/99 W2IS dusk 13.99 10.56 570 691 8.61 447 3/30/99 W2MD dusk 16.79 12.63 584 631 8.31 441 3/30/99 W2MS dusk 13.66 8.35 572 702 7.98 454 3/30/99 W 20D dusk 13.58 19.14 614 756 8.52 464 3/30/99 W 20S dusk 16.01 10.64 570 636 7.49 446 3/31/99 WIP dawn 11.75 10.5 581 766 8.08 454

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139 Appendix A, continued

Temp DO Cond Cond at 25 C Redox Date Site Time C mg/L liS/cm jiS/cm pH mV 3/31/99 WIID dawn 9.62 9.82 586 831 7.96 457 3/31/99 WHS dawn 8.98 7.31 580 840 7.68 462 3/31/99 WIMD dawn 6.43 8.58 587 921 7.89 372 3/31/99 WIMS dawn 6.12 7.65 557 882 8 457 3/31/99 WIOD dawn 7.12 11.03 547 841 8.08 499 3/31/99 WIOS dawn 7.67 8.16 530 801 7.77 465 3/31/99 W2P dawn 11.93 10.85 586 767 8.2 450 3/31/99 W2ID dawn 9.68 10.99 585 828 8.18 452 3/31/99 W2IS dawn 9.44 9.3 578 825 8.08 441 3/31/99 W2MD dawn 7.86 8.79 581 873 7.76 451 3/31/99 W2MS dawn 5.69 7.57 565 907 7.78 457 3/31/99 W 20D dawn 7.75 8.15 566 853 7.73 461 3/31/99 W 20S dawn 8.06 7.47 567 846 7.92 457 6/1/99 WIP dawn 22.72 5.61 660 685 7.85 495 6/1/99 WIID dawn 20.26 3.41 631 680 7.52 512 6/1/99 WHS dawn 21.23 0.87 597 634 7.27 488 6/1/99 WIMD dawn 20.84 0.64 584 624 7.28 454 6/1/99 WIMS dawn 20.16 0.93 550 594 7.11 448 6/1/99 WIOD dawn 21.16 2.21 523 556 7.39 480 6/1/99 WIOS dawn 20.78 1.43 515 551 7.32 312 6/1/99 W2P dawn 22.66 4.87 630 654 7.77 418 6/1/99 W2ID dawn 19.38 2.24 635 694 7.51 468 6/1/99 W2IS dawn 20.42 1.66 599 644 7.22 411 6/1/99 W2MD dawn 20.86 0.95 594 634 7.23 437 6/1/99 W2MS dawn 20.82 0.74 569 608 7.17 338 6/1/99 W 20D dawn 20.82 0.43 536 573 7.39 384 6/1/99 W 20S dawn 20.78 0.97 490 524 7.24 393 6/1/99 WIP dusk 22.74 7.6 650 674 7.99 477 6/1/99 WIID dusk 22.79 6.21 616 638 8.24 472 6/1/99 WHS dusk 23.26 5.88 600 617 7.92 656 6/1/99 WIMD dusk 23.31 9.06 597 614 8.5 490 6/1/99 WIMS dusk 22.09 0.78 599 628 7.2 328 6/1/99 WIOD dusk 23.82 7.11 550 561 7.73 400 6/1/99 WIOS dusk 22.99 4.21 540 558 7.49 400 6/1/99 W2P dusk 22.68 7.53 629 653 8.1 429 6/1/99 W2ID dusk 20.93 6.81 639 682 8.04 482 6/1/99 W2IS dusk 22.66 3.84 606 629 7.77 398 6/1/99 W2MD dusk 21.21 7.18 635 675 8.02 536 6/1/99 W2MS dusk 22.93 1.92 584 604 7.41 432 6/1/99 W 20D dusk 22.43 4.84 570 594 8.76 661 6/1/99 W 20S dusk 22.97 8.87 500 517 8.03 407 6/2/99 WIP dawn 22.16 6.82 616 645 7.94 492 6/2/99 WIID dawn 19.9 5.94 638 691 7.74 495 6/2/99 WHS dawn 21.24 1.74 618 656 7.43 467 6/2/99 WIMD dawn 19.74 1.11 630 684 7.26 531 6/2/99 WIMS dawn 20.26 1.39 620 668 7.12 489 6/2/99 WIOD dawn 20.86 2.35 592 632 7.33 451 6/2/99 WIOS dawn 19.58 1.12 535 583 7.03 474 6/2/99 W2P dawn 22.25 6.97 631 659 7.99 433 6/2/99 W2ID dawn 21.42 5.25 641 679 7.9 518 6/2/99 W2IS dawn 19.68 2.86 634 689 7.47 477 6/2/99 W2MD dawn 19.7 1.4 642 698 7.29 463 6/2/99 W2MS dawn 20.96 0.94 626 668 7.07 459 6/2/99 W 20D dawn 19.5 0.86 621 677 7.23 613 6/2/99 W20S dawn 20.68 1.07 542 580 7.07 441

140 APPENDIX B - ADDITIONAL WETLAND WATER QUALITY DATA

Additional water quality measurements in the experimental wetlands. The key to the site code is: W l= Wetland 1, W2 = Wetland 2. P=inflow pipe. I=inflow subbasin, M=middle subbasin, 0=outflow subbasin. D=deepwater area, S=shallow water area.

SRP TP Ca TDC D ie DOC TC TIC TOC Total Date Site Time Hg/L Hg/L mg/L 7/15/98 WIP dawn 59.5 148.3 51.7 55.0 45.0 10.1 50.1 41.4 8.7 151.5 7/15/98 WIID dawn 44.8 130.0 53.9 53.4 45.4 7.9 49.3 41.4 7.9 152.7 7/15/98 WHS dawn 19.9 113.6 47.3 62.6 52.9 9.6 54.3 45.4 8.9 148.4 7/15/98 WIMD dawn 1.2 89.1 51.7 57.3 48.9 8.4 42.2 35.7 6.6 147.7 7/15/98 WIMS dawn 0.0 118.8 49.5 64.4 53.0 11.4 46.1 37.0 9.1 158.2 7/15/98 WIOD dawn 0.0 25.7 48.4 57.9 48.6 9.3 41.0 35.0 6.0 148.8 7/15/98 WIOS dawn 0.0 94.9 42.9 59.2 47.9 11.3 43.0 35.7 7.3 137.0 7/15/98 W2P dawn 81.6 136.3 53.9 54.6 45.6 9.1 35.8 29.7 6.1 147.6 7/15/98 W2ID dawn 65.5 119.6 52.8 54.5 45.9 8.6 41.2 34.7 6.5 146.8 7/15/98 W2IS dawn 39.9 320.9 52.8 65.4 53.3 12.1 44.4 37.4 7.0 143.8 7/15/98 W2MD dawn 12.5 72.6 51.7 55.9 46.7 9.2 42.3 35.2 7.1 152.9 7/15/98 W2MS dawn 0.0 49.2 51.7 62.6 53.2 9.4 39.5 31.4 8.1 160.7 7/15/98 W20D dawn 0.0 48.7 50.6 57.9 48.4 9.5 38.4 30.9 7.5 149.1 7/15/98 W20S dawn 0.0 56.8 55.0 60.5 50.0 10.5 42.5 35.5 7.1 146.9 7/15/98 WIP dusk 67.1 114.6 52.8 45.5 38.4 7.1 38.6 31.3 7.3 154.1 7/15/98 WIID dusk 69.0 138.9 44.0 45.1 37.1 8.0 37.6 28.2 9.4 146.8 7/15/98 WHS dusk 2.1 108.8 40.7 51.7 43.3 8.4 43.3 34.6 8.7 151.7 7/15/98 V/IMD dusk 13.2 58.0 45.1 40.7 33.0 7.7 33.1 24.5 8.7 140.5 7/15/98 WIMS dusk 0.0 218.8 38.5 43.5 35.6 7.9 35.7 27.2 8.5 122.4 7/15/98 WIOD dusk 0.0 23.3 38.5 35.1 27.3 7.8 28.3 21.0 7.3 117.2 7/15/98 WIOS dusk 0.0 52.7 41.8 34.9 27.1 7.8 28.8 21.0 7.7 108.2 7/15/98 W2P dusk 75.1 119.6 60.5 44.8 37.2 7.6 36.9 30.7 6.2 154.9 7/15/98 W2ID dusk 39.8 123.8 62.7 45.5 36.9 8.6 35.9 28.9 7.0 148.3 7/15/98 W2IS dusk 42.0 224.2 47.3 48.1 39.4 8.7 36.9 30.2 6.7 142.3 7/15/98 W2MD dusk 0.0 44.6 42.9 35.9 28.7 7.2 32.5 25.1 7.4 122.8 7/15/98 W2MS dusk 1.3 92.4 46.2 41.9 34.5 7.4 37.9 29.6 8.4 136.8 7/15/98 W 20D dusk 0.0 51.1 47.3 43.3 35.7 7.5 34.8 27.0 7.8 143.3 7/15/98 W 20S dusk 0.0 181.7 47.3 49.0 41.2 7.9 39.5 31.6 7.9 153.0 7/16/98 WIP dawn 84.2 130.1 53.9 45.6 38.0 7.6 34.9 28.5 6.4 7/16/98 WIID dawn 47.9 112.5 53.9 47.1 39.0 8.2 42.9 35.6 7.3 7/16/98 WHS dawn 0.0 159.6 50.6 55.4 46.5 8.9 51.0 41.1 9.9 7/16/98 WIMD dawn 14.3 69.3 53.9 49.2 42.5 6.8 46.5 38.2 8.3 7/16/98 WIMS dawn 0.0 99.6 50.6 52.6 44.4 8.2 48.3 39.6 8.6 7/16/98 WIOD dawn 0.0 15.4 47.3 44.1 36.9 7.2 43.5 35.0 8.6 7/16/98 WIOS dawn 0.0 56.9 41.8 45.0 37.6 7.4 36.6 28.9 7.8 7/16/98 W2P dawn 60.3 105.2 55.0 45.7 37.9 7.8 34.7 27.8 6.9 7/16/98 W2ID dawn 56.0 143.3 53.9 46.0 38.4 7.7 32.8 27.2 5.5 7/16/98 W2IS dawn 37.4 460.6 57.2 54.1 47.5 6.6 36.5 29.2 7.3 7/16/98 W2MD dawn 0.0 81.7 53.9 49.7 42.4 7.3 36.0 29.0 7.0 7/16/98 W2MS dawn 0.0 77.3 52.8 54.0 43.5 10.5 39.1 31.0 8.1 7/16/98 W 20D dawn 0.0 41.4 46.2 48.2 40.0 8.2 36.7 28.9 7.8 7/16/98 W 20S dawn 0.0 79.2 46.2 48.7 40.1 8.6 36.6 29.1 7.5 8/14/98 WIP dawn 126.4 242.4 54.7 53.9 43.0 10.9 61.5 50.0 11.5 136.3 8/14/98 WIID dawn 82.4 262.6 54.1 58.2 47.3 10.9 62.8 51.6 11.3 139.0 8/14/98 WHS dawn 37.7 270.8 52.8 59.7 48.1 11.5 67.8 55.8 12.0 138.6 8/14/98 WIMD dawn 0.3 90.3 57.3 63.5 51.7 11.7 67.7 55.7 12.0 142.9 8/14/98 WIMS dawn 7.1 151.2 52.8 60.9 48.5 12.4 68.4 56.1 12.3 141.7 8/14/98 WIOD dawn 0.3 66.1 49.2 63.4 49.1 14.3 66.1 52.7 13.4 141.3 8/14/98 WIOS dawn 0.3 149.9 41.1 52.6 40.5 12.2 61.2 47.2 14.1 115.8

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141 Appendix B, continued

SRP TP Ca TDC D ie DOC TC TIC TOC Total Date Site Time lig/L lig/L mg/Lmg/L mg/L mg/L mg/L mg/L mg/L alkalinit 8/14/98 W2P dawn 141.2 248.7 49.5 55.7 45.7 10.0 61.8 50.3 11.6 133.8 8/14/98 W2ID dawn 124.3 243.7 51.2 59.0 47.5 11.6 63.8 51.7 12.1 133.6 8/14/98 W2IS dawn 58.4 377.2 51.5 61.9 50.3 11.7 67.7 56.0 11.7 134.7 8/14/98 W2MD dawn 17.0 191.7 50.9 62.1 50.4 11.7 67.5 56.0 11.4 137.2 8/14/98 W2MS dawn 56.2 201.6 52.1 64.2 52.1 12.2 69.8 57.7 12.1 141.5 8/14/98 W20D dawn 0.3 143.5 53.2 63.9 51.0 12.9 68.9 57.4 11.5 140.7 8/14/98 W 20S dawn 0.3 146.4 53.0 64.9 53.3 11.6 70.2 57.7 12.6 142.8 8/14/98 WIP dusk 135.5 245.0 58.4 55.7 45.2 10.5 61.0 50.4 10.6 116.2 8/14/98 WIID dusk 43.8 289.6 48.2 61.3 48.7 12.7 65.4 51.9 13.6 132.9 8/14/98 WHS dusk 75.5 233.9 50.5 61.2 49.5 11.7 65.5 54.0 11.5 133.5 8/14/98 WIMD dusk 40.7 155.2 46.3 48.1 36.8 11.4 49.9 38.9 11.0 115.9 8/14/98 WIMS dusk 25.9 155.5 51.4 63.1 52.0 11.1 65.9 54.0 11.9 134.1 8/14/98 WIOD dusk 4.5 49.5 24.5 34.2 21.6 12.6 29.8 18.0 11.8 74.1 8/14/98 WIOS dusk 0.3 129.0 30.6 41.9 30.6 11.2 88.1 8/14/98 W2P dusk 138.2 225.0 51.2 59.0 48.1 10.9 61.6 50.2 11.4 135.5 8/14/98 W2ID dusk 111.2 275.2 50.4 59.2 48.3 10.9 61.3 49.9 11.5 133.7 8/14/98 W2IS dusk 61.4 513.4 51.9 59.3 48.6 10.7 62.1 50.2 11.9 140.8 8/14/98 W2MD dusk 65.2 151.7 46.8 51.2 40.9 10.3 56.0 44.7 11.2 121.9 8/14/98 W2MS dusk 44.2 198.3 50.9 61.2 50.3 10.9 66.8 54.5 12.3 135.3 8/14/98 W20D dusk 0.3 78.9 49.3 55.9 45.3 10.6 59.7 48.6 11.1 132.1 8/14/98 W 20S dusk 12.6 174.9 46.8 57.7 46.7 11.0 59.6 47.6 12.0 128.6 8/15/98 WIP dawn 128.: 228.5 53.7 60.4 50.1 10.3 62.9 52.6 10.4 141.0 8/15/98 WIID dawn 100.2 208.3 34.9 61.4 50.4 11.0 65.2 53.0 12.2 140.5 8/15/98 WHS dawn 58.7 203.3 52.8 61.7 51.7 10.1 66.6 54.5 12.2 140.8 8/15/98 WIMD dawn 19.2 91.3 54.8 65.3 54.5 10.9 71.6 57.8 13.8 141.2 8/15/98 WIMS dawn 16.2 143.5 56.9 64.7 53.9 10.8 69.1 57.3 11.9 139.2 8/15/98 WIOD dawn 0.3 56.1 49.2 61.3 48.5 12.8 63.8 51.7 12.1 128.6 8/15/98 WIOS dawn 0.3 104.1 41.8 55.9 43.3 12.5 59.3 46.5 12.8 108.6 8/15/98 W2P dawn 136.1 233.8 54.9 60.3 49.3 11.0 64.7 53.5 11.2 137.3 8/15/98 W2ID dawn 126.8 227.6 54.6 61.2 50.7 10.5 64.6 53.6 11.0 137.6 8/15/98 W2IS dawn 88.1 280.9 37.8 65.2 54.2 11.0 69.5 56.9 12.6 137.4 8/15/98 W2MD dawn 39.7 151.4 49.8 64.4 54.4 10.0 68.3 57.5 10.7 118.4 8/15/98 W2MS dawn 30.5 190.0 58.7 67.8 56.3 11.5 72.0 60.7 11.3 143.4 8/15/98 W20D dawn 9.8 78.4 53.1 67.0 55.8 11.2 70.1 58.7 11.3 131.9 8/15/98 W20S dawn 6.0 105.0 54.3 69.1 57.8 11.3 72.0 60.3 11.7 145.9 10/21/98 WIP dawn 298.5 378.2 24.6 43.7 36.9 6.8 44.4 36.8 7.6 134.7 10/21/98 WIID dawn 303.8 374.6 27.0 43.2 36.2 7.1 38.7 31.4 7.3 126.3 10/21/98 WHS dawn 270.3 363.2 25.2 43.7 36.4 7.3 42.8 35.9 7.0 134.1 10/21/98 WIMD dawn 202.4 260.9 27.3 44.3 36.4 7.9 42.3 34.9 7.4 129.4 10/21/98 WIMS dawn 126.5 178.7 25.6 45.2 38.0 7.2 44.1 36.3 7.8 125.5 10/21/98 WIOD dawn 83.8 132.1 27.3 40.0 33.2 6.9 38.9 32.0 6.9 115.8 10/21/98 WIOS dawn 84.6 146.8 27.3 42.3 34.5 7.8 41.9 33.5 8.3 125.3 10/21/98 W2P dawn 302.9 383.8 29.4 44.0 37.4 6.5 41.9 34.5 7.4 138.7 10/21/98 W2ID dawn 282.9 346.9 29.4 43.1 36.2 6.9 42.2 35.3 6.9 124.1 10/21/98 W2IS dawn 287.7 344.4 31.1 43.5 36.6 6.9 32.8 26.2 6.6 134.3 10/21/98 W2MD dawn 195.3 298.7 28.5 43.6 36.5 7.1 40.6 33.9 6.8 116.8 10/21/98 W2MS dawn 213.0 276.3 29.2 45.3 37.3 7.9 37.8 30.9 6.9 123.4 10/21/98 W 20D dawn 104.2 210.2 25.4 43.9 36.0 7.8 38.6 30.9 7.7 130.2 10/21/98 W 20S dawn 145.7 187.2 26.6 44.6 36.2 8.3 35.9 28.8 7.1 122.2 10/21/98 WIP dusk 322.4 395.7 31.3 45.9 38.6 7.3 44.3 38.2 6.1 134.7 10/21/98 WIID dusk 304.0 368.6 31.1 44.5 37.5 7.1 42.2 35.6 6.6 137.2 10/21/98 WHS dusk 273.1 415.7 30.4 44.8 36.9 7.9 42.1 35.3 6.8 131.1 10/21/98 WIMD dusk 224.1 283.4 28.3 40.0 32.8 7.1 38.3 31.3 7.0 126.7

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142 Appendix B, continued

SRP TP Ca TDC DIG DOC TC TIC TOC Total Date Site Time Kg/i. mg/T- mg/L mg/L mg/Lmg/L mg/L mg/L 10/21/98 WIMS dusk 103.9 207.7 29.0 44.1 36.4 7.6 41.5 34.4 7.1 119.3 10/21/98 WIOD dusk 64.8 133.6 32.1 38.2 30.8 7.5 37.1 29.6 7.4 114.2 10/21/98 WIOS dusk 64.7 180.7 29.2 40.1 32.8 7.3 38.3 31.0 7.3 113.2 10/21/98 W2P dusk 325.8 398.1 28.1 46.3 39.0 7.3 43.6 36.9 6.7 134.4 10/21/98 W21D dusk 302.7 370.6 29.0 44.8 37.1 7.7 42.4 35.7 6.6 126.1 10/21/98 W21S dusk 287.3 398.0 21.3 44.2 37.2 7.1 41.9 35.6 6.3 133.0 10/21/98 W2MD dusk 238.3 307.3 31.5 41.6 34.7 6.8 39.2 32.4 6.8 122.5 10/21/98 W2MS dusk 223.6 304.2 31.7 42.7 35.3 7.4 42.1 34.7 7.3 127.3 10/21/98 W 20D dusk 135.3 191.7 28.3 41.1 33.3 7.8 38.8 31.7 7.0 116.7 10/21/98 W20S dusk 140.6 214.1 29.4 41.0 33.7 7.3 38.7 31.6 7.2 125.9 10/22/98 WIP dawn 281.5 354.9 33.2 46.4 39.9 6.5 45.7 39.3 6.5 149.1 10/22/98 WIID dawn 289.9 355.8 30.4 45.9 39.2 6.6 44.8 38.6 6.1 130.8 10/22/98 WHS dawn 282.4 383.9 31.3 46.5 39.7 6.8 46.7 37.6 9.1 137.5 10/22/98 WIMD dawn 197.4 271.4 30.6 45.8 38.8 7.0 43.6 37.2 6.4 133.4 10/22/98 WIMS dawn 159.6 203.2 29.8 45.0 37.5 7.5 44.7 37.2 7.5 137.9 10/22/98 WIOD dawn 107.4 155.7 31.3 42.0 34.6 7.4 41.3 34.0 7.3 121.7 10/22/98 WIOS dawn 69.3 177.5 29.8 42.7 34.2 8.5 39.9 32.7 7.2 128.2 10/22/98 W2P dawn 280.1 358.7 32.8 47.3 39.9 7.4 46.4 38.8 7.6 143.3 10/22/98 W21D dawn 264.1 360.5 32.6 46.1 39.0 7.2 45.1 38.2 7.0 131.1 10/22/98 W21S dawn 261.9 420.3 30.9 47.3 39.2 8.1 44.4 37.1 7.4 135.5 10/22/98 W2MD dawn 244.4 312.7 31.5 46.2 39.1 7.1 45.0 38.1 6.9 139.8 10/22/98 W2MS dawn 223.8 303.1 27.2 46.7 38.0 8.8 44.4 37.0 7.5 134.3 10/22/98 W 20D dawn 165.5 218.3 29.0 44.5 37.3 7.2 44.1 36.5 7.6 138.7 10/22/98 W 20S dawn 162.3 224.5 32.3 44.9 37.5 7.4 43.7 36.2 7.5 133.9 3/30/99 WIP dawn 28.9 80.9 80.1 41.5 35.7 5.8 41.6 36.9 4.7 153.6 3/30/99 WIID dawn 27.5 87.8 80.8 40.9 35.4 5.5 42.1 37.0 5.1 149.2 3/30/99 WHS dawn 25.4 114.5 79.4 40.5 34.7 5.7 42.0 36.4 5.6 152.0 3/30/99 WIMD dawn 11.7 53.4 80.8 40.6 34.6 6.0 43.0 37.1 5.9 148.7 3/30/99 WIMS dawn 6.1 52.3 73.9 39.5 32.8 6.7 40.4 34.5 5.8 135.8 3/30/99 WIOD dawn 0.0 35.5 72.6 38.3 31.4 6.9 39.2 33.4 5.8 134.5 3/30/99 WIOS dawn 0.1 131.7 71.3 38.4 31.2 7.2 40.7 34.0 6.7 132.5 3/30/99 W2P dawn 28.3 73.6 85.3 40.0 34.7 5.3 53.3 36.8 16.4 152.2 3/30/99 W21D dawn 21.2 81.0 80.1 39.9 34.4 5.6 42.3 36.0 6.3 152.7 3/30/99 W21S dawn 19.3 123.2 78.0 38.2 33.5 4.6 41.9 36.4 5.5 45.5 3/30/99 W2MD dawn 5.0 110.6 70.7 39.6 33.5 6.1 41.6 35.3 6.4 148.6 3/30/99 W2MS dawn 2.6 68.5 68.2 39.3 32.8 6.6 42.7 36.2 6.5 145.9 3/30/99 W 20D dawn 0.1 145.2 64.6 39.0 31.8 7.2 41.1 34.9 6.2 140.3 3/30/99 W20S dawn 1.3 182.8 72.6 38.3 31.8 6.5 41.2 34.3 6.9 143.7 3/30/99 WIP dusk 29.5 112.0 85.3 40.9 35.3 5.6 43.2 37.3 5.9 150.6 3/30/99 WHD dusk 18.1 123.3 72.6 36.4 30.8 5.5 39.0 32.9 6.1 143.7 3/30/99 WHS dusk 16.7 755.8 67.6 37.1 31.2 5.9 41.4 34.3 7.2 140.0 3/30/99 WIMD dusk 4.2 56.3 72.6 36.8 31.2 5.6 39.1 33.4 5.7 138.5 3/30/99 WIMS dusk 2.7 64.7 64.1 40.0 31.5 8.5 42.3 34.5 7.8 137.0 3/30/99 WIOD dusk 0.9 81.7 67.0 36.5 30.1 6.4 38.8 32.1 6.6 135.0 3/30/99 WIOS dusk 0.0 92.5 64.1 37.5 31.2 6.4 39.1 32.6 6.5 134.5 3/30/99 W2P dusk 28.9 79.8 72.0 41.2 35.8 5.4 43.7 37.3 6.4 153.3 3/30/99 W21D dusk 25.2 74.9 68.8 36.6 30.6 6.0 41.0 35.1 5.8 147.7 3/30/99 W21S dusk 20.4 134.1 65.2 38.5 33.0 5.4 40.4 34.8 5.6 141.2 3/30/99 W2MD dusk 4.6 54.1 35.3 28.8 6.5 37.2 31.1 6.1 130.7 3/30/99 W2MS dusk 0.0 54.8 65.2 34.6 28.0 6.6 39.5 33.1 6.4 132.6 3/30/99 W20D dusk 0.0 55.1 49.0 30.8 24.1 6.7 30.2 24.7 5.4 114.5 3/30/99 W20S dusk 1.8 154.6 63.5 32.5 25.4 7.1 33.5 26.9 6.6 117.0 3/31/99 WIP dawn 27.0 91.1 73.3 39.3 33.9 5.5 42.1 36.4 5.7 148.2

