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Phosphorus Release and Storage by Two Isolated Wetlands in the Northern Lake Okeechobee Drainage Basin

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Permanent Link: http://ufdc.ufl.edu/UFE0011847/00001

Material Information

Title: Phosphorus Release and Storage by Two Isolated Wetlands in the Northern Lake Okeechobee Drainage Basin
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0011847:00001

Permanent Link: http://ufdc.ufl.edu/UFE0011847/00001

Material Information

Title: Phosphorus Release and Storage by Two Isolated Wetlands in the Northern Lake Okeechobee Drainage Basin
Physical Description: Mixed Material
Copyright Date: 2008

Record Information

Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
System ID: UFE0011847:00001

Full Text












PHOSPHORUS RELEASE AND STORAGE BY TWO ISOLATED WETLANDS IN
THE NORTHERN LAKE OKEECHOBEE DRAINAGE BASIN















By

CHRISTY L. SACKFIELD


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

UNIVERSITY OF FLORIDA


2005





























Copyright 2005

by

CHRISTY L. SACKFIELD















ACKNOWLEDGMENTS

I would like to thank my committee chair, Dr. Kenneth L. Campbell, for providing

me the opportunities to study, learn, and grow academically under his guidance. His

support has played a tremendous role in the success of this project. I would also like to

thank committee member Dr. Mark Clark for his enthusiasm for wetlands and his

dedication to this project, and thanks to Dr. Sanjay Shukla for his time and support.

Several people in the