continued on next page

143 Appendix B, continued

SRP TP Ca TDC DIC DOC TC TIC TOC Total Date Site Time 3/31/99 WIID dawn 22.1 96.8 79.4 38.9 33.3 5.6 44.5 38.1 6.4 153.3 3/31/99 WHS dawn 22.1 573.5 78.0 41.7 35.5 6.2 45.7 39.8 6.0 157.7 3/31/99 WIMD dawn 5.0 60.0 80.1 35.8 29.6 6.2 42.1 36.4 5.7 144.6 3/31/99 WIMS dawn 0.0 75.6 71.3 38.6 31.4 7.1 41.5 34.8 6.7 137.2 3/31/99 WIOD dawn 0.0 69.8 61.8 37.9 31.1 6.8 41.3 33.3 7.9 132.6 3/31/99 WIOS dawn 0.0 98.6 64.6 35.3 27.9 7.5 38.8 31.9 7.0 126.9 3/31/99 W2P dawn 24.6 88.6 75.9 39.8 34.1 5.8 42.8 36.7 6.1 151.3 3/31/99 W2ID dawn 14.0 94.8 68.8 39.7 34.1 5.6 44.0 37.9 6.1 156.0 3/31/99 W21S dawn 13.6 203.2 72.0 40.5 35.0 5.5 43.9 37.5 6.4 155.4 3/31/99 W2MD dawn 3.8 83.7 61.8 40.5 35.1 5.4 43.5 37.5 6.0 149.0 3/31/99 W2MS dawn 23.7 89.3 64.1 42.3 35.1 7.2 43.6 36.6 7.0 145.1 3/31/99 W20D dawn 0.0 118.0 57.0 36.9 30.5 6.4 41.9 35.8 6.1 143.4 3/31/99 W20S dawn 0.0 69.8 49.0 40.6 33.7 6.9 42.3 35.7 6.6 142.0 6/1/99 WIP dawn 78.9 156.7 54.1 44.1 37.6 6.6 45.8 38.8 7.0 159.5 6/1/99 WHD dawn 41.9 71.7 46.8 45.1 38.0 7.1 45.2 38.1 7.1 159.7 6/1/99 WHS dawn 25.5 280.7 63.5 44.8 37.7 7.1 49.5 41.6 7.9 159.3 6/1/99 WIMD dawn 3.7 41.4 55.0 43.0 35.8 7.2 45.9 38.4 7.5 148.8 6/1/99 WIMS dawn 16.4 192.8 52.6 42.9 35.6 7.3 46.5 38.9 7.6 140.6 6/1/99 WIOD dawn 3.7 27.0 50.3 41.3 33.8 7.4 43.7 36.4 7.4 144.0 6/1/99 WIOS dawn 3.7 70.4 50.8 39.6 32.4 7.2 44.7 36.7 8.0 143.1 6/1/99 W2P dawn 87.4 2.7 54.1 44.1 37.5 6.5 46.1 38.6 7.5 158.2 6/1/99 W21D dawn 58.3 112.9 60.7 44.2 36.9 7.2 46.1 39.2 6.9 159.2 6/1/99 W21S dawn 25.8 269.2 62.4 44.8 38.0 6.7 52.2 42.9 9.3 173.3 6/1/99 W2MD dawn 3.7 52.3 49.9 40.1 32.7 7.5 48.3 40.1 8.2 155.0 6/1/99 W2MS dawn 3.7 46.0 45.4 37.1 8.3 49.6 41.5 8.1 156.5 6/1/99 W 20D dawn 3.7 28.3 52.6 37.0 28.3 8.7 49.4 40.6 8.8 153.4 6/1/99 W 20S dawn 3.7 63.8 65.2 45.3 36.9 8.4 49.7 40.6 9.1 154.2 6/1/99 WIP dusk 98.3 165.8 70.1 41.9 35.6 6.3 44.3 37.8 6.5 157.5 6/1/99 WHD dusk 84.2 167.9 64.1 41.7 35.3 6.5 44.4 37.5 6.8 156.2 6/1/99 WHS dusk 56.5 164.5 61.3 40.3 33.9 6.4 45.4 37.4 8.0 149.3 6/1/99 WIMD dusk 19.1 48.6 58.6 37.5 30.9 6.7 40.1 33.4 6.7 143.9 6/1/99 WIMS dusk 63.4 69.4 62.9 43.2 34.8 8.4 46.8 39.8 7.0 150.0 6/1/99 WIOD dusk 3.7 24.8 45.2 40.8 33.3 7.5 42.1 34.4 7.7 144.4 6/1/99 WIOS dusk 8.2 99.1 56.5 41.1 33.4 7.8 44.8 36.0 8.7 144.8 6/1/99 W2P dusk 72.9 179.6 70.1 41.3 35.4 5.9 44.5 37.4 7.2 157.2 6/1/99 W2ID dusk 101.6 162.9 67.0 38.6 32.5 6.1 45.3 38.4 6.9 158.0 6/1/99 W21S dusk 58.3 270.2 65.2 43.5 36.9 6.5 46.9 39.6 7.3 160.3 6/1/99 W2MD dusk 43.5 61.1 65.2 41.1 33.5 7.5 50.1 37.8 12.4 156.9 6/1/99 W2MS dusk 8.5 49.4 63.5 46.6 38.6 8.0 50.7 42.5 8.2 164.5 6/1/99 W 20D dusk 3.7 39.3 53.1 43.1 35.3 7.7 45.2 36.9 8.4 147.6 6/1/99 W 20S dusk 5.0 112.6 52.6 39.7 31.8 7.9 41.8 34.0 7.8 138.3 6/2/99 WIP dawn 81.4 232.1 70.1 43.0 36.0 7.0 44.2 37.5 6.7 154.0 6/2/99 WHD dawn 74.6 154.9 71.3 42.3 35.5 6.8 44.9 38.4 6.5 155.5 6/2/99 WHS dawn 51.7 124.2 74.6 45.0 37.7 7.3 49.0 40.6 8.3 156.7 6/2/99 WIMD dawn 12.0 40.5 68.8 45.6 38.7 6.9 48.0 40.9 7.1 157.9 6/2/99 WIMS dawn 34.3 74.9 75.9 45.1 38.2 6.9 49.0 41.9 7.0 158.0 6/2/99 WIOD dawn 54.3 26.5 52.6 44.3 37.1 7.2 46.5 38.9 7.6 151.8 6/2/99 WIOS dawn 6.5 41.5 47.3 46.2 36.8 9.4 48.3 38.9 9.5 143.1 6/2/99 W2P dawn 82.3 243.4 68.8 40.9 34.5 6.4 44.5 38.0 6.5 154.0 6/2/99 W2ID dawn 84.4 199.4 71.3 35.6 29.5 6.1 44.9 37.6 7.2 156.3 6/2/99 W2IS dawn 53.5 170.6 68.8 45.7 38.7 7.1 48.3 41.1 7.2 158.3 6/2/99 W2MD dawn 26.6 7.0 64.1 46.0 39.4 6.6 49.0 40.8 8.2 159.6 6/2/99 W2MS dawn 2.2 37.1 68.8 49.3 41.5 7.8 52.0 43.5 8.6 168.4 6/2/99 W20D dawn 2.2 63.5 45.3 38.0 7.3 49.0 41.3 7.7 158.8 6/2/99 W 20S dawn 5.8 78.6 56.0 47.4 39.2 8.2 50.8 42.0 8.8 156.5

144 APPENDIX C - WETLAND AQUATIC METABOLISM

Gross primary production (GPP) and respiration (R) in the experimental wetlands from dawn-dusk-dawn samples. The key to the site code is: W I= Wetland 1, W2 = Wetland 2. P=inflow pipe. I=inflow subbasin, M=middle subbasin, 0=outflow subbasin. D=deepwater area, S=shallow water area.

GPP R Date code Site name g 0-. m"” d" g 0 , m" d" 7/15/98 WIP -0.7 -1.2 7/15/98 WIID 3.8 5.1 7/15/98 WHS 4.1 4.9 7/15/98 WIMD 25.2 26.4 7/15/98 WIMS 18.1 18.1 7/15/98 WIOD 40.0 40.5 7/15/98 WIOS 21.6 22.7 7/15/98 W2P -0.1 -0.6 7/15/98 W2ID 3.8 6.0 7/15/98 W2IS 0.4 -0.7 7/15/98 W2MD 24.1 20.8 7/15/98 W2MS 16.2 16.2 7/15/98 W 20D 25.2 25.9 7/15/98 W 20S 5.3 4.9 8/14/98 WIP 4.5 3.8 8/14/98 WIID 3.1 3.5 8/14/98 WHS 2.4 2.7 8/14/98 WIMD 30.2 33.5 8/14/98 WIMS 2.8 2.9 8/14/98 WIOD 43.5 44.1 8/14/98 WIOS 29.2 30.6 8/14/98 W2P 4.3 3.6 8/14/98 W2ID 3.3 4.5 8/14/98 W2IS 2.4 2.9 8/14/98 W2MD 18.1 20.4 8/14/98 W2MS 4.4 4.9 8/14/98 W20D 17.8 20.0 8/14/98 W 20S 15.4 16.4 10/21/98 WIP -0.5 -0.9 10/21/98 WHD 1.8 0.0 10/21/98 WHS 0.4 1.5 10/21/98 WIMD 20.8 20.7 10/21/98 WIMS 4.5 1.5 10/21/98 WIOD 7.4 8.2 10/21/98 WIOS 0.8 -0.8 10/21/98 W2P -0.5 -0.8 10/21/98 W2ID 1.1 1.9 10/21/98 W2IS 1.2 0.8 10/21/98 W2MD 11.5 11.1 10/21/98 W2MS 2.1 2.0 10/21/98 W20D 7.6 8.4 10/21/98 W20S 7.3 6.8 3/30/99 WIP -0.5 -1.9 3/30/99 WHD 3.1 2.7 3/30/99 WHS 1.9 2.8 3/30/99 WIMD 7.9 8.6 3/30/99 WIMS 4.2 2.6 3/30/99 WIOD 13.6 13.0 3/30/99 WIOS 9.4 7.3 continued on next page

145 Appendix C, continued

GPP R Date code Site name g 0^ m'^ d ‘ g 0 , m" d- 3/30/99 W2P -0.9 -2.7 3/30/99 W2ID 7.7 7.6 3/30/99 W2IS 3.3 2.2 3/30/99 W2MD 7.1 6.6 3/30/99 W2MS 3.1 1.3 3/30/99 W 20D 18.0 18.8 3/30/99 W20S 5.3 5.4 6/1/99 WIP 2.8 1.6 6/1/99 WIID 3.1 0.6 6/1/99 WHS 9.5 8.6 6/1/99 WIMD 17.1 16.6 6/1/99 WIMS -0.8 -1.3 6/1/99 WIOD 10.1 9.9 6/1/99 WIOS 6.1 6.4 6/1/99 W2P 3.3 1.2 6/1/99 W2ID 6.3 3.3 6/1/99 W2IS 3.2 2.0 6/1/99 W2MD 12.5 12.1 6/1/99 W2MS 2.2 2.0 6/1/99 W 20D 8.7 8.3 6/1/99 W20S 16.4 16.3

146 APPENDIX D - CARBONATES IN METAPHYTON BIOMASS

Calcite, dolomite, and calcium carbonate equivalent in metaphyton biomass in the experimental wetlands. The key to the site code is: W l= Wetland I, W2 = Wetland 2. P=inflow pipe. I=inflow subbasin, M=middle subbasin, 0=outflow subbasin. D=deepwater area, S=shallow water area.

Sampling D Sample # Location Wt.(g) %Calcite %Dolomite %CCE 5/27/99 1 WIID 0.5246 5.9 12.4 19.4 5/27/99 2 WIID 0.5246 24.0 8.3 33.0 5/27/99 3 WIMD 0.5541 12.7 14.5 28.4 5/27/99 4 WIMD 0.5255 27.3 9.0 37.1 5/27/99 4 WIMD 1.1139 21.6 18.7 41.9 5/27/99 5 WIOD 0.5594 34.7 11.2 46.8 5/27/99 5 WIOD 1.0427 22.9 23.6 48.6 5/27/99 6 WIOD 0.6403 18.5 15.0 34.8 5/27/99 7 W2ID 0.9962 -2.2 0.8 -1.3 5/27/99 8 W2ID 0.5305 8.3 8.4 17.4 5/27/99 9 W2MD 0.545 4.9 5.9 11.3 5/27/99 10 W2MD 0.5051 17.4 8.0 26.1 5/27/99 11 W 20D 0.3895 13.6 7.3 21.5 5/27/99 12 W20D 0.3174 8.4 7.7 16.8 8/28/98 1 WIMD 0.5635 18.5 5.6 24.6 8/28/98 2 WIMD 0.6258 14.5 5.6 20.6 8/28/98 3 WIMD 0.7938 21.1 5.9 27.5 8/28/98 4 WIMD 0.526 19.7 6.0 26.2 8/28/98 4 WIMD 1.1139 21.5 18.5 41.6 8/28/98 5 WIMD 0.6502 22.0 5.4 27.9 8/28/98 5 WIMD 1.0427 23.0 23.7 48.8 8/28/98 6 WIOD 0.8944 33.4 3.9 37.6 8/28/98 7 WIOD 0.8112 20.0 6.8 27.4 8/28/98 8 WIOD 0.8027 28.2 6.3 35.0 8/28/98 9 WIOD 0.6694 27.8 6.3 34.7 8/28/98 10 WIOD 0.5767 12.7 6.2 19.4 8/28/98 11 WIOD 0.6974 19.6 6.7 26.9 8/28/98 12 WIOS 0.2639 -8.3 0.0 -8.3 8/28/98 13 WIOS 0.3736 -4.1 1.6 -2.3 8/28/98 15 WIMS 0.1757 -10.1 3.5 -6.3 8/28/98 16 W2ID 0.3798 -1.1 5.2 4.5 8/28/98 17 W2ID 0.2146 -8.3 4.8 -3.1 8/28/98 18 W2ID 0.3743 -4.6 4.2 0.0 8/28/98 19 W2ID 0.5262 1.7 4.7 6.8 8/28/98 20 W2ID 0.2391 -8.2 2.5 -5.5 8/28/98 21 W2MD 0.5409 25.3 5.8 31.6 8/28/98 22 W2MD 0.6497 22.6 5.7 28.8 8/28/98 23 W2MD 0.6405 23.9 6.1 30.5 8/28/98 24 W2MD 0.5545 26.1 6.2 32.8 8/28/98 25 W2MD 0.4846 20.4 7.3 28.4 8/28/98 26 W20D 0.4272 5.6 6.1 12.3 8/28/98 27 W20D 0.7136 11.0 4.5 15.9 8/28/98 28 W20D 0.1784 -4.9 6.8 2.5 8/28/98 29 W20D 0.5667 19.2 4.9 24.6 8/28/98 30 W 20D 0.4747 4.5 7.5 12.7

147 APPENDIX E -METAPHYTON ELEMENTAL ANALYSIS

Elemental makeup o f the metaphyton mat in the experimental wetlands, The key to the site code is: W H Wetland I, W2 - Wetland 2. P^inflow pipe. I = inflow subbasin, M = middle subbasin, O = outflow subbasin. D = deepwater area, S = shallow water area. Key to algal abbreviations: H Hydrodictyon, R = Rhizoclonium, C= Cladophora, S = Spirogyra, Pith =Pithophora, P = Potamogeton pectinatus, U Ulothrix.

P K Ca Mg AI B Cu Fe Mn Mo Na Zn Sample date Site Major spp. mg/g mg/g mg/g mg/g mg/g ug/g ug/g mg/g ug/g ug/g ug/g ug/g 8/28/98 WIMD H,R/C,Pith 3.5 21.8 102.5 3.2 1.7 117 7.5 3.8 1588 2.2 423 28 8/28/98 WIMD H,R/C,Pith 3.4 21.0 101.6 3.2 1.6 118 7.0 3.9 1691 1.7 374 30 8/28/98 WIMD H,R/C 2.7 26.3 92.6 3.1 2.0 101 6.8 3.4 2026 1.2 401 30 8/28/98 WIMD H,R/C 2.6 25.2 91.7 3.1 1.9 101 6.7 3.4 2155 2.2 346 32 8/28/98 WIMD C 2.8 21.1 106.4 3.4 1.9 140 6.3 4.2 1435 1.9 495 24 8/28/98 WIMD C 2.7 20.3 106.1 3.4 1.8 137 6.4 4.3 1536 2.0 429 26 8/28/98 WIMD R,H,Pith 2.3 22.0 109.8 3.5 2.9 80 6.7 4.7 2116 1.2 471 29 8/28/98 WIMD R,H,Pith 2.3 21.0 109.9 3.5 2.7 80 6.6 4.8 2266 1.8 409 31 8/28/98 WIMD U,P, C/R 2.4 20.0 107.9 3.7 2.3 103 6.7 4.2 1970 1.3 431 40 8/28/98 WIMD U,P, C/R 2.4 19.1 108.0 3.6 2.2 102 6.5 4.4 2110 1.7 354 43 8/28/98 WIOD S, C/R, U, 1.0 9.2 144.2 4.5 2.1 104 5.1 4.1 573 1.9 1457 26 8/28/98 WIOD S, C/R, U, 1.0 8.8 149.3 4.5 2.0 103 4.9 4.3 631 2.6 1325 29 4^ 00 8/28/98 WIOD C/R,S 1.3 20.3 107.8 4.5 2.4 217 10.3 5.7 1552 2.7 2061 27 8/28/98 WIOD C/R,S 1.3 19.5 108.9 4.4 2.3 214 10.0 5.9 1643 2.7 1929 29 8/28/98 WIOD S 1.5 10.5 131.9 4.9 2.0 86 5.4 3.4 1780 1.1 4800 17 8/28/98 WIOD S 1.5 10.3 134.5 4.9 1.9 88 5.4 3.6 1913 1.4 4491 19 8/28/98 WIOD S,C/R 1.5 6.2 125.7 4.3 2.5 78 6.8 5.5 1002 2.1 5305 26 8/28/98 WIOD S,C/R 1.5 6.0 126.2 4.2 2.4 78 6.8 5.6 1078 1.5 4949 28 8/28/98 WIOD S 2.1 5.9 104.8 3.4 2.1 45 5.3 4.4 1090 1.8 8786 18 8/28/98 WIOD S 2.1 6.0 103.9 3.4 2.0 45 5.1 4.6 1163 2.5 8411 19 8/28/98 WIOS C 2.4 26.0 16.1 2.3 0.7 228 6.6 2.6 1475 3.3 419 23 8/28/98 WIOS C 2.4 25.5 22.2 2.4 0.8 222 7.6 2.9 1510 2.0 903 25 8/28/98 WIOS C 2.3 24.6 14.5 2.1 1.0 198 10.8 2.4 763 2.7 328 32 8/28/98 WIOS C 2.2 23.7 14.1 2.0 1.0 190 10.3 2.4 757 2.7 347 31 8/28/98 WIMS H 2.1 36.9 19.2 1.8 1.0 284 8.1 3.5 352 2.3 735 29 8/28/98 WIMS H 2.0 35.4 17.7 1.7 0.9 268 9.4 3.3 336 0.7 603 29 8/28/98 W2ID H 6.6 30.2 31.2 2.5 1.8 20 13.7 5.1 442 2.1 491 64 8/28/98 W2ID H 6.1 29.5 28.8 2.3 1.7 22 12.5 5.0 431 2.3 412 63 8/28/98 W2ID H 6.6 17.6 38.0 2.9 2.0 29 12.7 4.7 486 3.2 595 75 8/28/98 W2ID H 6.6 19.5 36.9 2.9 1.9 32 13.1 4.9 492 8.7 487 80

Continued on next page APPENDIX E - Continued

K Ca Mg Al B Cu Fe Mn Mo Na Zn Sample date Site Major spp. mg/g mg/g mg/gmg/g mg/g ug/g ug/g mg/g ug/g ug/g ug/g ug/g 8/28/98 W2ID H 8.0 34.6 15.6 2.5 1.5 21 11.8 4.5 260 1.9 331 58 8/28/98 W2ID H 7.5 33.0 14.6 2.3 1.4 20 10.8 4.3 254 2.6 280 57 8/28/98 W21D H.C 7.1 34.8 37.7 2.8 1.7 11 12.0 3.7 724 1.3 344 50 8/28/98 W21D H.C 6.8 33.4 34.8 2.6 1.6 11 12.3 3.7 712 2.5 274 51 8/28/98 W21D H 9.6 43.9 14.4 2.6 0.9 9 12.2 2.1 289 1.8 490 60 8/28/98 W21D H 9.3 43.4 15.0 2.5 0.9 9 12.6 2.3 314 0.5 350 61 8/28/98 W2MD R/C 3.3 22.7 126.3 3.3 1.7 68 8.0 5.0 713 2.4 491 23 8/28/98 W2MD R/C 3.3 21.8 124.7 3.2 1.6 67 7.7 5.1 746 2.6 414 25 8/28/98 W2MD H, R/C, S 2.8 24.0 116.9 3.1 1.8 72 7.1 4.0 469 2.3 479 22 8/28/98 W2MD H, R/C, S 2.8 22.9 116.5 3.1 1.7 71 6.5 4.1 497 2.1 399 23 8/28/98 W2MD C/R 3.6 19.9 132.2 3.3 1.5 96 13.9 5.4 536 2.1 385 16 8/28/98 W2MD C/R 3.5 19.2 134.2 3.3 1.4 95 13.3 5.6 568 3.2 312 17 8/28/98 W2MD C/R.H 2.5 18.8 126.8 3.0 1.6 58 6.9 6.2 465 3.4 370 16 8/28/98 W2MD C/R,H 2.5 18.1 126.2 3.0 1.5 57 6.6 6.3 482 5.0 311 18 8/28/98 W2MD C/R 3.1 22.2 122.3 3.6 2.1 76 8.2 4.9 1351 1.6 612 25 8/28/98 W2MD C/R 3.0 21.1 124.0 3.5 1.9 74 7.5 5.0 1416 0.9 524 27 8/28/98 W20D R 2.6 27.3 68.2 2.3 2.4 75 7.9 9.3 437 3.2 651 29 8/28/98 W20D R 2.6 26.5 68.9 2.4 2.2 74 8.0 9.2 493 4.7 549 31 8/28/98 W20D C, Pot. Peel. 2.8 24.3 72.1 2.2 2.2 75 6.7 10.9 568 3.9 1275 23 8/28/98 W20D C, Pot. Pect. 2.6 23.1 69.0 2.1 2.0 71 6.3 10.6 576 4.5 1112 24 8/28/98 W20D R,S,U 2.7 31.1 63.8 2.1 3.5 81 15.0 18.1 1513 5.1 1084 66 8/28/98 W20D R,S,U 3.1 33.4 73.6 2.5 3.6 98 15.6 19.4 1567 5.6 1022 70 8/28/98 W20D R/C.S 1.9 13.5 107.6 2.8 1.6 88 6.1 8.1 1116 2.3 326 20 8/28/98 W20D R/C.S 1.8 12.9 103.8 2.7 1.5 85 5.8 8.2 1140 1.5 250 21 8/28/98 W20D C 2.0 22.7 59.0 2.4 4.7 59 12.6 11.7 564 3.2 876 55 8/28/98 W20D C 2.0 21.6 59.1 2.5 4.3 59 11.9 11.5 600 5.3 774 56 5/25/99 WIID H 7.2 34.2 80.5 3.5 0.6 17 15.0 1.2 1392 1.5 602 82 5/25/99 WIID H 4.5 18.8 137.8 3.9 2.6 41 12.3 3.5 2604 <0.5 460 73 5/25/99 WIMD H 1.8 22.4 129.7 3.4 1.4 20 7.3 2.5 630 1.0 342 30 5/25/99 WIMD H.C 0.8 17.7 171.6 4.9 1.1 67 4.1 1.4 397 <0.5 523 20 5/25/99 WIOD C 0.7 11.0 198.2 4.0 1.2 101 4.4 1.5 185 0.7 220 18 5/25/99 WIOD C 0.9 14.2 160.1 3.9 1.1 120 3.9 1.7 307 1.2 234 18 5/25/99 W21D S 4.8 7.5 10.3 3.7 1.7 13 8.3 2.6 591 3.6 6843 79 5/25/99 W2ID S,H 3.6 7.9 93.2 3.5 1.8 16 8.3 3.0 783 2.7 1193 56

Continued on next page APPENDIX E - Continued

P K Ca Mg AI B Cu Fe Mn Mo Na Zn Sample date Site Major spp. mg/g mg/g mg/g mg/g mg/g ug/g ug/g mg/g ug/g ug/g ug/g ug/g 5/25/99 W2MD H 3.9 27.0 68.2 3.1 1.7 19 7.9 3.1 836 1.9 280 52 5/25/99 W2MD H 2.0 28.9 111.2 3.7 0.6 14 5.7 1.1 634 1.2 187 28 5/25/99 W20D H.S 1.0 19.7 108.7 3.5 1.2 27 4.8 1.9 748 0.8 1136 26 5/25/99 W20D H.S 1.1 23.6 98.7 3.5 1.0 22 6.0 2.0 795 <0.5 1332 36

L/1 o APPENDIX F - TOTAL METAPHYTON CARBONATES

Dry biomass and calcium carbonate content o f metaphyton in the experimental wetlands. The key to the site code is: W1 - Wetland I, W2 = Wetland 2. P=inflow pipe. 1 = inflow subbasin, M = middle subbasin, O = outflow subbasin. D = deepwater area, S == shallow water area. Key to codes: H = Hydrodictyon, R = Rhizoclonium, C= Cladophora, S ^ Spirogyra, Pith = Pithophora, P = Potamogeton pectinatus, U = Ulothrix.

Area estimated estimated Net dry Dry Subbasin covered subbasin subbasin Sampling Sample Major weight biomass area by algae biomass CaC03 Date Location spp. g g m ’ % cover m^ m^ kg %CCE kg 8/28/98 WIMD H,R/C,P 4.0769 73.0 60 1884 1130 82.5 24.6 20.26 8/28/98 WIMD H,R/C 3.2041 57.4 60 1884 1130 64.8 20.6 13.37 8/28/98 WIMD C 3.482 62.3 60 1884 1130 70.5 27.5 19.37 8/28/98 WIMD R.H,P 4.2481 76.0 60 1884 1130 86.0 26.2 22.54 8/28/98 WIMD R,H,P 4.2481 76.0 60 1884 1130 86.0 41.6 35.77 u> 8/28/98 WIMD U,P,C/R 2.1846 39.1 60 1884 1130 44.2 27.9 12.31 8/28/98 WIMD U,P,C/R 2.1846 39.1 60 1884 1130 44.2 48.8 21.58 8/28/98 WIOD S,C/R, U 6.6369 118.8 60 964 578 68.7 37.6 25.82 8/28/98 WIOD C/R,S 3.3955 60.8 60 964 578 35.2 27.4 9.62 8/28/98 WIOD S.U 3.7277 66.7 60 964 578 38.6 35.0 13.53 8/28/98 WIOD S.C/R 4.0559 72.6 60 964 578 42.0 34.7 14.57 8/28/98 WIOD PP 2.5861 46.3 60 964 578 26.8 19.4 5.20 8/28/98 WIOD S 3.105 55.6 60 964 578 32.1 26.9 8.65 8/28/98 W21D H 0.7772 13.9 20 615 123 1.7 4.5 0.08 8/28/98 W21D H 0.3778 6.8 20 615 123 0.8 -3.1 -0.03 8/28/98 W21D H 0.59485 10.6 20 615 123 1.3 0.0 0.00 8/28/98 W21D H.C 1.1921 21.3 20 615 123 2.6 6.8 0.18 8/28/98 W21D H 0.5973 10.7 20 615 123 1.3 -5.5 -0.07

Continued on next page Appendix F, continued

Area estimated estimated Net dry Dry Subbasin covered subbasin subbasin Sampling Sample Major weight biomass area by algae biomass CaC03 Date Location spp. K g m ■ % cover m‘ m' kg %CCE kg 8/28/98 W2MD R/C.H 3.7436 67.0 80 1112 890 59.6 31.6 18.84 8/28/98 W2MD H.R/C.S 2.7023 48.4 80 1112 890 43.0 28.8 12.39 8/28/98 W2MD C/R 5.2316 93.6 80 1112 890 83.3 30.5 25.40 8/28/98 W2MD C/R,H 3.0693 54.9 80 1112 890 48.9 32.8 16.05 8/28/98 W2MD C/R.H.S 1.5366 27.5 80 1112 890 24.5 28.4 6.95 8/28/98 W20D R 0.8434 15.1 8 578 46 0.7 12.3 0.09 8/28/98 W20D C. Pp 1.9703 35.3 8 578 46 1.6 15.9 0.26 8/28/98 W 20D R,S,U 0.3242 5.8 8 578 46 0.3 2.5 0.01 8/28/98 W 20D R/C.S 1.2047 21.6 8 578 46 1.0 24.6 0.24 K>U\ 8/28/98 W20D C 0.8935 16.0 8 578 46 0.7 12.7 0.09 5/25/99 WHO H 2.9156 52.2 100 578 578 30.2 19.4 5.86 5/25/99 WIID H 4.9399 88.4 100 578 578 51.1 33.0 16.87 5/25/99 WIMD H 3.7722 67.5 99 1884 1865 125.9 28.4 35.79 5/25/99 WIMD H.C 4.9098 87.9 99 1884 1865 163.9 39.5 64.71 5/25/99 WIOD C 8.2038 146.9 5 964 48 7.1 47.7 3.38 5/25/99 WIOD C 6.9927 125.2 5 964 48 6.0 34.8 2.10 5/25/99 W2ID S* 50.9 911.1 60 615 369 -1.3 * 5/25/99 W2ID S.H 3.9089 70.0 60 615 369 25.8 17.4 4.49 5/25/99 W2MD H 1.6782 30.0 98 1112 1090 32.7 11.3 3.70 5/25/99 W2MD H 2.0243 36.2 98 1112 1090 39.5 26.1 10.29 5/25/99 W20D H.S 1.4498 26.0 95 578 549 14.3 21.5 3.07 5/25/99 W20D H.S 1.0976 19.6 95 578 549 10.8 16.8 1.81 APPENDIX G - PHYSICAL PROPERTIES OF WETLAND SEDIMENTS

Physical characteristics o f sediment samples taken from the experimental wetland basins on May 13, 1999. Coordinates refer to a permanent 10 m x 10 m grid set up on the experimental basins.

Coordinates Depth bulk density organic matter water content Sample date x,y cm g/mL % o f drv wt % o f wet wt 5/13/99 2,9 0-8 0.847 10.9 44.2 5/13/99 2,11 0-8 0.976 8.1 39.1 5/13/99 4,3 0-8 0.686 12.6 45.8 5/13/99 4,5 0-8 0.942 11.8 40.1 5/13/99 4,9 0-8 1.103 6.9 33.0 5/13/99 4,11 0-8 1.307 5.8 27.0 5/13/99 4,15 0-8 0.642 15.8 54.2 5/13/99 4,17 0-8 1.252 4.4 27.8 5/13/99 6,3 0-8 1.373 5.3 24.7 5/13/99 6,5 0-8 0.814 10.8 44.5 5/13/99 6,15 0-8 0.781 10.5 43.5 5/13/99 6,17 0-8 1.042 7.8 38.5 5/13/99 9,5 0-8 1.216 6.7 31.6 5/13/99 9,6 0-8 0.711 13.2 49.9 5/13/99 9,17 0-8 1.016 8.7 37.6 5/13/99 11,5 0-8 0.904 11.6 42.1 5/13/99 11,11 0-8 0.963 9.1 36.4 5/13/99 11,13 0-8 1.169 6.6 29.9 5/13/99 11,15 0-8 1.036 6.0 29.0 5/13/99 11,17 0-8 0.907 8.9 37.2 5/13/99 12,5 0-8 0.578 15.0 54.6 5/13/99 13,9 0-8 0.732 12.1 43.1 5/13/99 13,13 0-8 1.007 9.0 37.2 5/13/99 13,17 0-8 1.063 7.4 34.3 5/13/99 2,9 8-16 1.465 4.9 23.9 5/13/99 2,11 8-16 1.437 5.2 22.5 5/13/99 4,3 8-16 1.285 6.6 27.9 5/13/99 4,5 8-16 1.481 5.0 22.0 5/13/99 4,9 8-16 1.351 5.7 23.3 5/13/99 4,11 8-16 1.388 5.6 25.3 5/13/99 4,15 8-16 1.344 5.8 25.2 5/13/99 4,17 8-16 1.439 5.1 22.6 5/13/99 6,3 8-16 1.489 5.1 22.1 5/13/99 6,5 8-16 1.386 5.5 23.6 5/13/99 6,15 8-16 1.432 5.6 24.5 5/13/99 6,17 8-16 1.381 6.1 24.2 5/13/99 9,5 8-16 1.505 5.0 21.2 5/13/99 9,6 8-16 1.449 4.9 21.9 5/13/99 9,17 8-16 1.426 5.8 23.9 5/13/99 11,5 8-16 1.461 5.5 23.7 5/13/99 11,11 8-16 1.428 5.5 22.4 5/13/99 11,13 8-16 1.453 5.7 23.2 5/13/99 11,15 8-16 1.450 5.9 22.9 5/13/99 11,17 8-16 1.324 6.4 26.2 5/13/99 12,5 8-16 1.597 4.7 21.3 5/13/99 13,9 8-16 1.608 4.8 20.2 5/13/99 13,13 8-16 1.328 5.6 24.9 5/13/99 13,17 8-16 1.366 6.1 24.9

153 APPENDIX H - SOIL COLOR OF WETLAND SEDIMENTS

Munsell soil color of moist sediment samples taken from the experimental wetland basins on May 13, 1999. Coordinates refer to a permanent 10 m x 10 m grid set up on the experimental basins.

Coordinates Sample date X Y Depth(cm) Munsell Soil Color Notes 5/13/99 2 9 0-1.5 10 YR 3/2 5/13/99 2 9 1.5-7 7.5 YR 2/0 5/13/99 2 9 7-12 10 YR3/1 5/13/99 2 11 0-4 7.5YR 2/0 5/13/99 2 11 4-8 lOYR 3/1 5/13/99 2 11 12-16 10 YR 3/3 5/13/99 2 11 8-12 10YR3/1 5/13/99 4 3 0-8 10YR3/2,7.5YR2/0 5/13/99 4 3 8-16 10Y R 3/2. 10YR3/1 5/13/99 4 5 0-6 10 YR 3/1 5/13/99 4 5 6-12 10 YR 3/2 5/13/99 4 9 0-8 10 YR2/1 5/13/99 4 9 8-16 10 YR 3/2 Mottles 5YR 4/6 5/13/99 4 11 0-4 10 YR3/1 Mottles 5YR4/6 5/13/99 4 11 4-13 10 YR4/1 5/13/99 4 15 0-8 7.5 YR 2/0 5/13/99 4 15 8-16 10YR3/1 5/13/99 4 17 0-8 10 YR3/2 5/13/99 4 17 8-16 10 YR 3/2 5/13/99 6 3 0-8 10YR3/1 5/13/99 6 3 8-13 10 YR3/1 5/13/99 6 5 0-8 10 YR3/2 5/13/99 6 5 8-16 10 YR 3/2 5/13/99 6 15 0-8 7.5 YR 2/0 5/13/99 6 15 8-16 10YR3/1 5/13/99 6 17 0-7 10YR2/1 5/13/99 6 17 7-12 10 YR 3/1 Oxidized root channels 5/13/99 9 5 0-4 10 YR3/1 5/13/99 9 5 4-12 10 YR 3/2 5/13/99 9 6 0-8 10 YR3/1 Black inclusions 5/13/99 9 6 8-16 10 YR 4/I 5/13/99 9 17 0-8 10YR3/I 5/13/99 9 17 8-14 10YR3/1 5/13/99 11 5 0-8 10YR2/1 5/13/99 11 5 8-16 10YR3/1 5/13/99 11 11 0-8 10YR3/1 5/13/99 11 11 8-16 10YR3/1 5/13/99 11 13 0-6 10YR2/1 5/13/99 11 13 6-12 10YR3/1 5/13/99 11 15 0-8 10YR3/1 5/13/99 11 15 8-16 10YR3/I 5/13/99 11 17 0-6 7.5 YR 2/0 5/13/99 11 17 6-12 10\T13/1 5/13/99 12 5 0-4 10YR2/0 5/13/99 12 5 4-16 10Y R 4/2 5/13/99 13 9 0-12 7.5 YR 2/0 5/13/99 13 9 12-16 10Y R 3/2 5/13/99 13 13 0-8 7.5 YR 2/0 5/13/99 13 13 8-16 10YR3/1 5/13/99 13 17 0-8 10YR3/1 5/13/99 13 17 8-16 I0YR3/I Oxidized root channels

154 APPENDIX 1 - SOIL CHEMISTRY OF WETLAND SEDIMENTS

Chemical characteristics of sediment samples taken from the experimental wetland basins on May 13, 1999. Coordinates refer to a permanent lOm x 10m grid set up on the experimental basins.

exch. exch. exch. exch. CEC total total total total total total total total total total total total total Location Depth Soil P K Ca Mg meq/ P K Ca Mg AI B Cu Fe Mn Mo Na S Zn x y cm pH ug/g ug/gmg/g ug/g lOOg ug/g mg/g mg/g mg/g mg/g ug/g ug/gmg/g ug/g ug/g ug/gug/g ug/g 2 9 0-7 7.43 < 1 163 5.00 387 28.6 721 9.41 36.88 5.77 37.2 39 30 31 335 6 396 2.93 114 2 9 7-12 7.39 3 117 2.78 392 17.5 467 8.69 4.96 4.75 35.4 35 30 35 620 7 388 0.38 103 2 II 0-8 7.44 < I 156 4.74 376 27.2 628 9.72 25.01 5.23 37.6 36 30 32 316 7 390 1.88 120 2 II 8-16 7.32 I 118 2.36 370 15.2 441 9.14 4.07 4.65 36.2 34 30 35 672 7 374 0.33 97 4 3 0-8 7.51 < I 166 5.01 438 29.1 755 10.12 37.26 9.26 38.1 41 36 30 278 7 437 3.12 143 4 3 8-13 7.52 11 128 3.98 385 23.4 664 8.87 11.82 5.87 34.0 35 30 33 269 7 380 0.95 105 4 5 0-6 7.52 2 166 5.38 468 31.2 918 10.22 26.29 6.82 40.1 42 35 32 339 6 413 1.44 133 4 5 6-12 7.52 8 112 2.92 404 18.3 584 8.80 4.74 4.47 34.1 35 28 34 568 7 357 0.35 98 4 9 0-8 7.46 3 124 4.53 372 26.1 642 8.66 11.01 4.56 33.7 36 28 31 224 6 357 1.32 103 4 9 8-16 7.22 2 93 2.75 403 17.3 560 8.59 4.28 4.19 33.5 38 27 34 487 7 359 0.39 96 4 11 0-8 7.50 6 119 3.34 406 20.4 601 8.65 5.74 4.35 33.4 35 28 33 349 7 345 0.53 97 ^ 4 11 8-13 7.60 3 104 2.89 459 18.5 572 5.70 4.20 3.81 25.7 27 28 34 575 7 212 0.40 102 ^ 4 15 0-8 7.50 < 1 190 5.20 442 30.2 680 7.82 41.62 5.89 35.2 31 41 33 281 6 322 3.31 120 4 17 0-8 7.15 14 88 2.05 328 13.2 573 6.19 4.29 3.69 24.9 29 23 26 205 5 276 0.65 88 4 17 8-16 7.48 3 102 2.19 415 14.7 457 4.64 4.32 3.90 22.4 22 27 31 536 6 195 0.36 89 6 3 0-8 7.00 12 134 2.82 358 17.4 548 10.64 4.87 4.68 39.7 42 32 37 380 7 439 0.48 112 6 3 8-13 7.05 11 108 2.36 366 15.1 435 7.91 3.34 4.36 32.8 31 35 39 599 7 297 0.27 118 6 5 0-8 7.60 2 178 5.57 486 32.4 732 9.90 22.40 5.58 38.9 38 34 32 212 7 374 1.10 123 6 5 8-16 7.44 6 121 3.43 436 21.1 552 9.49 4.52 4.39 36.1 35 31 36 360 7 356 0.32 109 6 5 8-16 6 119 3.25 433 104.2 525 9.20 4.23 4.20 34.8 34 29 35 345 7 353 0.29 111 6 15 0-8 7.51 < 1 183 4.85 418 28.2 667 11.28 31.12 5.68 42.4 44 33 32 310 6 492 3.00 113 6 15 8-16 7.36 2 125 3.46 416 21.1 500 10.15 5.32 4.53 39.5 38 29 35 486 5 454 0.47 102 6 17 0-7 6.80 5 151 3.18 450 20.0 645 9.72 4.96 4.55 38.0 41 30 31 236 6 404 0.89 108 6 17 7-12 6.67 1 105 2.77 421 17.6 501 9.54 3.84 4.30 37.5 37 28 34 495 7 411 0.36 98 9 5 0-4 7.45 19 131 3.63 357 21.5 565 6.87 10.03 4.68 28.5 30 34 34 438 7 259 0.71 112 9 5 4-12 7.40 8 103 2.48 392 15.9 399 8.68 3.30 4.41 34.4 36 36 38 805 8 310 0.24 112 9 6 0-8 7.33 2 157 4.35 436 25.8 755 10.10 20.62 5.06 37.5 40 33 32 246 6 416 1.57 120 9 6 8-16 7.45 8 117 2.72 415 17.4 425 10.65 3.57 4.62 40.1 40 33 39 616 8 426 0.27 117 9 17 0-8 7.39 < 1 150 4.29 412 25.3 648 8.89 16.90 4.34 33.4 39 28 29 236 5 386 1.34 104 9 17 8-14 7.10 3 119 3.06 427 19.2 573 9.53 4.12 4.23 36.5 43 32 34 535 7 410 0.38 109

continued on next page Appendix I, continued

exch. exch. exch. exch. CEC total total total total total total total total total total total total total Location Depth P K Ca Mg meq/ P K Ca Mg A1 B Cu Fe Mn Mo Na S Zn X y cm pH ug/g ug/g mg/g ug/g lOOg ug/g mg/g mg/g mg/g mg/gug/gug/g mg/gug/g ug/g ug/gug/g ug/g 11 5 0-8 7.42 < 1 158 4.91 410 28.4 823 6.77 40.19 6.70 29.2 30 35 29 295 6 282 2.68 144 11 5 8-17 6.86 3 106 3.19 469 20.1 643 8.41 5.67 4.04 32.0 36 30 32 432 7 338 0.57 116 11 5 8-16 7.19 6 113 3.54 347 20.9 522 9.24 4.07 4.25 36.8 36 30 35 584 6 385 0.27 103 11 11 0-8 7.64 2 167 5.01 440 29.1 731 9.52 20.64 5.38 37.6 39 36 34 264 6 383 1.23 123 11 11 8-16 7.45 12 119 2.81 422 17.9 580 9.12 4.08 4.35 35.4 38 34 37 645 7 341 0.30 110 11 13 0-7 7.51 12 141 4.45 446 26.3 674 9.37 9.97 4.49 35.9 36 30 34 284 6 361 0.73 123 11 13 7-12 7.39 6 121 2.93 430 18.5 533 9.42 4.19 4.38 36.9 37 31 36 639 6 347 0.29 107 11 15 0-8 7.29 7 151 4.37 419 25.7 644 9.96 7.52 4.57 38.3 42 32 32 277 6 399 0.70 121 n 17 0-8 7.36 < I 131 4.41 370 25.5 642 8.85 17.44 3.99 32.5 38 27 28 295 5 384 1.58 97 11 17 8-16 6.97 2 104 3.00 384 18.5 701 9.43 4.30 4.00 34.3 41 29 31 475 7 379 0.68 109 12 5 0-4 — 1 190 5.15 489 114.3 1044 10.81 40.17 6.67 41.1 44 37 31 315 6 462 2.82 138 12 5 4-16 7.35 22 118 2.42 405 15.8 473 9.79 3.16 4.43 36.2 41 31 38 496 8 375 0.23 105 12 5 4-16 — 22 117 2.30 377 98.9 457 6.13 3.00 3.84 26.1 28 30 37 484 7 209 0.22 104 13 9 0-12 7.52 < 1 155 4.86 415 28.2 765 10.10 41.05 5.89 38.8 40 35 33 327 7 411 3.74 126 13 9 0-12 — < 1 158 4.97 417 112.7 767 9.37 40.96 5.75 37.5 39 35 33 321 7 396 3.82 129 o\ 13 9 12-16 7.33 15 111 2.48 377 15.8 431 10.07 3.29 4.69 38.5 42 36 41 617 8 364 0.28 120 13 13 0-8 7.36 5 161 4.46 420 26.2 600 11.25 8.64 4.73 41.5 42 33 34 230 7 470 0.92 116 13 13 0-8 7.46 < 1 152 4.81 407 27.8 743 9.50 32.63 4.97 36.0 37 33 31 318 7 379 3.09 117 13 13 8-16 6.75 4 109 3.00 447 19.0 500 10.55 3.78 4.49 40.4 38 32 37 490 7 438 0.30 125 13 13 8-16 7.15 6 103 2.66 367 16.6 556 6.04 3.86 3.73 26.4 26 32 34 614 6 220 0.37 112 APPENDIX J - SCANNING ELECTRON MICROANALYSIS

Elemental microanalysis results, presented as elemental percentages. Samples denoted as "calcite" are calcite precipitates associated with algal filaments. Samples denoted as "algae" are the algal filaments themselves. Samples denoted as "upper sed" are calcite inclusions in the sediment samples. * denotes periphyton samples. Italicized numbers are not significantly different firom zero and were changed to zero in all further analyses. Meso = mesocosm. The key to the site code is: Wl= Wetland 1, W2 = Wetland 2. P=inflow pipe. 1 = inflow subbasin, M = middle subbasin, O = outflow subbasin, D = deepwater area, S = shallow water area.

Sample Sampling Sample Elemental percentages site date tlTC C 0 Na Mr Si P C! K Ca WIMD 5/27/99 calcite —— 0.48 2.10 4.96 0.89 0.47 0.67 90.44 WIMD 5/27/99 calcite 85.86 0.32 0.95 0.78 0.21 0.35 2.64 8.89 WIMD 5/27/99 calcite 68.33 — 0.27 1.48 0.56 0.18 0.04 0.29 28.85 WIMD 5/27/99 calcite 64.62 — -0.15 0.86 0.81 0.32 0.36 0.46 32.71 WIMD 5/27/99 calcite 55.81 — -0.37 1.48 0.35 0.35 0.21 0.45 41.72 WIMD 5/27/99 calcite 59.79 — -O.I 1.07 0.57 0.4 0.42 0.22 37.62 WIMD 5/27/99 calcite — -0.48 0.47 0.35 0.51 0.84 -0.41 98.70 WIMD 5/27/99 calcite 20.92 56.00 0.11 0.50 1.14 0.20 0.11 0.17 20.85 WIMD 5/27/99 calcite 20.26 61.33 0.05 0.44 0.24 0.13 0.05 0.28 17.22 WIMD 5/27/99 calcite 25.75 59.08 0.07 0.53 0.27 0.11 0.06 0.16 13.97 WIMD 5/27/99 calcite 16.48 61.83 0.07 0.83 0.10 0.01 0.12 0.19 20.38 WIOD 5/27/99 calcite 30.60 54.03 0.07 0.46 1.13 0.16 0.13 0.24 13.17 WIOD 5/27/99 calcite 18.33 61.93 -0.01 0.41 0.12 -0.01 0.07 0.01 19.15 WIOD 5/27/99 calcite 21.12 59.12 0.09 0.61 1.38 -0.04 0.14 -0.02 17.58 WIOD 5/27/99 calcite 24.39 48.30 0.06 0.36 0.19 0.13 0.10 0.12 26.35 WIOD 5/27/99 calcite 23.65 53.45 0.37 0.76 0.77 0.06 0.29 0.14 20.51 WIOD 5/27/99 calcite 17.65 39.63 -0.06 0.45 0.33 0.20 0.11 0.00 41.70 WllD 5/27/99 calcite 21.08 53.92 -0.13 0.42 0.35 0.38 0.17 0.27 23.56 WllD 5/27/99 calcite 24.58 42.64 -0.08 0.48 0.15 0.69 0.38 1.13 30.01 WllD 5/27/99 calcite 25.89 33.42 -0.06 0.33 0.19 0.50 0.12 0.50 39.10 WllD 5/27/99 calcite 28.63 53.14 -0.04 0.26 0.36 0.15 0.17 0.18 17.17 WllD 5/27/99 calcite 17.36 54.62 0.17 0.46 0.21 0.37 0.09 0.37 26.35 W21D 5/27/99 calcite 23.88 47.94 -0.01 0.53 1.05 0.21 0.17 0.35 25.89 W21D 5/27/99 calcite 71.35 — 0.17 0.38 0.25 0.22 0.1 0.44 27.08 W21D 5/27/99 calcite 68.63 — -0.03 0.73 0.49 0.36 0.11 0.16 29.56

W21D 5/27/99 calcite 77.95 — 0.07 0.77 1.19 0.32 0.1 0.93 18.68 W21D 5/27/99 calcite 72.18 —— 0.54 0.92 2.4 0.3 0.52 1.45 21.69 W2ID 5/27/99 calcite 38.38 35.08 0.01 0.21 0.16 0.04 0.06 0.23 25.81 W21D 5/27/99 calcite 29.02 42.99 0.13 0.45 0.23 0.19 0.12 0.44 26.43 W21D 5/27/99 calcite 30.95 56.75 0.20 0.62 0.08 0.07 0.03 0.06 11.24 W21D 5/27/99 calcite 35.06 39.11 0.15 0.31 0.94 0.25 0.10 0.61 23.48 W21D 5/27/99 calcite 23.83 55.91 0.03 0.63 0.13 0.16 0.05 0.05 19.20 WIOD 5/27/99 algae 56.26 36.66 0.10 -0.02 2.81 0.27 0.28 1.50 2.13 W21D 5/27/99 algae 58.53 37.40 1.11 0.29 0.15 0.32 0.96 0.73 0.50 W2MD 5/27/99 algae 77.74 18.16 0.18 0.20 0.32 0.11 1.28 1.69 0.31 WIMD 8/28/98 algae 51.78 38.93 -0.17 0.31 1.37 0.71 0.48 2.23 4.35 WIMD 8/28/98 calcite 29.78 36.95 0.18 0.43 0.43 0.33 0.20 0.43 31.27 WIMD 8/28/98 calcite 29.03 49.94 0.03 0.60 0.25 0.53 0.20 0.42 19.00 WIMD 8/28/98 calcite 29.84 50.18 -0.22 0.29 1.21 0.26 0.58 0.82 17.04

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157 Appendix J, continued

Sample Sampling Sample Elemental percentages site date type C 0 Na Mg Si P Cl K Ca WIMD 8/28/98 calcite 26.63 47.12 0.13 0.45 2.85 0.16 1.32 1.56 19.79 WIMD 8/28/98 calcite 24.10 52.72 0.23 0.68 0.57 0.18 0.28 0.41 20.84 W2MD 8/28/98 calcite 27.42 52.14 0.06 0.61 0.77 0.05 0.03 0.11 18.81 W2MD 8/28/98 calcite 31.27 56.24 0.01 0.48 1.02 0.18 0.10 0.23 10.47 W2MD 8/28/98 calcite 16.98 57.11 0.10 0.56 1.13 0.16 0.17 0.22 23.56 W2MD 8/28/98 calcite 29.74 55.32 0.02 0.46 1.44 0.05 0.06 0.25 12.66 W2MD 8/28/98 calcite 25.39 55.19 0.01 0.44 2.30 0.25 0.19 0.59 15.64 Meso 4 9/8/98 calcite 63.54 31.62 0.09 0.39 0.35 0.05 0.2 0.44 3.32 Meso 4 9/8/98 calcite 58.79 0.01 1.96 1.52 0.14 0.03 0.45 37.09 Meso 4 9/8/98 calcite 79.12 —— -0.09 1.21 0.67 0.21 0.1 0.17 18.59 Meso 4 9/8/98 calcite 84.84 0.41 1.77 0.33 0.14 0.13 0.18 12.2 Meso 6 9/8/98 calcite 20.60 55.37 -0.04 0.57 0.34 0.09 0.16 0.17 22.74 Meso 6 9/8/98 calcite 26.80 56.53 0.08 0.63 2.52 0.12 0.21 0.21 12.89 Meso 6 9/8/98 calcite 40.43 48.40 0.04 0.63 2.68 0.06 0.15 0.54 7.06 Meso 6 9/8/98 calcite 25.23 57.34 -0.07 1.57 1.10 0.14 0.17 0.38 14.15 Meso 6 9/8/98 calcite 26.41 57.00 0.04 1.01 1.52 0.12 0.49 0.39 13.03 Meso 9 9/8/98 calcite 92.89 — 0.02 0.28 0.3 0.05 0.47 0.37 5.61 Meso 9 9/8/98 calcite 82.19 — -0.18 1.46 0.52 0 0.3 0.34 15.37 Meso 9 9/8/98 calcite 84.71 — 0.09 1.67 0.27 -0.03 0.21 0.26 12.83 Meso 15* 9/8/98 calcite 76.81 -0.15 1.28 0.83 0.12 0.39 0.3 20.42 Meso 15* 9/8/98 calcite 73.87 0.09 2.21 0.46 0 0.13 0.05 23.19 Meso 15* 9/8/98 calcite 76.46 -0.2 1.98 0.56 -0.01 0.18 0.22 20.81 Meso 15* 9/8/98 calcite 78.95 — -0.19 1.41 1.52 0.07 0.47 0.67 17.11 Meso 15* 9/8/98 calcite 77.77 0.04 1.99 0.27 0.06 0.17 0.16 19.54 Meso 15* 9/8/98 calcite 74.43 — -0.03 1.4 0.63 0.25 0.7 0.68 21.94 Meso 16 9/8/98 calcite 85.04 •— 0.07 0.9 3.72 0.21 0.51 0.73 8.84 Meso 16 9/8/98 calcite 83.66 — 0.17 1.37 0.39 0.08 0.13 0.11 14.09 Meso 16 9/8/98 calcite 56.52 -- 0.09 1.82 2.06 0.24 0.46 0.48 38.32 Meso 16 9/8/98 calcite 72.67 -0.02 1.5 0.39 0.18 0.19 0.2 24.88 11,5 5/13/99 upper sed 16.37 63.61 0.34 8.42 2.40 0.04 -0.03 0.19 8.65 11,5 5/13/99 upper sed 19.26 57.15 0.68 0.43 1.75 0.04 0.02 0.10 20.58 11,5 5/13/99 upper sed 11.49 61.90 0.25 10.16 1.53 -0.04 0.04 0.16 14.51 11,17 5/13/99 upper sed 12.57 63.75 0.53 0.36 1.78 0.13 0.04 0.05 20.79 13,13 5/13/99 upper sed 67.16 -- 0.45 1.04 0.99 -0.3 0.25 0.28 30.12 13,13 5/13/99 upper sed 29.62 — 0.17 1.33 0.4 -0.22 -0.43 -0.2 69.34 13,13 5/13/99 upper sed 13.64 -- 1.45 1.03 0.5 0.79 -0.14 0.16 82.61 13,13 5/13/99 upper sed 48.89 0.7 2.16 3.23 0.35 0.39 -0.3 44.53 13,13 5/13/99 upper sed 21.09 54.60 0.36 1.09 1.57 0.17 0.19 -0.1 21.07

158 APPENDIX K - CALCIUM CARBONATES IN WETLAND SEDIMENTS

Pre-flooding samples were taken in September 1993 (Naim 1996). Post-flooding samples were taken in September 1995(Naim 1996) and May 1999. All samples were analyzed for carbonates in 1999. X,Y coordinates refer to permanent 10 m x 10 m grid set up in 1993 (See Fig 3.2). CCE = Calcium carbonate equivalent.

Sampling Depth Calcite Dolomite CCE Bulk density Calcite Dolomite CCE Date x,y cm % % % g dry wt/mL mg/mL mg/mL mg/mL 1993 2,9 0-8 0.9 0.8 1.8 0.98 9.1 7.4 17.2 1993 2,9 0-8 0.7 0.8 1.5 0.98 6.6 7.8 15.0 1993 2,9 8-16 0.2 0.0 0.3 1.25 0.6 3.3 1993 2,11 0-8 0.9 0.4 1.3 1.45 13.4 5.5 19.4 1993 2,11 8-16 0.5 0.0 0.5 1.21 5.9 0.0 5.8 1993 4,3 0-8 0.7 -0.2 0.4 1.45 9.5 -2.9 6.3 1993 4,3 8-16 1.0 -0.2 0.9 1.25 12.9 -2.0 10.8 1993 4,3 8-16 0.2 0.3 0.5 1.25 2.2 3.3 5.8 1993 4,5 0-8 0.4 0.0 0.4 1.28 4.5 0.1 4.6 1993 4,5 8-16 0.7 -0.2 0.5 1.04 7.6 -2.5 5.0 1993 4,9 8-16 0.8 0.1 0.9 1.01 8.0 0.9 9.0 1993 4,9 0-8 0.7 -0.2 0.5 1.15 8.1 -2.5 5.4 1993 4,11 8-16 0.2 -0.6 -0.4 1.24 2.3 -6.8 -5.1 1993 4,15 0-8 0.9 0.4 1.3 1.18 11.0 4.5 15.8 1993 4,15 8-16 -0.3 -0.5 -0.8 1.24 -3.2 -6.7 -10.5 1993 4,17 8-16 -0.2 0.6 0.4 1.12 -2.4 6.8 5.0 1993 4,17 0-8 0.7 0.7 1.4 1.56 10.2 11.3 22.5 1993 6,3 8-16 -0.1 0.0 -0.1 1.39 -2.0 0.5 -1.5 1993 6,3 0-8 -0.1 -0.2 -0.4 1.25 -1.3 -2.9 -4.5 1993 6,5 0-8 -0.2 -0.6 -0.8 1.48 -3.1 -8.5 -12.3 1993 6,5 8-16 -0.3 -0.7 -1.1 1.30 -3.4 -9.5 -13.7 1993 6,15 0-8 0.0 -0.3 -0.3 1.11 0.4 -3.4 -3.4 1993 6,15 8-16 0.5 0.0 0.5 1.34 6.9 0.0 6.9 1993 6,15 8-16 -0.2 0.0 -0.2 1.34 -2.8 0.7 -2.1 1993 6,17 8-16 0.1 -0.1 0.0 1.15 1.4 -1.6 -0.3 1993 6,17 8-16 -0.2 0.2 0.0 1.15 -2.4 2.6 0.4 1993 6,17 0-8 0.3 -0.2 0.1 1.53 5.2 -3.7 1.2 1993 9,5 8-16 -0.1 -0.2 -0.3 1.14 -1.0 -2.5 -3.7 1993 9,17 0-8 -0.1 -0.2 -0.4 1.41 -1.5 -3.2 -5.0 1993 11,5 0-8 -0.1 -0.9 -1.1 1.25 -0.8 -11.5 -13.3 1993 11,11 0-8 0.7 -0.2 0.4 1.62 10.7 -3.3 7.2 1993 11,11 8-16 0.5 -0.4 0.1 1.06 5.2 -3.8 1.0 1993 11,13 0-8 0.3 0.4 0.7 1.15 3.1 4.7 8.2 1993 11,13 8-16 -0.1 -0.2 -0.3 1.15 -1.6 -1.8 -3.6 1993 11,15 0-8 0.3 -0.2 0.0 1.03 3.0 -2.3 0.5 1993 11,15 8-16 0.8 0.0 0.8 1.28 9.7 0.0 9.6 1993 11,17 8-16 0.3 -0.2 0.0 1.05 2.9 -2.3 0.4 1993 11,17 0-8 -0.2 0.2 0.0 1.33 -2.1 2.3 0.5 1993 13,9 0-8 0.2 -0.2 0.0 1.39 3.4 -2.8 0.4 1993 13,9 8-16 0.1 -0.1 0.0 1.23 1.1 -1.4 -0.4 1993 13,13 8-16 -0.1 0.2 0.1 1.12 -0.9 2.1 1.4

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159 Appendix ÎC, continued

Sampling Depth Calcite Dolomite CCE Bulk density Calcite Dolomite CCE Date x,y cm % % % g dry Wt/mL mg/mL mg/mL mg/mL 1993 13,13 0-8 0.0 0.4 0.5 1.19 0.4 4.7 5.6 1993 13,17 0-8 0.2 0.2 0.4 1.11 2.2 2.5 4.9 1993 13,17 8-16 0.0 0.0 0.0 1.22 0.0 0.0 0.0 1995 2,9 0-8 2.7 1.8 4.7 0.780 21.1 14.3 36.7 1995 2,9 8-16 1.0 0.0 1.0 0.780 7.6 0.2 7.8 1995 2,11 0-8 1.5 0.9 2.5 0.760 11.2 7.1 18.9 1995 2,11 8-16 I.O 0.5 1.6 1.130 11.4 5.9 17.9 1995 4,3 0-8 3.1 3.3 6.7 0.470 14.3 15.6 31.3 1995 4,3 8-16 -0.1 -0.1 -0.2 1.130 -1.7 -0.7 -2.4 1995 4,3 0-8 2.7 4.0 7.1 0.470 12.7 19.0 33.3 1995 4,5 8-16 1.2 -0.2 0.9 1.080 12.5 -2.4 9.8 1995 4,9 0-8 6.8 2.1 9.1 0.530 36.1 11.3 48.4 1995 4,9 8-16 0.9 -0.1 0.8 1.030 9.2 -0.6 8.6 1995 4,11 0-8 3.6 0.7 4.3 0.740 26.5 4.8 31.7 1995 4,11 8-16 -0.1 -0.4 -0.5 1.020 -1.3 -3.9 -5.5 1995 4,15 0-8 0.7 0.6 1.3 0.890 6.1 5.1 11.6 1995 4,5 0-8 3.6 1.3 5.0 0.820 29.4 10.9 41.3 1995 4,15 8-16 0.2 -0.3 -0.1 1.020 2.3 -3.0 -1.0 1995 4,17 0-8 1.1 0.1 1.2 0.760 8.4 0.8 9.2 1995 4,17 8-16 0.7 0.1 0.9 1.010 7.2 1.3 8.6 1995 6,3 0-8 0.4 0.0 0.4 0.790 3.0 0.3 3.4 1995 6,3 8-16 0.3 0.2 0.5 1.060 2.9 2.0 5.1 1995 6,5 0-8 1.3 0.2 1.5 0.780 10.2 1.3 11.6 1995 6,5 8-16 0.6 -0.2 0.4 1.2 7.5 -2.6 4.6 1995 6,15 0-8 0.9 -0.3 0.6 0.660 5.7 -1.7 3.9 1995 6,15 8-16 1.0 -0.5 0.4 0.980 9.6 -4.9 4.3 1995 6,17 0-8 -0.2 -0.5 -0.8 0.870 -1.7 -4.8 -6.9 1995 6,17 8-16 0.4 0.2 0.5 1.120 4.1 1.9 6.1 1995 9,5 0-8 1.6 0.5 2.1 0.620 9.9 3.1 13.3 1995 9,17 0-8 0.7 0.0 0.7 0.750 5.1 0.2 5.4 1995 9,17 8-16 0.9 -0.3 0.6 0.910 8.3 -2.4 5.7 1995 11.5 0-8 9.6 3.0 12.8 0.300 28.9 8.9 38.5 1995 11,5 8-16 4.2 1.5 5.9 0.710 29.8 11.0 41.7 1995 11,11 0-8 0.4 0.3 0.7 0.680 2.9 1.8 4.9 1995 11,11 8-16 1.0 -0.2 0.8 0.950 9.5 -2.2 7.1 1995 11,13 0-8 1.2 0.3 1.5 0.660 7.7 1.7 9.6 1995 11,13 8-16 1.0 -0.3 0.7 0.670 6.9 -1.9 4.8 1995 11,15 8-16 0.7 -0.6 0.0 1.020 7.3 -6.5 0.3 1995 11,17 8-16 0.1 -0.5 -0.4 0.910 0.8 -4.3 -3.8 1995 13,9 0-8 3.2 0.6 3.9 0.740 23.7 4.6 28.7 1995 13,9 8-16 0.6 -0.2 0.4 0.870 5.3 -1.9 3.3 1995 13,13 0-8 3.1 0.6 3.8 0.600 18.7 3.6 22.6 1995 13,13 8-16 0.5 -0.5 -0.1 1.290 6.2 -6.7 -1.2 1995 13,17 0-8 0.9 0.1 1.0 0.770 7.0 0.9 8.0 1995 13,17 8-16 0.5 0.2 0.7 0.720 3.3 1.4 4.9

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160 Appendix K, continued

Sampling Depth Calcite Dolomite CCE Bulk density Calcite Dolomite CCE Date x,y cm % % % g dry Wt/mL mg/mL mg/mL mg/mL 1995 9,5 8-16 1.2 -0.2 0.9 1.060 12.5 -2.5 9.8 1995 11,17 0-8 0.7 0.1 0.7 0.640 4.2 0.5 4.7 1999 2,9 0-8 7.7 1.8 9.6 1.465 112.1 26.4 140.9 1999 2,9 8-16 0.4 0.5 0.9 0.847 3.1 3.8 7.3 1999 2,11 0-8 4.6 1.5 6.2 0.976 44.5 14.9 60.7 1999 2,11 8-16 0.3 0.5 0.9 1.437 4.7 7.1 12.4 1999 4,3 0-8 6.5 4.9 11.9 0.6S6 44.6 33.9 81.4 1999 4,3 8-16 1.8 1.4 3.4 1.285 23.7 17.9 43.1 1999 4,5 0-8 4.2 1.7 6.1 0.942 39.4 16.2 57.0 1999 4,5 0-8 3.8 2.5 6.5 1.481 56.5 36.9 96.6 1999 4,5 8-16 1.0 0.3 1.3 1.481 14.3 4.0 18.7 1999 4,9 0-8 1.6 0.9 2.5 1.103 17.5 9.5 27.8 1999 4,9 8-16 0.3 0.2 0.5 1.351 4.5 2.2 6.9 1999 4,11 0-8 1.3 -0.2 1.1 1.307 17.3 -3.0 14.0 1999 4,11 8-16 0.6 -0.7 -0.2 1.388 7.9 -9.3 -2.2 1999 4,15 0-8 8.3 1.6 10.0 0.642 53.0 10.4 64.4 1999 4,17 8-16 0.3 0.4 0.7 1.439 4.3 5.0 9.7 1999 4,17 0-8 0.1 0.4 0.5 1.252 1.1 4.6 6.1 1999 6,3 0-8 0.2 0.2 0.4 1.489 3.0 3.4 6.6 1999 6,3 8-16 0.1 0.0 0.1 1.373 0.8 0.0 0.8 1999 6,3 8-16 -0.4 0.0 -0.4 1.373 -5.5 0.6 -4.9 1999 6,5 8-16 0.4 -0.1 0.3 1.386 5.7 -1.1 4.6 1999 6,5 0-8 3.7 1.4 5.3 0.814 30.3 11.5 42.8 1999 6,15 0-8 5.8 1.5 7.4 0.781 45.6 11.5 58.1 1999 6,15 8-16 0.6 -0.3 0.3 1.432 9.0 -4.7 3.9 1999 6,17 0-8 0.2 0.4 0.7 1.042 2.3 4.6 7.3 1999 6,17 8-16 0.4 -0.1 0.3 1.381 4.9 -0.8 4.0 1999 9,5 0-8 1.6 0.7 2.3 1.505 23.5 10.1 34.5 1999 9,5 8-16 1.1 -0.6 0.4 1.216 13.1 -7.1 5.4 1999 9,6 0-8 3.1 1.6 4.9 0.711 22.1 11.6 34.6 1999 9,6 8-16 -0.1 0.1 0.0 1.449 -1.4 1.0 -0.4 1999 9,17 0-8 1.9 1.0 3.0 1.016 19.1 10.2 30.2 1999 9,17 8-16 0.3 0.2 0.5 1.426 3.9 2.8 7.0 1999 11,5 0-8 8.4 2.4 11.1 0.904 76.1 22.0 100.0 1999 11,5 8-16 1.3 -0.2 1.2 1.461 19.5 -2.2 17.1 1999 11,11 0-8 3.5 1.0 4.6 0.963 33.4 10.0 44.2 1999 11,11 8-16 0.5 0.0 0.5 1.428 7.5 -0.3 7.1 1999 11,13 0-8 1.5 0.4 2.0 1.169 17.6 4.9 22.9 1999 11,13 0-8 1.4 0.3 1.7 1.169 15.8 3.3 19.4 1999 11,13 8-16 0.0 0.1 0.1 1.453 -0.5 2.0 1.7 1999 11,15 8-16 0.3 -0.2 0.1 1.450 4.4 -3.3 0.8 1999 11,15 8-16 0.2 -0.4 -0.2 1.450 3.4 -5.6 -2.8 1999 11,15 0-8 0.1 -0.2 0.0 1.036 1.5 -1.6 -0.2 1999 11,17 0-8 2.8 0.6 3.5 0.907 25.4 5.9 31.8 1999 11,17 8-16 0.3 0.2 0.5 1.324 3.7 2.6 6.5

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161 Appendix K, continued

Sampling Depth Calcite Dolomite CCE Bulk density Calcite Dolomite CCE Date x,y cm % % % g drv Wt/mL mg/mL mg/mL mg/mL 1999 12,5 0-8 7.9 2.4 10.5 1.597 126.0 38.4 167.8 1999 12,5 8-16 0.9 -0.1 0.8 0.578 5.2 -0.6 4.5 1999 13,9 0-8 8.1 1.8 10.1 0.732 59.6 13.2 73.9 1999 13,9 8-16 0.3 0.0 0.3 1.608 4.4 0.3 4.7 1999 13,13 0-8 5.9 1.8 7.9 1.007 59.4 18.3 79.3 1999 13,13 8-16 0.3 0.0 0.3 1.328 3.4 0.0 3.5 1999 13,17 0-8 0.6 0.2 0.8 1.007 6.4 1.9 8.5 1999 13,17 8-16 -0.6 -0.3 -0.9 1.328 -7.4 -4.3 -12.0

162 APPENDIX L - MESOCOSM WATER QUALITY DATA

Water quality parameters in wetland mesocosms, 1998. C=control, A=algal treatment.

Cond Temp DO at 25 C Redox SRP Total P Ca Date Time Meso Treat C mg/L llS/cm pH mV ug/L ug/I mg/L 7/8/98 dawn I C 23.62 5.51 359 7.17 366 36.6 76.3 31.9 7/8/98 dawn 2 A 24.11 6.73 279 8.46 331 7.4 22.8 27.5 7/8/98 dawn 3 C 23.37 6.05 344 7.32 343 28.9 71.9 35.2 7/8/98 dawn 4 A 23.78 6.77 281 8.45 325 7.8 23.1 24.2 7/8/98 dawn 5 C 23.78 6.60 336 7.44 336 32.8 67.1 36.3 7/8/98 dawn 6 A 24.08 4.28 300 7.51 335 7.3 23.6 27.5 7/8/98 dawn 7 A 24.09 4.81 273 8.13 324 4.6 21.7 23.1 7/8/98 dawn 8 C 24.17 6.23 301 7.48 329 31.5 62.0 28.6 7/8/98 dawn 9 A 23.91 6.34 272 8.39 317 4.6 21.3 20.9 7/8/98 dawn 10 C 23.76 5.74 310 7.43 326 23.7 59.6 27.5 7/8/98 dawn II C 23.91 6.03 331 7.45 330 43.7 93.2 29.7 7/8/98 dawn 12 A 23.98 6.27 275 8.68 310 25.1 35.6 19.8 7/8/98 dawn 13 C 24.02 5.54 342 7.42 323 17.3 55.0 30.8 7/8/98 dawn 14 A 24.09 4.86 296 8.01 319 6.8 33.7 24.2 7/8/98 dawn 15 A 24.13 5.71 293 7.97 317 12.2 19.1 24.2 7/8/98 dawn 16 A 24.19 5.21 290 8.15 314 7.1 9.3 23.1 7/8/98 dawn 17 C 23.97 5.52 330 7.39 324 21.0 53.7 30.8 7/8/98 dawn 18 A 24.04 6.14 294 8.17 310 4.6 29.0 25.3 7/8/98 dawn 19 C 23.86 6.02 351 7.56 319 26.1 53.2 34.1 7/8/98 dawn 20 C 23.98 5.27 335 7.42 323 24.9 54.2 30.8 7/8/98 dusk I C 25.12 4.65 392 7.55 417 38.3 73.0 33.0 7/8/98 dusk 2 A 28.36 17.71 287 9.82 388 14.6 25.1 19.8 7/8/98 dusk 3 C 26.78 5.87 362 7.73 423 28.9 63.2 36.3 7/8/98 dusk 4 A 27.41 12.24 294 10.00 384 7.9 20.5 20.9 7/8/98 dusk 5 C 27.08 6.37 365 7.88 422 36.3 60.6 31.9 7/8/98 dusk 6 A 29.34 15.19 284 9.40 394 7.4 23.9 20.9 7/8/98 dusk 7 A 29.26 14.51 267 9.67 392 8.2 24.3 19.8 7/8/98 dusk 8 C 27.20 6.24 322 7.80 424 28.5 56.5 28.6 7/8/98 dusk 9 A 29.22 15.61 275 10.01 394 7.8 24.5 18.7 7/8/98 dusk 10 C 26.47 5.79 343 7.65 428 21.7 47.3 29.7 7/8/98 dusk II C 26.25 6.06 362 7.84 423 35.7 77.8 30.8 7/8/98 dusk 12 A 28.46 14.51 283 9.97 390 9.5 25.4 17.6 7/8/98 dusk 13 C 26.19 5.41 373 7.75 421 20.4 57.0 28.6 7/8/98 dusk 14 A 28.53 15.13 289 9.66 391 8.1 26.1 19.8 7/8/98 dusk 15 A 28.57 12.53 281 9.81 393 8.3 14.5 19.8 7/8/98 dusk 16 A 28.61 11.78 289 9.75 396 9.0 26.3 20.9 7/8/98 dusk 17 C 26.01 5.08 369 7.78 427 8.1 38.2 28.6 7/8/98 dusk 18 A 28.03 15.22 301 9.67 403 4.6 22.4 23.1 7/8/98 dusk 19 C 26.04 6.38 390 7.80 428 14.0 49.5 36.3 7/8/98 dusk 20 C 25.81 4.61 363 7.89 427 24.9 49.8 29.7 7/9/98 dawn IC 23.91 5.14 378 6.86 437 40.3 67.2 31.9 7/9/98 dawn 2 A 24.79 11.62 277 8.75 398 12.9 13.9 22.0 7/9/98 dawn 3 C 23.88 5.64 370 7.42 418 24.2 56.1 30.8 7/9/98 dawn 4 A 24.64 10.89 279 8.68 394 4.6 20.4 17.6 7/9/98 dawn 5 C 24.19 6.24 359 7.54 415 33.6 152.2 28.6 7/9/98 dawn 6 A 25.22 8.47 294 8.09 399 15.8 41.8 27.5 7/9/98 dawn 7 A 25.09 8.54 274 8.48 393 18.8 27.5 7/9/98 dawn 8 C 24.35 5.89 322 7.54 406 33.9 55.6 25.3 7/9/98 dawn 9 A 24.76 11.56 270 8.81 384 17.6 14.9 20.9 7/9/98 dawn 10 C 24.17 5.07 325 7.52 408 24.2 42.8 30.8

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163 Appendix L, continued

Cond Temp DO at25C Redox SRP Total P Ca Date Time Meso Treat C mg/L |iS/cm pH mV ug/L ug/I mg/L 7/9/98 dawn 11 C 24.06 5.84 349 7.41 404 33.7 75.6 29.7 7/9/98 dawn 12 A 24.66 9.34 276 8.79 382 8.1 88.1 18.7 7/9/98 dawn 13 C 24.13 5.27 354 7.50 396 21.7 64.6 29.7 7/9/98 dawn 14 A 24.83 9.39 287 8.48 378 7.8 13.8 20.9 7/9/98 dawn 15 A 24.81 10.05 288 8.46 381 3.6 27.8 26.4 7/9/98 dawn 16 A 24.92 9.66 286 8.56 382 6.4 14.4 20.9 7/9/98 dawn 17 C 24.04 4.98 352 7.47 395 19.8 35.8 29.7 7/9/98 dawn 18 A 24.70 10.65 289 8.58 382 9.6 23.2 23.1 7/9/98 dawn 19 C 24.09 4.92 370 7.50 394 26.8 48.3 30.8 7/9/98 dawn 20 C 24.28 4.59 352 7.33 396 25.7 44.6 29.7 7/28/98 dawn 1 C 23.53 5.48 497 7.88 184 27.4 27.9 54.8 7/28/98 dawn 2 A 24.09 8.67 314 8.52 172 2.4 23.8 21.5 7/28/98 dawn 3 C 23.35 5.69 504 8.03 186 36.7 61.6 51.7 7/28/98 dawn 4 A 24.13 9.27 339 8.52 176 7.5 5.4 22.6 7/28/98 dawn 5 C 23.29 6.18 479 8.15 189 15.4 46.8 55.9 7/28/98 dawn 6 A 24.66 13.30 309 9.21 159 2.4 7.0 20.6 7/28/98 dawn 7 A 24.52 9.54 371 8.26 187 2.4 25.9 31.5 7/28/98 dawn 8 C 23.84 5.58 459 8.04 191 43.8 38.3 49.8 7/28/98 dawn 9 A 23.93 10.40 311 8.65 183 2.4 21.9 24.3 7/28/98 dawn 10 C 23.39 5.68 453 8.16 194 41.8 60.1 51.7 7/28/98 dawn 11 C 24.31 5.54 486 8.78 196 24.0 34.4 57.8 7/28/98 dawn 12 A 24.44 14.04 311 9.82 157 8.8 12.3 23.1 7/28/98 dawn 13 C 23.86 5.61 470 8.20 198 25.1 16.4 52.3 7/28/98 dawn 14 A 24.70 12.56 312 9.25 159 6.1 0.0 21.3 7/28/98 dawn 15 A 24.20 10.87 337 8.66 178 19.8 8.1 25.4 7/28/98 dawn 16 A 24.53 13.55 320 9.47 170 5.1 12.3 22.7 7/28/98 dawn 17 C 23.24 5.03 493 8.21 202 21.0 31.2 53.1 7/28/98 dawn 18 A 24.42 12.26 322 9.12 177 15.1 7.3 25.3 7/28/98 dawn 19 C 23.39 6.09 491 8.14 201 47.9 42.9 54.1 7/28/98 dawn 20 C 23.73 5.27 494 7.89 202 27.9 33.1 54.2 7/28/98 dusk 1 C 25.52 4.53 473 7.64 253 40.3 50.4 55.0 7/28/98 dusk 2 A 28.36 17.02 287 9.51 242 8.6 9.1 20.4 7/28/98 dusk 3 C 25.59 5.24 480 8.05 259 41.6 51.3 53.2 7/28/98 dusk 4 A 28.30 16.05 305 9.26 231 2.4 12.4 25.5 7/28/98 dusk 5 C 25.25 5.22 462 7.90 262 58.9 42.2 53.5 7/28/98 dusk 6 A 28.16 21.81 329 9.99 206 4.6 9.1 21.8 7/28/98 dusk 7 A 27.72 13.98 344 9.14 223 2.4 6.8 27.9 7/28/98 dusk 8 C 26.55 5.65 441 7.92 263 37.3 44.1 51.9 7/28/98 dusk 9 A 27.89 14.49 285 9.67 211 23.6 21.4 24.2 7/28/98 dusk 10 C 24.92 5.30 442 7.83 267 31.3 42.4 48.8 7/28/98 dusk 11 C 25.91 5.39 479 7.81 255 27.2 39.5 54.6 7/28/98 dusk 12 A 28.08 19.62 335 10.24 192 8.2 18.0 22.1 7/28/98 dusk 13 C 24.53 5.27 472 7.77 277 15.2 22.0 51.8 7/28/98 dusk 14 A 28.38 19.44 317 10.05 186 25.4 5.6 21.3 7/28/98 dusk 15 A 27.89 15.95 312 9.45 198 26.5 4.9 24.4 7/28/98 dusk 16 A 28.55 17.41 326 10.11 187 2.4 5.5 23.7 7/28/98 dusk 17 C 25.11 4.82 488 7.78 280 24.5 26.5 54.7 7/28/98 dusk 18 A 28.22 16.61 306 9.69 192 5.9 24.6 7/28/98 dusk 19 C 26.61 5.61 464 7.93 278 45.2 52.7 7/28/98 dusk 20 C 26.30 4.61 473 7.79 278 32.7 35.8 55.4 7/29/98 dawn 1 c 24.00 5.53 496 7.84 295 35.3 62.4 54.0 7/29/98 dawn 2 A 23.95 7.64 309 8.93 285 4.9 33.0 22.2

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164 Appendix L, continued

Cond Temp DO at 25 C Redox SRP Total P Ca Date Time Meso Treat C mg/L |j,S/cm pH mV ug/L ug/1 mg/L 7/29/98 dawn 3 C 23.60 5.67 505 7.85 299 37.0 159.3 53.8 7/29/98 dawn 4 A 24.09 8.87 331 8.85 284 29.3 10.7 25.0 7/29/98 dawn 5 C 23.49 5.91 481 8.10 302 36.7 52.7 7/29/98 dawn 6 A 24.00 13.18 313 9.75 267 6.1 33.6 26.4 7/29/98 dawn 7 A 23.91 9.22 374 8.44 284 4.1 6.4 28.9 7/29/98 dawn 8 C 24.06 6.11 459 7.87 304 32.6 50.6 52.3 7/29/98 dawn 9 A 23.86 9.73 307 8.97 275 2.4 7.9 25.9 7/29/98 dawn 10 C 23.75 5.91 450 7.93 305 37.5 47.0 49.9 7/29/98 dawn 11 C 24.55 5.28 486 7.93 307 33.6 37.9 55.8 7/29/98 dawn 12 A 24.28 12.81 309 10.01 252 2.4 11.9 20.9 7/29/98 dawn 13 C 23.91 5.85 474 7.95 309 23.5 34.1 53.8 7/29/98 dawn 14 A 24.19 11.74 314 9.65 252 2.4 21.1 20.5 7/29/98 dawn 15 A 24.13 10.36 334 8.95 262 14.8 11.7 23.7 7/29/98 dawn 16 A 24.24 12.66 323 9.73 251 2.4 10.1 23.0 7/29/98 dawn 17 C 23.62 5.28 494 7.86 311 26.9 49.8 47.2 7/29/98 dawn 18 A 24.31 11.15 320 9.34 253 14.4 5.9 22.8 7/29/98 dawn 19 C 23.77 6.04 486 7.95 309 42.2 66.6 53.5 7/29/98 dawn 20 C 24.13 5.49 492 7.87 310 24.9 40.1 52.9 8/20/98 dawn 1 C 21.14 5.16 541 7.50 416 52.2 64.4 56.3 8/20/98 dawn 2 A 20.87 8.33 339 9.12 382 3.4 24.2 21.0 8/20/98 dawn 3 C 21.12 5.05 563 7.74 406 32.6 38.8 59.1 8/20/98 dawn 4 A 21.09 10.63 368 9.28 378 0.3 17.2 22.8 8/20/98 dawn 5 C 21.61 6.14 563 7.95 401 55.3 71.3 56.3 8/20/98 dawn 6 A 21.37 10.10 419 8.82 384 0.3 13.0 26.1 8/20/98 dawn 7 A 20.94 5.42 489 7.87 397 0.3 52.5 35.5 8/20/98 dawn 8 C 22.18 6.13 546 7.86 392 61.5 70.2 55.4 8/20/98 dawn 9 A 21.30 5.49 460 8.02 387 0.3 27.0 31.5 8/20/98 dawn 10 C 21.99 5.71 567 7.90 394 64.4 81.9 58.2 8/20/98 dawn 11 C 21.40 5.57 531 7.89 392 39.7 67.5 55.0 8/20/98 dawn 12 A 21.37 11.59 370 9.56 359 0.3 17.7 24.4 8/20/98 dawn 13 C 22.18 5.04 532 7.87 388 38.9 48.8 54.5 8/20/98 dawn 14 A 22.16 9.47 372 9.11 367 0.3 23.0 27.7 8/20/98 dawn 15 A 21.19 6.40 452 8.06 381 0.3 10.7 32.6 8/20/98 dawn 16 A 21.44 10.29 416 9.04 365 0.3 18.8 27.4 8/20/98 dawn 17 C 21.77 4.44 577 7.92 388 36.2 41.9 60.3 8/20/98 dawn 18 A 21.33 12.62 411 9.38 356 0.3 11.2 25.0 8/20/98 dawn 19 C 21.60 5.99 589 7.88 383 69.5 87.9 62.8 8/20/98 dawn 20 C 21.70 4.69 603 7.86 391 45.5 56.6 62.4 8/20/98 dusk 1 C 24.37 5.28 530 7.70 440 51.8 70.6 54.9 8/20/98 dusk 2 A 27.08 18.81 329 10.21 383 3.2 20.1 19.4 8/20/98 dusk 3 C 23.84 4.64 557 7.83 424 30.9 41.8 57.3 8/20/98 dusk 4 A 27.03 18.42 359 10.15 383 2.8 29.8 24.5 8/20/98 dusk 5 C 24.01 6.16 560 8.10 416 56.0 63.8 58.2 8/20/98 dusk 6 A 27.04 12.72 389 9.84 393 0.3 11.7 24.9 8/20/98 dusk 7 A 27.01 14.68 426 9.20 397 3.5 17.4 28.7 8/20/98 dusk 8 C 25.03 5.66 537 8.14 420 61.8 70.0 57.4 8/20/98 dusk 9 A 27.08 11.57 404 9.42 397 0.9 16.8 24.1 8/20/98 dusk 10 C 24.81 5.16 553 8.05 420 66.5 76.5 56.4 8/20/98 dusk 11 C 24.30 5.45 520 8.01 424 43.1 50.0 55.3 8/20/98 dusk 12 A 27.25 16.37 378 10.32 384 3.8 8.3 31.0 8/20/98 dusk 13 C 24.57 5.31 532 8.00 413 39.0 50.0 54.5 8/20/98 dusk 14 A 26.72 15.14 352 10.03 377 0.9 12.2 21.5

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165 Appendix L, continued

Cond Temp DO at25C Redox SRP Total P Ca Date Time Meso Treat C mg/L pS/cm pH mV ug/L ug/1 mg/L 8/20/98 dusk 15 A 26.21 12.02 407 9.33 390 0.9 20.5 28.5 8/20/98 dusk 16 A 26.85 12.66 389 10.23 376 3.3 16.3 26.6 8/20/98 dusk 17 C 24.39 5.35 580 7.97 412 36.7 40.7 60.3 8/20/98 dusk 18 A 26.08 17.67 401 10.18 369 3.8 20.2 24.3 8/20/98 dusk 19 C 24.35 5.71 581 8.06 406 74.4 85.9 57.4 8/20/98 dusk 20 C 24.88 4.31 590 7.94 410 45.3 56.7 63.5 8/21/98 dawn 1 C 21.61 4.99 533 7.73 477 44.6 54.7 56.4 8/21/98 dawn 2 A 21.26 8.22 329 9.31 441 8.7 8.5 20.1 8/21/98 dawn 3 C 21.92 5.61 554 7.88 471 31.7 36.2 60.1 8/21/98 dawn 4 A 21.77 10.63 358 9.45 437 10.8 41.5 29.6 8/21/98 dawn 5 C 21.90 6.28 554 8.06 462 45.6 68.2 59.1 8/21/98 dawn 6 A 21.70 8.28 419 8.79 447 3.1 15.8 29.0 8/21/98 dawn 7 A 21.65 5.61 477 7.92 459 0.9 17.8 36.5 8/21/98 dawn 8 C 22.43 6.21 542 8.02 461 51.8 67.0 58.3 8/21/98 dawn 9 A 21.69 6.75 447 8.16 451 4.5 17.3 21.8 8/21/98 dawn 10 C 22.24 5.76 562 7.99 434 55.9 87.6 57.8 8/21/98 dawn 11 C 22.13 5.67 518 7.98 454 42.1 52.7 56.2 8/21/98 dawn 12 A 21.95 11.52 365 9.78 421 4.3 14.3 24.8 8/21/98 dawn 13 C 22.40 5.69 530 7.94 440 38.7 47.5 55.1 8/21/98 dawn 14 A 21.72 10.32 368 9.30 416 4.1 18.7 22.2 8/21/98 dawn 15 A 21.24 6.15 448 8.05 424 5.7 15.7 32.6 8/21/98 dawn 16 A 21.99 10.13 408 9.18 411 7.0 8.9 27.2 8/21/98 dawn 17 C 22.00 5.28 572 7.91 434 34.1 38.7 59.4 8/21/98 dawn 18 A 21.83 11.42 409 9.60 403 0.9 7.9 24.4 8/21/98 dawn 19 C 21.97 5.51 583 8.01 421 69.7 83.5 61.9 8/21/98 dawn 20 C 22.08 4.44 600 7.94 428 46.0 52.9 62.0 9/22/98 dawn 1 C 22.58 5.60 714 8.14 580 78.9 104.8 71.9 9/22/98 dawn 2 A 22.99 4.49 646 7.75 550 0.0 50.3 47.4 9/22/98 dawn 3 C 22.40 4.81 717 7.88 546 40.2 56.3 72.1 9/22/98 dawn 4 A 22.59 4.44 582 7.85 540 0.0 16.7 37.6 9/22/98 dawn 5 C 22.59 5.28 702 8.12 536 30.5 46.1 68.2 9/22/98 dawn 6 A 22.75 4.39 648 7.84 535 0.0 19.5 44.4 9/22/98 dawn 7 A 22.95 4.12 738 7.72 537 0.0 66.7 59.8 9/22/98 dawn 8 C 22.79 4.84 715 8.03 532 53.1 80.1 70.0 9/22/98 dawn 9 A 22.90 3.95 673 7.72 510 0.0 20.8 47.9 9/22/98 dawn 10 C 22.56 4.99 715 8.05 497 43.6 107.2 67.7 9/22/98 dawn 11 C 22.81 5.61 749 8.18 495 79.2 108.9 73.2 9/22/98 dawn 12 A 22.77 7.18 605 8.46 487 0.0 26.2 38.6 9/22/98 dawn 13 C 22.74 5.25 730 8.09 496 40.6 63.3 72.4 9/22/98 dawn 14 A 22.84 2.98 641 7.72 493 0.0 27.9 46.2 9/22/98 dawn 15 A 22.97 6.04 636 7.98 484 0.0 20.4 46.1 9/22/98 dawn 16 A 22.61 5.77 612 8.15 479 0.0 11.0 34.9 9/22/98 dawn 17 C 22.81 5.45 727 8.17 484 62.5 86.6 71.6 9/22/98 dawn 18 A 22.81 6.91 606 8.44 475 0.0 11.8 33.4 9/22/98 dawn 19 C 22.58 4.81 758 7.95 486 60.6 76.9 73.6 9/22/98 dawn 20 C 23.20 4.93 740 8.16 485 65.0 87.6 74.0 9/22/98 dusk 1 c 22.59 5.28 733 8.11 480 75.6 109.9 74.8 9/22/98 dusk 2 A 23.28 9.53 649 8.42 472 0.0 40.8 55.2 9/22/98 dusk 3 c 22.54 5.18 725 7.91 480 37.6 64.6 69.9 9/22/98 dusk 4 A 22.79 8.10 587 8.49 468 0.0 26.6 36.9 9/22/98 dusk 5 C 22.61 5.21 709 8.17 476 29.8 52.4 67.0 9/22/98 dusk 6 A 23.01 8.45 644 8.38 470 0.0 16.0 44.1

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166 Appendix L, continued

Cond Temp DO at 25 C Redox SRP Total P Ca Date Time Meso Treat C mg/L pS/cm pH mV ug/L ug/1 mg/L 9/22/98 dusk 7 A 23.48 8.20 729 8.09 473 0.0 66.6 62.0 9/22/98 dusk 8 C 22.68 5.51 712 8.05 472 53.4 72.2 71.8 9/22/98 dusk 9 A 23.29 8.27 672 8.29 424 0.0 20.5 48.7 9/22/98 dusk 10 C 22.36 5.33 720 8.09 433 46.6 81.0 70.7 9/22/98 dusk 11 C 22.58 5.61 758 8.17 433 80.8 109.9 75.0 9/22/98 dusk 12 A 22.86 9.57 600 8.90 419 0.0 14.9 39.1 9/22/98 dusk 13 C 22.59 5.27 736 8.11 434 35.9 50.1 71.5 9/22/98 dusk 14 A 22.92 5.63 645 8.04 434 0.0 34.2 47.2 9/22/98 dusk 15 A 23.06 10.18 629 8.56 425 0.0 19.6 43.2 9/22/98 dusk 16 A 22.75 10.34 606 8.97 416 0.0 13.4 34.7 9/22/98 dusk 17 C 22.41 5.37 740 8.18 434 61.4 85.4 77.2 9/22/98 dusk 18 A 22.86 9.73 603 8.99 416 0.0 12.7 33.3 9/22/98 dusk 19 C 22.29 4.96 765 8.00 436 56.0 80.3 74.7 9/22/98 dusk 20 C 22.83 5.09 750 8.16 436 63.3 86.1 73.6 9/23/98 dawn 1 C 19.00 5.54 779 8.11 509 73.3 110.2 73.7 9/23/98 dawn 2 A 17.22 4.22 731 7.77 512 0.0 46.7 47.6 9/23/98 dawn 3 C 18.26 5.07 783 7.89 511 35.7 48.6 73.0 9/23/98 dawn 4 A 17.22 4.59 654 7.89 506 0.0 13.1 38.1 9/23/98 dawn 5 C 18.74 5.66 761 8.14 505 28.9 41.4 69.0 9/23/98 dawn 6 A 17.02 4.35 730 7.81 501 0.0 20.8 46.2 9/23/98 dawn 7 A 17.36 4.71 813 7.69 503 0.0 57.6 62.3 9/23/98 dawn 8 C 19.19 5.47 764 8.03 497 41.8 74.9 71.2 9/23/98 dawn 9 A 17.02 4.22 754 7.77 494 0.0 29.8 51.2 9/23/98 dawn 10 C 18.67 5.27 765 8.07 489 65.4 70.2 71.7 9/23/98 dawn 11 C 19.57 5.65 794 8.19 483 75.6 103.1 65.2 9/23/98 dawn 12 A 17.94 8.01 653 8.65 471 0.0 12.8 38.2 9/23/98 dawn 13 C 19.27 5.30 782 8.10 482 30.7 58.0 70.8 9/23/98 dawn 14 A 17.19 2.60 728 7.68 480 0.0 19.8 50.5 9/23/98 dawn 15 A 17.43 6.31 703 8.02 470 0.0 29.7 45.8 9/23/98 dawn 16 A 17.34 6.53 672 8.39 462 0.0 15.3 35.4 9/23/98 dawn 17 C 18.86 5.16 788 8.17 467 58.1 79.5 68.8 9/23/98 dawn 18 A 17.46 7.06 669 8.52 455 0.0 14.4 34.1 9/23/98 dawn 19 C 18.24 5.13 825 7.97 466 51.6 75.8 72.2 9/23/98 dawn 20 C 19.10 5.22 802 8.17 464 60.6 82.1 76.6 12/3/98 dawn 1 C 7.96 8.72 978 8.06 566 17.8 61.3 44.4 12/3/98 dawn 2 A 7.67 14.58 742 9.07 537 0.0 37.7 28.2 12/3/98 dawn 3 C 7.73 9.24 959 8.13 543 3.8 53.6 54.3 12/3/98 dawn 4 A 7.85 11.14 808 8.67 529 0.0 12.5 47.2 12/3/98 dawn 5 C 7.85 9.11 953 8.15 539 0.0 38.4 53.5 12/3/98 dawn 6 A 7.90 11.60 896 8.49 527 0.0 21.5 39.2 12/3/98 dawn 7 A 7.88 13.30 764 9.02 510 0.0 18.6 34.8 12/3/98 dawn 8 C 7.81 9.08 946 8.18 524 1.1 40.1 53.9 12/3/98 dawn 9 A 8.39 10.55 876 8.34 522 0.0 23.1 46.1 12/3/98 dawn 10 C 8.17 9.57 958 8.18 526 9.7 48.5 80.3 12/3/98 dawn 11 C 7.71 8.25 964 8.04 522 10.0 56.1 84.8 12/3/98 dawn 12 A 8.14 10.50 864 8.35 518 0.0 21.8 53.9 12/3/98 dawn 13 C 7.73 8.95 964 8.08 522 3.2 38.2 42.7 12/3/98 dawn 14 A 7.96 9.18 955 8.23 510 0.0 46.6 42.3 12/3/98 dawn 15 A 7.94 10.73 850 8.48 507 0.0 20.1 24.4 12/3/98 dawn 16 A 8.11 9.32 916 8.20 508 0.0 21.7 37.8 12/3/98 dawn 17 C 7.78 8.56 994 8.05 510 12.9 76.8 60.1 12)0/98 dawn 18 A 8.09 9.64 920 8.21 507 0.0 24.6 51.0

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167 Appendix L, continued

Cond Temp DO at25C Redox SRP Total P Ca Date Time Meso Treat C mg/L |j.S/cm pH mV ug/L ug/1 mg/L 12/3/98 dawn 19 C 8.16 9.42 961 8.10 511 7.1 54.2 56.3 12/3/98 dawn 20 C 8.16 9.23 934 8.03 511 0.0 83.7 42.7 12/3/98 dusk 1 c 8.50 8.76 951 7.97 571 11.9 60.1 82.7 12/3/98 dusk 2 A 11.48 20.64 631 9.30 532 0.0 36.6 36.6 12/3/98 dusk 3 C 8.88 9.45 935 8.22 551 5.5 35.4 73.3 12/3/98 dusk 4 A 10.68 13.27 719 8.83 537 0.0 25.2 36.6 12/3/98 dusk 5 C 9.22 9.18 910 8.15 547 3.5 6.6 70.9 12/3/98 dusk 6 A 9.75 13.57 838 8.59 533 0.0 1.6 43.7 12/3/98 dusk 7 A 10.62 16.48 720 9.20 517 0.0 0.0 23.1 12/3/98 dusk 8 C 8.81 9.04 909 8.21 539 2.4 16.9 58.8 12/3/98 dusk 9 A 10.84 12.08 789 8.64 532 0.0 3.2 35.0 12/3/98 dusk 10 C 9.25 9.03 906 8.20 540 9.0 17.9 59.4 12/3/98 dusk 11 C 8.67 8.43 925 8.03 539 6.0 19.5 60.1 12/3/98 dusk 12 A 11.02 11.57 767 8.54 532 0.0 0.0 39.6 12/3/98 dusk 13 C 8.88 8.98 925 8.10 538 1.6 12.0 53.8 12/3/98 dusk 14 A 10.52 10.52 863 8.29 526 0.0 7.2 51.0 12/3/98 dusk 15 A 10.57 12.81 772 8.59 519 0.0 3.3 51.5 12/3/98 dusk 16 A 10.17 10.62 848 8.27 521 0.0 2.2 64.2 12/3/98 dusk 17 C 8.35 8.51 980 8.08 527 12.2 40.2 80.0 12/3/98 dusk 18 A 11.57 10.45 800 8.37 520 0.0 8.4 44.6 12/3/98 dusk 19 C 8.81 9.52 934 8.13 526 7.5 25.1 56.9 12/3/98 dusk 20 C 9.11 8.75 899 8.04 527 0.0 41.9 54.4 12/4/98 dawn 1 C 9.75 8.39 946 8.07 618 16.0 35.1 70.1 12/4/98 dawn 2 A 11.47 17.58 640 9.22 559 0.0 1.3 25.2 12/4/98 dawn 3 C 9.95 8.36 911 8.12 574 3.6 2.1 57.5 12/4/98 dawn 4 A 11.52 12.45 719 8.79 556 0.0 17.7 33.2 12/4/98 dawn 5 C 10.33 8.25 891 8.10 569 0.0 2.5 89.3 12/4/98 dawn 6 A 10.81 12.84 828 8.65 553 0.0 4.9 59.4 12/4/98 dawn 7 A 12.02 15.45 658 9.18 540 0.0 0.0 32.4 12/4/98 dawn 8 C 10.17 8.57 898 8.11 559 3.7 35.3 70.9 12/4/98 dawn 9 A 11.62 11.33 791 8.55 552 0.0 3.6 51.0 12/4/98 dawn 10 C 10.15 9.39 911 8.19 559 9.7 14.4 74.1 12/4/98 dawn 11 C 9.71 7.69 927 8.02 557 8.8 0.0 51.0 12/4/98 dawn 12 A 11.39 10.92 778 8.52 550 3.3 23.0 70.9 12/4/98 dawn 13 C 9.94 8.46 912 8.05 554 0.0 3.5 64.9 12/4/98 dawn 14 A 10.91 10.04 880 8.34 539 0.0 2.0 59.4 12/4/98 dawn 15 A 11.41 11.73 758 8.66 535 0.0 3.6 37.8 12/4/98 dawn 16 A 11.22 10.03 850 8.31 538 0.0 3.9 61.4 12/4/98 dawn 17 C 9.99 8.14 929 8.07 542 12.8 31.3 82.7 12/4/98 dawn 18 A 11.88 9.58 812 8.40 538 0.0 2.4 54.4 12/4/98 dawn 19 C 10.72 8.85 892 8.12 542 4.5 13.4 61.4 12/4/98 dawn 20 C 10.11 8.53 909 8.11 543 0.0 26.8 51.5

168 APPENDIX M - ADDITIONAL MESOCOSM WATER QUALITY DATA

Additional water quality parameters in wetland mesocosms, 1998. C=control, A-algal treatment.

TDC D ie DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 7/8/98 dawn I C 30.8 23.2 7.7 33.3 25.1 8.2 94.7 4.16 7/8/98 dawn 2 A 23.4 15.0 8.3 23.8 16.0 7.7 65.7 5.23 7/8/98 dawn 3 C 29.4 21.2 8.2 32.9 24.7 8.2 92.2 4.33 7/8/98 dawn 4 A 24.1 16.1 7.9 25.2 17.1 8.1 69.3 5.18 7/8/98 dawn 5 C 28.4 20.7 7.7 30.7 23.0 7.8 87.2 4.45 7/8/98 dawn 6 A 30.9 20.6 10.3 31.9 21.8 10.1 82.4 4.38 7/8/Q8 dawn 7 A 25.3 16.7 8.6 25.7 17.4 8.4 71.2 4.86 7/8/98 dawn 8 C 25.2 18.1 7.1 27.1 20.1 7.0 75.0 4.33 7/8/98 dawn 9 A 22.7 14.6 8.0 23.6 15.8 7.8 63.6 5.02 7/8/98 dawn 10 C 26.6 19.6 6.9 29.1 21.5 7.7 78.4 4.27 7/8/98 dawn 11 C 27.0 19.2 7.9 31.1 22.6 8.5 87.8 4.38 7/8/98 dawn 12 A 28.5 20.8 7.7 21.6 13.8 7.8 54.5 5.22 7/8/98 dawn 13 C 20.3 12.6 7.7 30.7 23.3 7.4 86.6 4.36 7/8/98 dawn 14 A 28.3 20.5 7.8 25.9 18.8 7.2 72.6 4.77 7/8/98 dawn 15 A 25.3 17.5 7.7 27.3 18.9 8.5 72.7 4.73 7/8/98 dawn 16 A 25.9 17.0 8.9 24.9 17.1 7.8 65.8 4.85 7/8/98 dawn 17 C 22.3 13.9 8.4 26.2 18.3 8.0 91.5 4.35 7/8/98 dawn 18 A 30.9 22.5 8.4 32.0 23.2 8.8 71.6 4.94 7/8/98 dawn 19 C 25.1 17.1 8.0 31.9 23.9 8.0 91.3 4.56 7/8/98 dawn 20 C 29.1 21.7 7.4 32.0 24.3 7.7 88.6 4.37 7/8/98 dusk 1 c 31.6 24.3 7.3 30.7 22.8 7.9 95.1 4.57 7/8/98 dusk 2 A 32.3 24.4 7.9 33.9 25.4 8.5 59.9 6.40 7/8/98 dusk 3 c 17.4 9.6 7.7 17.4 9.7 7.6 95.9 4.82 7/8/98 dusk 4 A 31.1 23.3 7.8 33.8 24.9 8.9 65.4 6.60 7/8/98 dusk 5 C 17.6 9.8 7.8 17.1 8.6 8.5 90.1 4.89 7/8/98 dusk 6 A 28.1 21.0 7.1 32.7 23.7 9.1 72.0 6.14 7/8/98 dusk 7 A 23.8 14.5 9.4 25.3 15.5 9.8 65.7 6.32 7/8/98 dusk 8 C 19.2 11.0 8.2 20.7 12.6 8.0 77.9 4.70 7/8/98 dusk 9 A 26.4 19.2 7.1 27.7 20.0 7.6 60.2 6.55 7/8/98 dusk 10 C 18.0 9.7 8.3 18.4 10.1 8.3 81.8 4.58 7/8/98 dusk 11 C 27.9 20.1 7.8 29.2 21.5 7.6 85.6 4.80 7/8/98 dusk 12 A 30.4 22.9 7.5 31.4 22.8 8.6 — — 7/8/98 dusk 13 C 15.6 8.1 7.5 16.0 8.2 7.8 —— 7/8/98 dusk 14 A 29.7 22.3 7.4 31.6 23.2 8.4 — —— 7/8/98 dusk 15 A 18.5 11.2 7.3 19.3 11.4 7.8 ——» 7/8/98 dusk 16 A 18.7 10.6 8.1 19.8 11.8 8.1 — —— 7/8/98 dusk 17 C 18.5 10.8 7.7 18.4 10.8 7.6 — —— 7/8/98 dusk 18 A 29.0 21.3 7.6 31.6 24.0 7.6 —— 7/8/98 dusk 19 C 20.5 12.4 8.1 21.3 13.3 8.0 —« 7/8/98 dusk 20 C 29.4 22.1 7.4 32.2 24.4 7.8 —— 7/9/98 dawn 1 C 38.0 29.1 8.9 30.8 23.1 7.8 95.3 3.85 7/9/98 dawn 2 A 36.5 27.7 8.8 34.3 23.8 10.5 64.3 5.42 7/9/98 dawn 3 C 22.4 13.3 9.1 22.3 13.6 8.8 93.3 4.39 7/9/98 dawn 4 A 37.0 28.0 9.1 34.1 25.0 9.1 68.9 5.28 7/9/98 dawn 5 C 25.2 15.4 9.8 23.4 15.1 8.3 87.9 4.45 7/9/98 dawn 6 A 32.7 24.2 8.4 31.4 23.0 8.3 77.2 4.95 7/9/98 dawn 7 A 30.9 20.0 11.0 29.0 19.5 9.5 65.4 5.26 7/9/98 dawn 8 C 26.7 17.1 9.6 24.5 16.1 8.4 76.7 4.34 7/9/98 dawn 9 A 29.0 21.1 7.9 32.2 23.9 8.3 59.9 5.42 7/9/98 dawn 10 C 22.0 12.6 9.4 27.1 16.8 10.3 78.6 4.42

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169 Appendix M, continued

TDC DIG DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 7/9/98 dawn 11 C 31.6 23.4 8.3 33.7 25.0 8.7 84.9 4.32 7/9/98 dawn 12 A 32.9 24.2 8.7 36.4 27.7 8.7 55.1 5.32 7/9/98 dawn 13 C 22.5 13.7 8.8 23.0 14.5 8.5 88.5 4.43 7/9/98 dawn 14 A 34.5 26.3 8.1 36.4 28.1 8.3 67.9 5.15 7/9/98 dawn 15 A 26.5 17.4 9.1 28.0 19.2 8.8 68.3 5.24 7/9/98 dawn 16 A 27.6 18.1 9.4 29.8 20.1 9.7 68.2 5.24 7/9/98 dawn 17 C 25.2 16.4 8.8 27.3 18.1 9.1 88.2 4.40 7/9/98 dawn 18 A 33.4 25.1 8.3 37.5 28.7 8.8 79.7 5.36 7/9/98 dawn 19 C 28.2 18.4 9.8 29.0 19.6 9.4 93.6 4.47 7/9/98 dawn 20 C 35.6 27.2 8.4 38.3 29.8 8.6 88.5 4.26 7/28/98 dawn 1 C 44.6 36.5 8.1 40.6 33.5 7.1 137.0 5.26 7/28/98 dawn 2 A 28.0 17.8 10.3 26.5 16.6 9.8 75.5 5.24 7/28/98 dawn 3 C 44.4 35.8 8.7 40.2 32.8 7.4 132.9 5.37 7/28/98 dawn 4 A 27.9 18.1 9.7 26.4 17.3 9.2 79.0 5.28 7/28/98 dawn 5 C 39.8 31.9 7.9 39.0 32.1 6.9 123.1 5.49 7/28/98 dawn 6 A 16.9 9.1 7.8 16.0 8.7 7.3 53.6 5.76 7/28/98 dawn 7 A 29.8 20.1 9.7 29.6 21.3 8.3 90.3 5.23 7/28/98 dawn 8 C 40.3 32.5 7.9 37.1 30.3 6.8 125.1 5.34 7/28/98 dawn 9 A 25.2 16.2 9.0 23.1 14.9 8.2 68.1 5.38 7/28/98 dawn 10 C 41.5 33.5 8.0 37.0 31.0 6.0 125.0 5.47 7/28/98 dawn 11 C 44.9 36.9 8.0 40.9 34.0 6.9 143.1 6.20 7/28/98 dawn 12 A 14.7 5.9 8.9 13.5 5.6 8.0 44.5 6.29 7/28/98 dawn 13 C 41.5 34.3 7.2 38.2 31.7 6.5 128.7 5.53 7/28/98 dawn 14 A 19.0 10.3 8.7 19.0 10.7 8.3 56.9 5.84 7/28/98 dawn 15 A 24.7 15.2 9.5 25.1 16.4 8.6 74.2 5.45 7/28/98 dawn 16 A 17.4 9.0 8.4 15.8 8.0 7.8 49.4 6.01 7/28/98 dawn 17 C 44.2 35.9 8.3 40.6 33.0 7.6 134.6 5.56 7/28/98 dawn 18 A 23.1 13.8 9.3 20.8 12.6 8.2 65.9 5.85 7/28/98 dawn 19 C 44.2 35.6 8.6 45.0 36.5 8.5 136.6 5.51 7/28/98 dawn 20 C 43.0 35.3 7.7 45.7 37.6 8.2 137.3 5.27 7/28/98 dusk 1 C 41.4 33.5 7.9 45.4 37.3 8.1 126.7 5.01 7/28/98 dusk 2 A 21.7 11.4 10.3 23.2 12.4 10.7 67.8 6.19 7/28/98 dusk 3 C 43.9 35.8 8.1 44.7 36.8 7.9 133.9 5.43 7/28/98 dusk 4 A 23.2 13.5 9.7 24.3 14.5 9.9 70.8 6.07 7/28/98 dusk 5 C 40.5 33.7 6.8 43.0 35.4 7.6 124.9 5.25 7/28/98 dusk 6 A 11.9 4.3 7.6 12.8 4.9 7.8 50.1 6.50 7/28/98 dusk 7 A 25.7 16.6 9.2 28.0 18.4 9.5 75.9 6.02 7/28/98 dusk 8 C 39.9 32.6 7.3 41.5 33.8 7.7 123.4 5.27 7/28/98 dusk 9 A 19.6 10.5 9.1 20.2 10.9 9.4 62.5 6.37 7/28/98 dusk 10 C 41.1 33.1 7.9 41.8 33.9 7.9 126.0 5.14 7/28/98 dusk 11 C 44.0 37.0 7.0 45.9 37.8 8.0 138.1 5.22 7/28/98 dusk 12 A 12.0 2.7 9.4 11.9 2.8 9.1 44.3 6.64 7/28/98 dusk 13 C 42.8 34.7 8.1 43.3 35.2 8.1 127.9 5.11 7/28/98 dusk 14 A 15.6 6.3 9.3 15.3 6.7 8.6 66.0 6.67 7/28/98 dusk 15 A 23.4 13.5 9.9 23.1 13.6 9.5 47.0 6.05 7/28/98 dusk 16 A 12.8 4.4 8.4 14.1 5.5 8.6 135.6 7.07 7/28/98 dusk 17 C 46.2 37.7 8.4 45.5 37.5 8.0 58.2 4.81 7/28/98 dusk 18 A 19.4 9.6 9.8 18.9 9.6 9.3 125.2 6.70 7/28/98 dusk 19 C 44.9 36.7 8.2 44.2 36.5 7.7 138.6 5.34 7/28/98 dusk 20 C 45.7 37.2 8.5 45.4 37.7 7.7 66.0 4.90 7/29/98 dawn I c 44.9 36.6 8.3 46.6 38.8 7.8 135.2 5.21 7/29/98 dawn 2 A 28.6 17.9 10.7 29.3 18.5 10.8 66.0 5.60

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TDC DIG DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 7/29/98 dawn 3 C 48.3 39.6 8.8 46.3 37.6 8.7 133.8 5.21 7/29/98 dawn 4 A 31.0 20.0 II.I 28.9 18.7 10.2 74.2 5.62 7/29/98 dawn 5 C 47.1 38.7 8.4 44.9 36.5 8.5 131.5 5.44 7/29/98 dawn 6 A 18.5 9.7 8.8 17.0 9.0 8.0 49.3 6.32 7/29/98 dawn 7 A 34.0 23.7 10.3 33.3 23.8 9.5 87.0 5.35 7/29/98 dawn 8 C 44.9 36.8 8.1 42.8 35.2 7.6 124.3 5.19 7/29/98 dawn 9 A 27.1 17.0 lO.I 26.1 16.6 9.5 65.8 5.70 7/29/98 dawn 10 C 45.5 37.1 8.4 43.7 35.2 8.5 125.9 5.23 7/29/98 dawn II C 49.8 41.8 8.0 47.2 39.2 8.0 134.2 5.32 7/29/98 dawn 12 A 16.3 6.6 9.7 15.4 6.2 9.2 40.4 6.36 7/29/98 dawn 13 C 45.2 37.0 8.2 45.0 36.7 8.3 132.5 5.31 7/29/98 dawn 14 A 20.7 II.I 9.6 20.1 10.9 9.2 57.5 6.19 7/29/98 dawn 15 A 28.0 17.8 10.3 28.1 18.3 9.8 69.8 5.67 7/29/98 dawn 16 A 18.0 8.4 9.6 17.4 8.9 8.6 50.5 6.26 7/29/98 dawn 17 C 41.9 33.4 8.5 47.4 38.8 8.6 136.7 5.17 7/29/98 dawn 18 A 19.2 9.6 9.6 25.2 13.7 11.5 62.6 5.99 7/29/98 dawn 19 C 43.9 35.8 8.1 46.5 38.0 8.5 137.1 5.32 7/29/98 dawn 20 C 46.1 37.6 8.6 47.7 39.2 8.5 143.4 5.26 8/20/98 dawn I C 34.3 28.5 5.9 35.5 29.2 6.3 131.7 4.84 8/20/98 dawn 2 A 20.6 12.2 8.4 22.9 12.7 10.2 68.9 5.73 8/20/98 dawn 3 C 36.9 30.7 6.2 37.5 31.6 5.9 142.3 5.13 8/20/98 dawn 4 A 18.1 II.I 7.0 18.3 11.2 7.1 64.2 5.90 8/20/98 dawn 5 C 34.6 28.6 5.9 35.4 29.6 5.8 136.6 5.31 8/20/98 dawn 6 A 18.5 12.2 6.4 19.2 12.7 6.5 62.9 5.50 8/20/98 dawn 7 A 30.4 23.9 6.5 32.1 25.0 7.1 113.1 4.94 8/20/98 dawn 8 C 34.0 28.7 5.3 35.4 29.5 5.8 135.2 5.22 8/20/98 dawn 9 A 26.3 19.5 6.8 27.1 19.8 7.2 89.4 4.94 8/20/98 dawn 10 C 34.5 29.1 5.4 36.2 30.0 6.2 137.1 5.28 8/20/98 dawn II C 35.6 29.2 6.4 35.6 29.8 5.8 135.3 5.23 8/20/98 dawn 12 A 13.0 6.0 7.0 13.3 6.2 7.1 42.7 6.02 8/20/98 dawn 13 C 33.9 28.6 5.3 35.3 29.5 5.8 133.4 5.21 8/20/98 dawn 14 A 19.3 11.2 8.2 21.1 12.0 9.2 65.6 5.84 8/20/98 dawn 15 A 27.5 20.3 7.2 28.6 21.4 7.2 96.8 5.03 8/20/98 dawn 16 A 17.5 11.0 6.5 18.3 11.7 6.6 58.5 5.71 8/20/98 dawn 17 C 37.5 31.2 6.3 38.2 32.2 6.0 145 5.34 8/20/98 dawn 18 A 15.4 8.5 6.9 16.2 9.0 7.2 55.1 5.97 8/20/98 dawn 19 C 35.4 29.8 5.6 37.0 31.1 5.9 142.7 5.31 8/20/98 dawn 20 C 37.3 30.9 6.4 38.3 32.0 6.3 144.3 5.29 8/20/98 dusk I C 34.2 28.4 5.8 35.6 29.2 6.4 133.7 5.08 8/20/98 dusk 2 A 16.0 7.3 8.7 15.3 7.1 8.2 64.8 6.72 8/20/98 dusk 3 C 37.5 31.4 6.1 38.3 31.6 6.6 142.5 5.25 8/20/98 dusk 4 A 13.9 6.6 7.2 13.8 5.9 7.9 58.2 6.73 8/20/98 dusk 5 C 35.9 29.9 6.0 35.6 29.8 5.8 136.5 5.51 8/20/98 dusk 6 A 16.7 lO.I 6.6 16.6 lO.O 6.6 59.6 6.50 8/20/98 dusk 7 A 24.1 17.4 6.7 23.1 16.3 6.8 88.1 6.14 8/20/98 dusk 8 C 35.0 29.2 5.8 34.8 29.2 5.6 134.9 5.55 8/20/98 dusk 9 A 21.3 14.3 7.1 19.6 12.0 7.5 77 6.22 8/20/98 dusk 10 C 35.3 29.6 5.7 35.8 30.0 5.8 137.6 5.46 8/20/98 dusk II c 36.0 30.1 5.9 35.5 29.8 5.7 138.6 5.41 8/20/98 dusk 12 A 10.2 3.3 6.9 10.6 3.3 7.3 41.4 6.81 8/20/98 dusk 13 C 34.6 28.8 5.8 35.2 29.4 5.8 135.8 5.39 8/20/98 dusk 14 A 14.9 6.7 8.2 16.8 7.5 9.3 58.2 6.58

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TDC D ie DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 8/20/98 dusk 15 A 23.4 15.3 8.1 21.8 14.6 7.2 79.3 6.20 8/20/98 dusk 16 A 13.6 7.0 6.6 11.9 5.1 6.7 49.8 6.75 8/20/98 dusk 17 C 39.0 32.5 6.5 38.3 32.1 6.2 148.2 5.43 8/20/98 dusk 18 A 12.3 5.1 7.1 12.8 5.1 7.7 49.9 6.67 8/20/98 dusk 19 C 36.7 30.5 6.2 37.3 31.2 6.1 144.4 5.49 8/20/98 dusk 20 C 37.9 31.8 6.0 38.5 32.5 6.0 147.3 5.43 8/21/98 dawn 1 C 33.9 29.4 5.4 35.6 30.0 5.6 133.8 5.08 8/21/98 dawn 2 A 19.6 10.9 8.7 21.4 12.8 8.6 68.3 5.90 8/21/98 dawn 3 C 32.7 26.4 6.3 38.4 32.0 6.4 143.9 5.29 8/21/98 dawn 4 A 17.3 10.2 7.1 19.2 10.9 8.3 62.3 6.17 8/21/98 dawn 5 C 32.6 26.8 5.8 27.5 20.8 6.7 138.6 5.45 8/21/98 dawn 6 A 19.5 12.8 6.7 28.1 21.8 6.2 64.5 5.53 8/21/98 dawn 7 A 29.0 22.2 6.8 31.9 25.1 6.8 109.8 5.00 8/21/98 dawn 8 C 32.2 26.3 5.9 36.0 30.3 5.7 137.4 5.41 8/21/98 dawn 9 A 23.8 16.5 7.2 26.1 19.0 7.1 87.7 4.92 8/21/98 dawn 10 C 29.6 23.1 6.5 36.9 30.9 6.1 141 5.38 8/21/98 dawn 11 C 32.4 27.1 5.4 36.3 30.8 5.5 141 5.36 8/21/98 dawn 12 A 11.7 4.6 7.0 13.3 5.9 7.4 43.1 6.23 8/21/98 dawn 13 C 30.6 24.2 6.4 36.1 30.3 5.7 138 5.31 8/21/98 dawn 14 A 18.8 10.2 8.6 20.9 12.4 8.4 66.1 5.93 8/21/98 dawn 15 A 24.8 17.9 7.0 29.2 21.8 7.5 98.9 5.03 8/21/98 dawn 16 A 15.8 9.1 6.7 18.0 11.4 6.5 59.9 5.86 8/21/98 dawn 17 C 34.8 28.2 6.7 39.4 33.1 6.3 148 5.33 8/21/98 dawn 18 A 14.1 7.1 7.0 15.8 8.7 7.1 54.2 6.16 8/21/98 dawn 19 C ——— 38.3 32.1 6.1 145.8 5.44 8/21/98 dawn 20 C 37.4 30.6 6.8 39.4 33.1 6.3 151.2 5.39 9/22/98 dawn 1 C 47.6 41.3 6.3 47.8 41.9 5.9 176.5 5.73 9/22/98 dawn 2 A 52.4 39.2 13.1 53.1 41.6 11.5 159.3 5.12 9/22/98 dawn 3 C 48.5 42.1 6.4 49.4 42.7 6.7 174.6 5.46 9/22/98 dawn 4 A 36.0 27.7 8.3 36.5 28.7 7.8 113.9 4.97 9/22/98 dawn 5 C 45.9 39.4 6.5 46.2 39.6 6.6 164.1 5.65 9/22/98 dawn 6 A 38.9 31.1 7.7 39.6 32.3 7.3 126.5 5.08 9/22/98 dawn 7 A 55.4 46.5 9.0 58.5 49.7 8.8 189.0 5.27 9/22/98 dawn 8 C 45.8 39.6 6.1 47.1 40.9 6.1 169.2 5.59 9/22/98 dawn 9 A 41.4 34.6 6.8 42.9 35.6 7.2 138.6 5.03 9/22/98 dawn 10 C 46.1 39.5 6.6 46.7 40.2 6.4 165.4 5.58 9/22/98 dawn 11 C 46.4 40.3 6.0 47.3 41.0 6.3 172.5 5.77 9/22/98 dawn 12 A 25.5 18.3 7.2 25.9 18.9 6.9 78.7 5.43 9/22/98 dawn 13 C 47.2 40.7 6.5 48.3 41.7 6.5 173.9 5.68 9/22/98 dawn 14 A 48.1 36.2 11.9 52.6 40.4 12.2 148.7 5.05 9/22/98 dawn 15 A 38.1 30.8 7.4 39.7 32.4 7.3 129.7 5.25 9/22/98 dawn 16 A 26.1 19.3 6.9 27.9 21.0 6.9 84.6 5.11 9/22/98 dawn 17 C 46.0 39.5 6.5 48.9 42.4 6.5 175.4 5.76 9/22/98 dawn 18 A 26.2 18.5 7.8 27.1 19.8 7.4 80.6 5.36 9/22/98 dawn 19 C 48.1 41.0 7.0 48.6 42.0 6.6 171.8 5.54 9/22/98 dawn 20 C 48.9 42.2 6.8 48.7 42.4 6.2 176.2 5.77 9/22/98 dusk 1 C 51.5 44.9 6.6 47.6 42.1 5.5 180.5 5.73 9/22/98 dusk 2 A 54.7 40.4 14.4 52.2 39.9 12.3 166.0 5.88 9/22/98 dusk 3 C 52.6 45.3 7.3 49.1 42.6 6.5 176.3 5.49 9/22/98 dusk 4 A 36.9 27.8 9.1 34.4 26.9 7.5 116.3 5.61 9/22/98 dusk 5 C 49.3 42.0 7.3 45.5 39.3 6.2 166.2 5.70 9/22/98 dusk 6 A 40.4 32.1 8.3 38.7 30.8 7.9 129.0 5.63

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172 Appendix M, continued

TDC DIG DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 9/22/98 dusk 7 A 58.0 48.7 9.2 57.3 47.8 9.5 194.9 5.67 9/22/98 dusk 8 C 51.0 43.4 7.6 46.8 41.5 5.3 171.5 5.63 9/22/98 dusk 9 A 42.9 35.4 7.5 40.7 34.1 6.6 143.8 5.63 9/22/98 dusk 10 C 49.1 42.0 7.0 46.1 39.7 6.3 168.6 5.65 9/22/98 dusk 11 C 49.2 42.4 6.8 46.8 40.7 6.1 165.0 5.75 9/22/98 dusk 12 A 25.4 17.6 7.8 23.5 16.6 6.9 77.0 5.86 9/22/98 dusk 13 C 51.0 43.9 7.1 47.5 41.6 5.9 174.5 5.69 9/22/98 dusk 14 A 52.0 39.5 12.4 48.4 37.4 11.0 149.6 5.38 9/22/98 dusk 15 A 39.1 30.9 8.3 37.5 3Û.Ü 7.5 128.3 5.80 9/22/98 dusk 16 A 25.9 18.8 7.1 24.7 17.9 6.8 79.6 5.89 9/22/98 dusk 17 C 52.5 45.1 7.4 48.4 42.0 6.4 178.4 5.80 9/22/98 dusk 18 A 26.6 18.1 8.5 25.1 17.8 7.3 77.5 5.88 9/22/98 dusk 19 C 51.7 44.4 7.3 48.7 41.9 6.8 173.4 5.59 9/22/98 dusk 20 C 52.2 45.3 7.0 49.1 42.4 6.7 180.5 5.77 9/23/98 dawn 1 c 51.3 44.9 6.4 53.6 45.8 7.8 182.7 5.67 9/23/98 dawn 2 A 57.8 43.5 14.3 58.7 46.1 12.7 171.9 5.09 9/23/98 dawn 3 C 51.9 44.7 7.2 53.2 46.0 7.2 169.0 5.40 9/23/98 dawn 4 A 39.0 30.4 8.6 39.8 31.6 8.3 119.5 4.95 9/23/98 dawn 5 C 48.0 41.3 6.7 49.5 43.0 6.5 169.8 5.64 9/23/98 dawn 6 A 43.3 35.4 7.8 44.9 36.6 8.3 136.2 5.01 9/23/98 dawn 7 A 61.4 51.8 9.6 63.3 54.4 8.8 198.8 5.19 9/23/98 dawn 8 C 50.0 43.0 7.0 51.4 44.6 6.8 173.1 5.56 9/23/98 dawn 9 A 42.9 35.7 7.2 47.0 39.6 7.4 148.7 5.05 9/23/98 dawn 10 C 47.0 40.1 6.9 50.9 44.0 7.0 169.0 5.58 9/23/98 dawn 11 C 49.5 43.1 6.4 51.3 44.5 6.8 175.4 5.69 9/23/98 dawn 12 A 25.1 17.6 7.5 27.5 19.7 7.8 79.0 5.54 9/23/98 dawn 13 C 50.8 44.2 6.6 51.4 45.3 6.1 166.1 5.61 9/23/98 dawn 14 A 53.8 41.3 12.5 55.4 43.5 11.9 151.9 4.97 9/23/98 dawn 15 A 40.0 33.2 6.8 42.6 34.9 7.7 133.3 5.21 9/23/98 dawn 16 A 28.4 21.0 7.4 29.4 22.0 7.4 86.3 5.28 9/23/98 dawn 17 C 51.8 45.2 6.6 53.3 45.9 7.4 178.8 5.69 9/23/98 dawn 18 A 28.8 20.4 8.4 29.6 21.1 8.5 80.1 5.36 9/23/98 dawn 19 C 51.3 44.0 7.3 52.9 46.0 6.9 175.4 5.49 9/23/98 dawn 20 C 51.2 44.1 7.2 53.3 46.4 6.8 182.1 5.75 12/3/98 dawn 1 C 47.6 40.3 7.3 48.1 40.9 7.2 203.8 5.28 12/3/98 dawn 2 A 31.9 22.4 9.5 32.5 23.4 9.1 102.9 5.78 12/3/98 dawn 3 C 44.2 36.6 7.7 46.0 38.1 7.9 184.0 5.38 12/3/98 dawn 4 A 33.4 26.0 7.4 34.0 26.6 7.4 114.2 5.66 12/3/98 dawn 5 C 44.2 36.9 7.3 44.3 37.2 7.1 191.3 5.42 12/3/98 dawn 6 A 40.2 32.9 7.3 41.0 33.9 7.1 198.5 5.64 12/3/98 dawn 7 A 27.5 20.5 7.0 28.9 21.6 7.3 125.9 5.91 12/3/98 dawn 8 C 44.4 36.8 7.7 45.6 37.6 8.0 173.3 5.41 12/3/98 dawn 9 A 36.1 29.4 6.7 37.0 30.2 6.8 133.6 5.40 12/3/98 dawn 10 C 46.2 38.2 8.0 47.6 39.6 8.0 192.5 5.63 12/3/98 dawn 11 C 47.2 39.4 7.8 48.1 40.0 8.1 210.4 5.55 12/3/98 dawn 12 A 37.1 30.2 6.9 37.4 30.3 7.1 147.3 5.51 12/3/98 dawn 13 C 45.6 38.4 7.2 47.0 38.8 8.2 185.4 5.23 12/3/98 dawn 14 A 48.7 40.2 8.6 49.8 41.0 8.8 204.7 5.43 12/3/98 dawn 15 A 34.2 28.7 5.6 36.6 29.5 7.1 130.1 5.24 12/3/98 dawn 16 A 41.8 34.5 7.3 42.3 35.4 6.9 173.9 5.28 12/3/98 dawn 17 C 49.2 40.5 8.7 49.3 41.9 7.4 197.9 5.38 12/3/98 dawn 18 A 39.9 32.7 7.2 41.3 34.5 6.7 168.8 5.41

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173 Appendix M, continued

TDC DIG DOC TC TIC TOC Total Date Time Meso Treat mg/L mg/L mg/L mg/L mg/L mg/L alkalinity SI 12/3/98 dawn 19 C 46.6 39.1 7.5 47.5 39.6 7.9 189.5 5.39 12/3/98 dawn 20 C 45.0 36.5 8.4 45.8 37.4 8.4 167.0 5.15 12/3/98 dusk 1 C 47.2 39.7 7.5 48.3 40.7 7.6 207.4 5.47 12/3/98 dusk 2 A 28.9 19.6 9.2 28.7 19.9 8.9 92.9 6.13 12/3/98 dusk 3 C 45.3 37.6 7.7 45.4 37.9 7.5 183.3 5.62 12/3/98 dusk 4 A 31.6 24.7 7.0 33.0 25.5 7.5 109.9 5.73 12/3/98 dusk 5 C 44.6 37.0 7.6 45.0 38.1 6.9 182.9 5.54 12/3/98 dusk 6 A 39.6 32.2 7.4 39.5 32.4 7.1 165.3 5.73 12/3/98 dusk 7 A 25.1 18.2 7.0 26.8 19.7 7.1 94.0 5.83 12/3/98 dusk 8 C 44.5 36.7 7.8 44.6 36.6 8.0 175.2 5.50 12/3/98 dusk 9 A 34.6 28.1 6.4 35.8 28.9 6.9 120.4 5.57 12/3/98 dusk 10 C 46.7 38.7 8.0 47.6 39.7 7.8 192.8 5.54 12/3/98 dusk 11 C 46.3 38.2 8.2 47.2 39.2 8.0 188.1 5.35 12/3/98 dusk 12 A 36.1 28.6 7.5 36.3 29.2 7.0 136.0 5.58 12/3/98 dusk 13 C 46.3 38.6 7.7 47.4 39.7 7.7 189.6 5.38 12/3/98 dusk 14 A 48.0 39.6 8.4 49.6 41.0 8.6 201.3 5.60 12/3/98 dusk 15 A 34.5 28.1 6.4 35.0 28.3 6.7 123.2 5.69 12/3/98 dusk 16 A 41.8 34.1 7.7 41.9 34.6 7.3 172.0 5.61 12/3/98 dusk 17 C 48.9 41.3 7.6 49.4 42.0 7.4 204.3 5.56 12/3/98 dusk 18 A 39.1 32.0 7.1 40.5 33.4 7.1 158.2 5.54 12/3/98 dusk 19 C 46.8 39.0 7.8 48.0 40.3 7.7 197.8 5.45 12/3/98 dusk 20 C 43.7 36.1 7.6 44.1 36.0 8.0 167.3 5.28 12/4/98 dawn 1 C 47.3 39.8 7.5 48.3 41.1 7.3 204.1 5.51 12/4/98 dawn 2 A 29.5 19.9 9.6 29.5 20.5 9.0 97.4 5.91 12/4/98 dawn 3 C 45.0 37.3 7.7 45.6 37.7 7.9 205.9 5.48 12/4/98 dawn 4 A 31.5 24.4 7.1 32.6 25.7 6.9 108.5 5.66 12/4/98 dawn 5 C 41.8 34.8 7.1 44.7 37.6 7.1 177.3 5.60 12/4/98 dawn 6 A 39.7 32.3 7.4 40.2 32.6 7.6 165.0 5.94 12/4/98 dawn 7 A 25.4 18.7 6.7 26.2 19.6 6.6 95.8 5.99 12/4/98 dawn 8 C 39.1 32.0 7.1 46.1 37.9 8.2 172.0 5.49 12/4/98 dawn 9 A 34.4 27.7 6.7 35.6 29.0 6.6 129.5 5.69 12/4/98 dawn 10 C 45.7 38.3 7.4 47.4 39.5 7.9 194.3 5.64 12/4/98 dawn 11 C 36.3 29.3 7.0 48.5 40.4 8.2 135.5 5.15 12/4/98 dawn 12 A 46.1 38.4 7.7 36.9 30.2 6.7 200.5 5.99 12/4/98 dawn 13 C 44.7 37.3 7.5 46.6 39.2 7.4 153.8 5.34 12/4/98 dawn 14 A 47.8 39.5 8.3 48.9 40.6 8.3 208.7 5.74 12/4/98 dawn 15 A 35.4 28.3 7.1 35.2 28.5 6.8 125.7 5.65 12/4/98 dawn 16 A 41.5 34.2 7.3 42.1 34.6 7.5 172.5 5.65 12/4/98 dawn 17 C 47.3 39.7 7.6 49.5 41.4 8.1 164.2 5.49 12/4/98 dawn 18 A 39.1 32.2 6.9 40.6 33.5 7.1 177.4 5.71 12/4/98 dawn 19 C 46.7 38.9 7.8 47.8 40.1 7.7 152.1 5.39 12/4/98 dawn 20 C 43.7 35.9 7.9 44.8 36.9 7.9 17.9 4.37

174 APPENDIX N - MESOCOSM AQUATIC METABOLISM

Gross primary production (GPP) and respiration (R) in wetland mesocosms. C=control, A=algal treatment. GPP R Date Mesocosm Treatment g 0 , m - d" g 0 : m" 7/8/98 I C -0.49 0.37 7/8/98 2 A 6.19 -4.56 7/8/98 3 C 0.04 -0.17 7/8/98 4 A 2.38 -1.01 7/8/98 5 C -0.02 -0.10 7/8/98 6 A 6.43 -5.03 7/8/98 7 A 5.71 -4.47 7/8/98 8 C 0.15 -0.26 7/8/98 9 A 4.77 -3.03 7/8/98 10 C 0.32 -0.54 7/8/98 II C 0.10 -0.16 7/8/98 12 A 4.90 -3.87 7/8/98 13 C 0.01 -0.10 7/8/98 14 A 5.81 -4.30 7/8/98 15 A 3.30 -1.86 7/8/98 16 A 3.07 -1.59 7/8/98 17 C -0.10 -0.07 7/8/98 18 A 4.93 -3.42 7/8/98 19 C 0.73 -1.09 7/8/98 20 C -0.21 -0.01 7/28/98 1 C -0.65 0.71 7/28/98 2 A 5.95 -6.61 7/28/98 3 C -0.30 0.30 7/28/98 4 A 4.68 -5.06 7/28/98 5 C -0.55 0.49 7/28/98 6 A 5.75 -6.09 7/28/98 7 A 3.09 -3.36 7/28/98 8 C -0.13 0.32 7/28/98 9 A 2.97 -3.36 7/28/98 10 C -0.33 0.43 7/28/98 11 C -0.01 -0.08 7/28/98 12 A 4.16 -4.80 7/28/98 13 C -0.31 0.41 7/28/98 14 A 4.89 -5.43 7/28/98 15 A 3.58 -3.94 7/28/98 16 A 2.89 -3.35 7/28/98 17 C -0.23 0.32 7/28/98 18 A 3.29 -3.85 7/28/98 19 C -0.31 0.30 7/28/98 20 C -0.52 0.62 8/20/98 1 c 0.13 -0.19 8/20/98 2 A 6.64 -6.86 8/20/98 3 C -0.42 0.63 8/20/98 4 A 4.91 -5.05 8/20/98 5 C -0.03 0.08 8/20/98 6 A 2.19 -2.88 8/20/98 7 A 5.78 -5.88 8/20/98 8 C -0.32 0.36 8/20/98 9 A 3.46 -3.12 8/20/98 10 C -0.36 0.39 8/20/98 11 C -0.11 0.14 continued on next page

175 Appendix N, continued

GPP R Date Mesocosm Treatment g 0 : m 'd" g O. m - d" 8/20/98 12 A 3.03 -3.14 8/20/98 13 C -0.02 0.25 8/20/98 14 A 3.32 -3.12 8/20/98 15 A 3.61 -3.80 8/20/98 16 A 1.54 -1.64 8/20/98 17 C 0.32 -0.05 8/20/98 18 A 3.54 -4.05 8/20/98 19 C -0.05 -0.13 8/20/98 20 C -0.17 0.08 9/22/98 1 C -0.18 0.16 9/22/98 2 A 3.15 -3.31 9/22/98 3 C 0.15 -0.07 9/22/98 4 A 2.19 -2.19 9/22/98 5 C -0.15 0.28 9/22/98 6 A 2.49 -2.55 9/22/98 7 A 2.32 -2.17 9/22/98 8 C 0.23 -0.02 9/22/98 9 A 2.56 -2.52 9/22/98 10 C 0.13 -0.04 9/22/98 11 C -0.01 0.02 9/22/98 12 A 1.23 -0.97 9/22/98 13 C 0.00 0.02 9/22/98 14 A 1.72 -1.89 9/22/98 15 A 2.45 -2.41 9/22/98 16 A 2.58 -2.37 9/22/98 17 C 0.03 -0.13 9/22/98 18 A 1.68 -1.66 9/22/98 19 C 0.00 0.11 9/22/98 20 C 0.02 0.08 12/3/98 1 C 0.08 -0.19 12/3/98 2 A 2.55 -1.55 12/3/98 3 C 0.26 -0.55 12/3/98 4 A 0.85 -0.42 12/3/98 5 C 0.19 -0.47 12/3/98 6 A 0.78 -0.37 12/3/98 7 A 1.24 -0.52 12/3/98 8 C 0.07 -0.24 12/3/98 9 A 0.64 -0.38 12/3/98 10 C -0.24 0.18 12/3/98 11 C 0.19 -0.38 12/3/98 12 A 0.47 -0.33 12/3/98 13 C 0.10 -0.26 12/3/98 14 A 0.53 -0.24 12/3/98 15 A 0.88 -0.55 12/3/98 16 A 0.54 -0.30 12/3/98 17 C 0.05 -0.19 12/3/98 18 A 0.42 -0.44 12/3/98 19 C 0.15 -0.34 12/3/98 20 C -0.12 -0.11

176 APPENDIX O - CALCIUM CARBONATES IN MESOCOSMS

Calcium carbonate precipitates in dry algae and sediment samples from wetland mesocosms. C=control, A=algal treatment.

dry wt Calcite Dolomite CCE Date Mesocosm Sample type Treatment g % % % 6/98 Initial soil sediment A ,C 2.6801 1.5 0.1 1.6 6/98 Initial soil sediment A ,C 2.1835 1.0 -0.3 0.6 6/98 Initial soil sediment A ,C 2.6611 0.3 0.6 0.9 5/17/99 1 sediment C 2.0218 0.7 0.8 1.5 5/17/99 2 sediment A 2.0897 1.5 0.2 1.7 5/17/99 3 sediment C 2.0909 0.5 0.4 0.9 5/17/99 4 sediment A 2.1460 1.4 0.3 1.7 5/17/99 5 sediment C 3.3254 1.4 0.2 1.6 5/17/99 6 sediment A 2.1865 0.4 1.2 1.8 5/17/99 7 sediment A 2.3230 0.9 0.8 1.8 5/17/99 8 sediment C 2.3922 1.4 0.3 1.6 5/17/99 9 sediment A 2.5568 0.7 0.6 1.4 5/17/99 10 sediment C 2.0868 1.4 0.5 1.9 5/17/99 10 sediment C 2.1967 1.2 -0.2 0.9 5/17/99 11 sediment C 2.0492 0.0 0.4 0.4 5/17/99 12 sediment A 2.1899 0.5 0.4 0.9 5/17/99 13 sediment C 1.9961 1.1 0.6 1.7 5/17/99 14 sediment A 1.9980 0.4 0.3 0.7 5/17/99 15 sediment A 2.9611 1.5 0.8 2.3 5/17/99 16 sediment A 2.0239 0.9 -0.4 0.4 5/17/99 17 sediment C 2.1711 0.2 0.9 1.2 5/17/99 18 sediment A 2.3200 0.6 1.0 1.6 5/17/99 19 sediment C 2.1406 1.1 0.9 2.1 5/17/99 20 sediment C 2.2022 0.5 0.4 0.9 6/22/98 Initial algae algal mat A 0.8785 17.1 4.6 22.1 6/22/98 Initial algae algal mat A 0.8196 16.1 4.9 21.4 9/8/98 2 algal mat A 1.0033 23.2 3.2 26.7 9/8/98 2 algal mat A 0.9999 25.4 3.6 29.3 9/8/98 2 algal mat A 1.0578 22.5 3.4 26.2 9/8/98 4 algal mat A 1.0539 15.6 3.9 19.8 9/8/98 4 algal mat A 0.9933 10.4 4.6 15.3 9/8/98 4 algal mat A 1.0406 14.5 4.7 19.6 9/8/98 4 periphyton A 0.7308 6.7 6.7 14.0 9/8/98 4 periphyton A 0.4968 1.8 9.1 11.7 9/8/98 4 periphyton A 0.5226 6.0 7.5 14.1 9/8/98 6 algal mat A 0.9822 10.9 5.0 16.3 9/8/98 6 algal mat A 0.9401 12.8 5.2 18.4 9/8/98 6 algal mat A 0.9814 9.1 5.8 15.4 9/8/98 7 algal mat A 1.0336 18.0 4.7 23.1 9/8/98 7 algal mat A 0.9467 17.8 5.5 23.8 9/8/98 7 algal mat A 1.0262 18.9 5.1 24.5

Continued on next page 177 Appendix O, continued

dry wt Calcite Dolomite CCE Date Mesocosm Sample type Treatment g % % % 9/8/98 9 algal mat A 0.9453 8.5 5.6 14.6 9/8/98 9 algal mat A 0.8382 13.3 5.3 19.1 9/8/98 9 algal mat A 1.0115 11.1 5.3 16.8 9/8/98 11 algal mat A 1.0651 18.8 3.0 22.1 9/8/98 11 algal mat A 1.0460 10.3 4.7 15.4 9/8/98 11 algal mat A 1.0361 8.3 4.4 13.0 9/8/98 14 algal mat A 0.9809 13.3 4.6 18.4 9/8/98 14 algal mat A 0.9564 9.4 4.7 14.6 9/8/98 14 algal mat A 0.9381 12.9 3.9 17.2 9/8/98 15 algal mat A 0.9650 18.1 4.0 22.4 9/8/98 15 algal mat A 0.9574 17.2 3.8 21.4 9/8/98 15 algal mat A 0.9723 20.2 3.7 24.2 9/8/98 15 periphyton A 0.8737 5.6 4.5 10.5 9/8/98 15 periphyton A 0.7097 10.6 6.9 18.1 9/8/98 16 algal mat A 1.0268 10.1 5.6 16.1 9/8/98 16 algal mat A 1.0485 11.1 5.1 16.6 9/8/98 16 algal mat A 1.1543 11.6 4.3 16.2 9/8/98 18 algal mat A 1.0247 12.6 4.8 17.8 9/8/98 18 algal mat A 0.9503 8.0 5.2 13.6

178 APPENDIX F- MESOCOSM METAPHYTON BIOMASS Mesocosm biomass at initial stocking (6/22798) and final harvest(9/8/98). M=Metaphyton sample. P= P=periphyton sample. If sample is not marked with P or M, it is a metaphyton sample.

Date Sample # net wet w t s net dry wt, g 6/22/98 1 13.1963 1.5405 6/22/98 2 11.4324 1.2559 6/22/98 3 14.7617 2.7213 6/22/98 4 3.2291 0.1988 6/22/98 5 41.3362 4.5631 6/22/98 6 16.4957 3.2294 6/22/98 7 16.774 2.9052 6/22/98 8 14.386 0.8513 6/22/98 9 18.5279 1.2473 6/22/98 10 12.0882 1.1058 6/22/98 11 11.1845 1.9139 6/22/98 12 8.6926 1.203 6/22/98 13 16.6842 2.0425 6/22/98 14 9.4339 1.6228 6/22/98 15 6.3491 0.9965 6/22/98 16 8.1406 1.0935 6/22/98 17 4.2315 0.7802 6/22/98 18 7.5064 0.8702 6/22/98 19 6.8906 0.932 6/22/98 20 9.7766 1.129 Date Sample # Net dry w t g Net ash w t g % Organic Matter 6/22/98 2 1.2599 0.4222 0.34 6/22/98 4 0.1460 0.0289 0.20 6/22/98 5 1.0134 0.2633 0.26 6/22/98 6 0.7222 0.4274 0.59 6/22/98 7 0.8476 0.3612 0.43 6/22/98 7 0.7974 0.3324 0.42 6/22/98 8 0.4695 0.0810 0.17 6/22/98 9 0.6324 0.1695 0.27 6/22/98 10 0.4754 0.1532 0.32 6/22/98 12 0.6083 0.2346 0.39 6/22/98 14 0.5350 0.2892 0.54 6/22/98 15 0.4830 0.1863 0.39 6/22/98 16 0.5292 0.2051 0.39 6/22/98 17 0.2831 0.1564 0.55 6/22/98 18 0.6069 0.1474 0.24

Total Unwashed Washed Washed Calculated Calculated unwashed mat subsample subsample subsample Calculated M+P total Date Mesocosm wetwt(g) netwetwt(g) wetwt(g) drywt(g) total dry wt(g) dry wt(g) 9/8/98 2M 1533 301.6 129.07 15.612 79.3 79.3 9/8/98 4 M 1437 302.5 140.86 20.0903 95.4 101.6 9/8/98 6 M 1649 300.6 120.24 22.2452 122.0 122.0 9/8/98 7 M 1256 305.3 123.25 20.9354 86.1 86.1 9/8/98 9 M 1894 322.7 149.27 23.7673 139.5 139.5 9/8/98 12 M 1504 313.5 204.32 26.0765 125.1 125.1 9/8/98 14 M 1738 306.2 110.67 17.565 99.7 99.7 9/8/98 15 M 1317 313.2 132.52 15.9718 67.1 74.6 9/8/98 16 M 1326 301.8 190.40 28.1104 123.5 123.5 9/8/98 18 M 1324 301.1 134.29 21.6617 95.2 95.2 9/8/98 15 P 143 142.7 51.65 7.4719 7.5 9/8/98 4 P 108 107.7 49.05 6.1865 6.2

continued on next page 179 Appendix P, continued

Net washed Net washed Date Subsample wet wt(g) dry wt(g) 9/8/98 2a 44.2705 5.4827 9/8/98 2b 41.3860 5.0817 9/8/98 2c 43.4152 5.0476 9/8/98 4a 36.0051 5.6631 9/8/98 4b 61.6050 8.4639 9/8/98 4c 43.2477 5.9633 9/8/98 6a 43.5548 8.8013 9/8/98 6b 43.0315 7.5943 9/8/98 6c 33.6512 5.8496 9/8/98 4P - a 18.0550 1.4900 9/8/98 4P - b 11.3771 2.1856 9/8/98 4P - c 19.6196 2.5109 9/8/98 I5P-a 19.2752 2.6339 9/8/98 l5P-b 16.8996 2.5346 9/8/98 15P-C 15.4734 2.3034 9/8/98 7a 42.2611 6.9996 9/8/98 7b 39.0950 6.7582 9/8/98 7c 41.8953 7.1776 9/8/98 9a 48.5810 7.7778 9/8/98 9b 52.2880 8.7006 9/8/98 9c 48.4035 7.2889 9/8/98 12a 85.6118 10.5253 9/8/98 12b 70.9335 6.1037 9/8/98 12c 47.7720 9.4475 9/8/98 14a 46.4446 7.1764 9/8/98 14b 34.4598 5.4603 9/8/98 14c 29.7694 4.9283 9/8/98 15a 56.1817 6.5961 9/8/98 15b 40.4347 4.8551 9/8/98 15c 35.9038 4.5206 9/8/98 16a 70.1507 10.1607 9/8/98 16b 66.0692 9.7901 9/8/98 16c 54.1759 8.1596 9/8/98 18a 58.0353 9.0185 9/8/98 18b 39.9691 6.6334 9/8/98 18c 36.2825 6.0098

180 APPENDIX Q - ELEMENTAL ANALYSES OF MESOCOSM METAPHYTON

Major species and elemental concentrations in the metaphyton and periphyton of the algal mesocosms. R =Rhizaclonium , C = Cladophora S = Spirogyra .

Sample Major P K Ca Mg AI B Cu Fe Mn Mo Na Zn Date Mcso SITE spp. Mg/g mg/g mg/g mg/g mg/g Pg/g Pg/g mg/g mg/g Pg/g Pg/g pg/g 6/22/98 All Initial algae R/C 1673 15.95 123.8 3.87 2.45 95 6.3 2.83 0.45 1.4 810 42.1 6/22/98 All Initial algae R/C 1612 15.30 123.3 3.79 2.31 92 6.2 3.03 0.47 2.4 712 45.0 6/22/98 All Initial algae R/C 1699 16.25 120.0 3.88 2.50 97 5.9 2.89 0.47 1.3 810 43.1 6/22/98 All Initial algae R/C 1645 15.61 120.2 3.84 2.37 95 5.7 3.02 0.49 1.9 709 45.9 6/22/98 All Initial algae R/C 1665 16.12 117.6 3.78 2.43 97 5.9 2.80 0.47 1.5 826 41.5 6/22/98 All Initial algae R/C 1633 15.72 118.4 3.77 2.33 96 5.3 2.94 0.49 2.3 725 44.2 9/8/98 2A algal mat R/C 781 II 69 108.4 6.08 3.14 116 7.7 3.76 0.27 1.5 1482 25.4 9/8/98 2A algal mat R/C 786 11.47 110.3 5.97 2.99 114 7.2 3.92 0.31 2.2 1329 27.8 9/8/98 2B algal mat R/C 856 12.56 117.1 5.56 2.37 126 7.3 3.04 0.16 2.2 1629 21.5 9/8/98 2B algal mat R/C 823 12.10 116.5 5.42 2.26 123 6.6 3.17 0.17 2.7 1474 22.7 9/8/98 2C algal mat R/C 888 12.32 107.3 5.61 2.73 127 7.4 3.35 0.18 2.6 1551 23.9 00 9/8/98 2C algal mat R/C 857 11.95 106.7 5.48 2.58 124 6.8 3.47 0.19 2.0 1388 24.8 9/8/98 4A algal mat R/C 688 23.32 86.8 5.64 1.37 231 7.3 1.92 2.04 2.3 650 18.9 9/8/98 4A algal mat R/C 658 22.55 84.3 5.39 1.33 222 7.0 2.01 2.20 1.7 583 19.4 9/8/98 4B algal mat R/C 886 22.80 72.1 5.51 1.55 231 6.6 2.26 2.04 1.0 1162 17.9 9/8/98 4B algal mat R/C 845 22.27 69.5 5.26 1.47 223 6.1 2.31 2.32 1.8 1032 18.6 9/8/98 4C algal mat R/C 726 22.35 88.5 5.93 1.55 243 7.5 2.07 2.08 2.2 627 21.3 9/8/98 4C algal mat R/C 685 21.69 84.4 5.62 1.46 233 6.8 2.11 2.35 2.7 545 21.7 9/8/98 4PA periphyton R/C 1033 19.73 67.1 5.25 2.47 206 8.1 3.47 1.81 1.2 2464 26.8 9/8/98 4PA periphyton R/C 981 19.02 64.2 4.96 2.32 200 7.7 3.45 2.07 1.0 2220 27.3 9/8/98 4PB periphyton R/C 991 18.07 79.5 5.14 2.62 210 7.5 3.22 2.06 0.8 2240 26.3 9/8/98 4PB periphyton R/C 964 17.57 75.5 4.92 2.49 205 7.3 3.26 2.32 1.0 2033 27.1 9/8/98 4PC periphyton R/C 921 17.09 80.8 5.06 2.57 188 8.2 3.33 1.99 1.4 2169 28.5 9/8/98 4PC periphyton R/C 870 16.27 76.9 4.77 2.40 180 8.2 3.34 2.25 2.0 1973 28.7 9/8/98 6A algal mat R/C 612 16.88 77.2 5.69 1.39 238 6.1 1.87 2.06 2.1 209 20.8 9/8/98 6A algal mat R/C 556 16.29 70.9 5.03 136 225 5.9 1.79 2.33 2.1 198 18.1 9/8/98 6A algal mat R/C 583 16.13 73.3 5.33 133 229 5.9 191 2.59 3.4 181 21.3

Continued on next page Appendix Q, conlinued

Sample Major P K Ca Mg A1 B Cu Fe Mn Mo Na Zn Date Meso SITE spp. pg/g mg/g mg/g mg/g mg/g pg/g pg/g mg/g mg/g pg/g pg/g pg/g 9/8/98 6B algal mat R/C 644 16.97 87.2 5.32 1.29 214 6.7 1.79 3.01 1.7 269 19.3 9/8/98 6B algal mat R/C 590 16.55 81.0 4.75 1.27 203 6.5 1.73 2.96 1.5 263 16.8 9/8/98 6B algal mat R/C 616 16.18 83.4 5.05 1.22 206 6.0 1.82 0.61 1.7 218 20.1 9/8/98 6C algal mat R/C 599 17.43 77.1 5.60 1.37 225 6.1 1.85 0.61 2.2 216 20.2 9/8/98 6C algal mat R/C 544 17.06 71.2 4.99 1.34 216 5.9 1.78 0.65 1.7 209 17.6 9/8/98 6C algal mat R/C 566 16.64 73.2 5.26 1.28 217 5.8 1.86 0.77 3.7 155 20.3 9/8/98 7A algal mat R/C 702 14.79 102.2 5.07 1.03 221 4.8 1.74 1.23 1.2 202 18.3 9/8/98 7A algal mat R/C 645 14.26 93.5 4.46 1.01 212 4.7 1.66 0.76 1.3 195 16.0 9/8/98 7A algal mat C 679 14.33 98.6 4.89 0.99 217 4.5 1.79 2.56 0.7 137 19.1 9/8/98 7B algal mat R/C 647 13.76 105.8 4.99 0.97 202 4.9 1.67 2.72 1.1 201 17.8 9/8/98 7B algal mat R/C 576 12.75 94.8 4.29 0.91 186 4.7 1.55 2.55 1.0 188 15.3 9/8/98 7B algal mat C 617 13.33 102.5 4.80 0.93 197 4.5 1.71 2.71 1.8 135 18.4 9/8/98 7C algal mat R/C 675 14.37 103.9 5.11 1.14 214 5.1 1.89 2.28 1.2 207 19.3 9/8/98 7C algal mat R/C 600 13.28 94.6 4.45 1.07 196 4.7 1.76 2.44 1.1 194 16.7 00 NJ 9/8/98 7C algal mat C 640 13.95 101.8 4.93 1.09 209 4.5 1.94 2.18 1.3 145 20.2 9/8/98 9A algal mat C 715 19.11 78.5 4.44 0.86 266 5.8 1.61 2.28 2.2 202 19.7 9/8/98 9A algal mat C 642 18.09 70.2 3.81 0.83 247 5.6 1.50 2.01 1.9 195 16.9 9/8/98 9A algal mat R/C 674 18.34 74.4 4.18 0.82 256 5.2 1.62 2.09 2.5 149 19.9 9/8/98 9B algal mat C 702 16.84 99.8 5.10 0.90 271 4.5 1.47 2.06 1.9 193 19.4 9/8/98 9B algal mat C 631 16.21 88.9 4.35 0.87 254 4.4 1.38 2.13 1.9 178 16.4 9/8/98 9B algal mat R/C 665 16.36 94.7 4.79 0.85 263 4.5 1.50 1.95 1.0 122 19.8 9/8/98 9C algal mat C 601 18.84 76.3 4.30 0.76 257 4.7 1.38 2.03 2.3 197 19.8 9/8/98 9C algal mat C 546 18.12 68.9 3.71 0.74 241 4.5 1.29 1.98 2.3 190 16.9 9/8/98 9C algal mat R/C 568 18.19 73.0 4.10 0.72 249 4.7 1.39 2.04 2.3 142 20.5 9/8/98 llA algal mat R/C 674 22.08 87.7 4.85 0.63 189 8.6 0.87 2.03 2.1 229 10.3 9/8/98 IIA algal mat R/C 734 22.25 94.4 5.39 0.64 200 8.8 0.96 2.10 3.2 199 13.1 9/8/98 IIB algal mat R/C 368 23.13 61.6 7.30 0.72 235 6.6 1.09 1.57 2.1 206 12.7 9/8/98 MB algal mat R/C 407 23.22 65.6 7.92 0.71 243 6.5 1.18 1.46 1.7 142 15.3 9/8/98 l i e algal mat R/C 504 17.76 57.8 6.29 0.92 233 7.1 1.38 1.62 1.9 182 15.5 9/8/98 l i e algal mat R/C 546 17.70 60.9 6.86 0.90 242 7.1 1.48 1.88 1.8 125 19.1

Continued on next page Appendix Q, continued

Sample Major P K Ca Mg AI B Cu Fe Mn Mo Na Zn Date Meso SITE spp. Mg/g ing/g mg/g mg/g mg/g Mg/g Mg/g mg/g mg/g Mg/g Mg/g Mg/g 9/8/98 I4A algal mat R.C.S S48 18.32 69.6 4.74 1.28 I9S 4.9 1.80 1.77 2.1 675 I5.S 9/8/98 14 A algal mat C S63 I7.S2 71.6 SIS 1.19 19S 4.6 1.88 195 3.1 572 18.5 9/8/98 I4B algal mat R/C.S SSS 17.66 72.2 4.77 1.26 18S 4.7 175 1.73 1.4 647 15 1 9/8/98 I4B algal mat C S99 17.97 76.6 S.24 1.26 19S 4.7 1.91 1.62 1.6 614 18.1 9/8/98 I4C algal mat R/C.S 611 17.98 70.0 4S I 1.26 190 S.l 1.79 1.78 1.4 696 14.9 9/8/98 14C algal mat C 643 18.08 74.0 4.9S 1.24 197 S.2 1.93 2.29 1.7 642 17.8 9/8/98 15A algal mat R/C.S 481 18.84 90.7 4.19 111 261 6.1 1.62 2.16 3.3 172 20.1 9/8/98 ISA algal mat R/C S24 18.99 97.9 4.71 1.10 272 6.1 1.77 2.41 4.2 100 24.3 9/8/98 15B algal mat R,C,S S49 21.S3 83.4 4.03 1.23 287 6.2 1.89 2.29 3.3 191 20.1 9/8/98 I5B algal mat R/C S88 21.40 88.8 4.48 1.20 296 6.4 2.03 2.10 4.3 124 24.1 9/8/98 ISC algal mat R/C.S 467 18.52 96.2 4.31 1.24 253 7.2 1.87 2.42 3.3 187 19.6 9/8/98 ISC algal mat R/C 497 18.30 103.4 4.84 1.20 260 7.2 2.03 2.44 2.S 120 23.8 9/8/98 ISPA periphyton R/C.S 771 22.84 S IS 2.94 1.78 342 S.8 3.10 2.24 1.4 366 15.4 9/8/98 ISPA periphyton R/C.S 80S 23.33 S2.4 3.00 1.8S 373 6.0 3.31 2 59 1.3 343 17.6 00 w 9/8/98 ISPB periphyton R/C.S 628 20.97 77.6 3.63 1.40 333 6.0 2.49 1.39 1.6 321 18.2 9/8/98 ISPB periphyton R/C.S 678 21.60 79.7 3.74 1.47 370 6.S 2.74 1.28 2.1 284 20.6 9/8/98 I SPC periphyton R/C.S 691 22.04 76.7 3.7S 1.46 376 7.1 2.71 1.44 3.1 275 19.2 9/8/98 I6A algal mat R/C.S 639 17.21 70.2 SSI 0.97 238 6.9 1.36 1.39 2.0 226 19.9 9/8/98 I6B algal mat R/C.S S93 19.11 71.0 S.S6 1.02 260 7.1 1.42 1.28 2.4 235 20.7 9/8/98 16C algal mat R/C.S 640 17.S2 7S.7 S.88 1.24 242 6.7 1.77 1.44 2.4 203 21.0 9/8/98 18A algal mat R/C.S 471 20.S8 79.7 6.62 0.96 248 S.l 1.46 1.21 2.3 337 18.6 9/8/98 18B algal mat R/C.S 6SI 21.91 63.1 6.61 1.2S 263 S.8 1.90 1.12 2.2 435 20.3 9/8/98 18C algal mat R/C.S S2S 21.36 61.3 7.13 0.79 261 S.8 1.2S 1.24 2.9 384 19.9 APPENDIX R - ELEMENTAL ANALYSES OF MESOCOSM SEDIMENTS

C=control, A=algal treatment, Initial = samples taken on date o f initial stocking.

Sample P K Ca Mg A1 B Cu Fe Mn Mo Na S Zn Date Meso Treatment ug/g mg/g mg/g mg/g mg/g ug/g ug/g mg/g ug/g ug/g ug/g ug/g ug/g 6/98 Initial A.C 555 8.84 5.28 4.56 32.68 35 28 30.59 636 6 344 310 105 6/98 Initial A .C 547 8.71 5.31 4.56 31.90 32 27 29.51 622 6 334 308 101 6/98 Initial A .C 521 8.41 5.02 4.33 30.97 29 27 29.09 604 6 330 289 96 5/17/99 1 C 619 8.84 5.53 4.77 33.41 40 30 32.56 678 7 372 379 115 5/17/99 2 A 594 8.94 5.80 4.63 33.28 44 32 31.80 613 6 375 587 106 5/17/99 3 C 558 9.04 6.05 4.88 34.05 40 29 32.41 610 6 373 324 105 5/17/99 4 A 594 8.73 5.73 4.70 32.40 40 30 30.67 568 6 384 704 106 5/17/99 5 C 597 8.89 5.61 4.73 33.11 36 28 31.44 653 6 378 344 105 5/17/99 6 A 605 9.16 7.59 5.30 33.87 37 30 31.82 631 7 386 598 106 5/17/99 7 A 561 9.07 7.52 5.36 33.33 36 27 31.50 579 7 382 619 101 5/17/99 8 C 572 8.94 4.74 4.43 33.05 35 28 31.39 619 7 372 313 104 5/17/99 9 A 580 8.71 5.92 4.76 32.81 41 28 31.28 594 361 386 104 5/17/99 10 C 595 9.06 5.72 4.85 34.41 39 32 33.22 682 7 382 339 107 5/17/99 11 C 562 9.03 4.32 4.37 33.77 37 28 32.10 663 7 361 291 115 5/17/99 12 A 561 9.23 5.30 4.90 34.14 36 35 31.95 641 7 378 331 109 5/17/99 13 C 568 8.91 4.87 4.36 32.48 35 27 30.16 655 7 370 376 106 5/17/99 14 A 589 9.32 4.93 4.47 33.87 37 28 31.51 606 7 384 503 105 5/17/99 15 A 541 9.42 5.61 4.95 34.28 34 28 31.29 605 7 389 459 102 5/17/99 16 A 495 9.54 4.34 4.51 35.54 34 30 32.14 668 384 287 99 5/17/99 17 C 584 9.16 7.17 5.31 33.83 39 29 31.06 589 7 366 393 105 5/17/99 18 A 553 8.64 5.01 4.46 32.19 34 32 30.06 605 7 337 341 117 5/17/99 19 C 482 9.01 5.87 4.96 34.05 39 29 31.88 687 7 374 291 99 5/17/99 20 C 579 9.14 5.64 4.82 33.68 40 28 31.02 595 7 384 363 105 APPENDIX S - MESOCOSM SEDIMENT CHEMISTRY

Soil chemical parameters in mesocosms. C=control, A=algal treatment. Initial = samples taken o f the upland soil used in the mesocosms. Exch. = exchangeable, CEC= cation exchange capacity.

Sampling exchg. P exchg. K. exch. Ca exch. Mg CEC Date Mesocosm Treatment pH ug/g ug/g ug/g ug/g meq/100 g 12/19/98 Initial A ,C 7.64 13 79 2930 458 18.7 12/19/98 Initial A ,C 7.59 13 78 2870 442 18.2 12/19/98 Initial A ,C 7.72 13 78 2930 453 18.6 5/17/99 I C 7.42 9 84 2560 406 16.4 5/17/99 2 A 7.53 3 101 2900 430 18.3 5/17/99 3 C 7.40 9 86 2660 427 17.1 5/17/99 4 A 7.16 3 104 2720 429 17.4 5/17/99 5 C 7.48 12 87 2650 405 16.8 5/17/99 6 A 7.48 5 91 3180 422 19.7 5/17/99 7 A 7.45 4 94 3120 399 19.2 5/17/99 8 C 7.49 10 85 2720 427 17.4 5/17/99 9 A 7.39 9 89 2770 450 17.8 5/17/99 10 C 7.64 11 85 3030 432 19.0 5/17/99 11 C 7.35 10 87 2790 445 17.9 5/17/99 12 A 7.33 10 90 2680 467 17.5 5/17/99 13 C 7.45 12 87 2680 447 17.3 5/17/99 14 A 7.23 8 92 2900 428 18.3 5/17/99 15 A 7.26 7 90 2840 523 18.8 5/17/99 16 A 7.30 6 85 2780 465 18.0 5/17/99 17 C 7.48 9 88 2820 421 17.8 5/17/99 18 A 7.49 11 85 2870 453 18.3 5/17/99 19 C 7.65 6 82 3000 472 19.1 5/17/99 20 C 7.52 9 89 2900 450 18.5

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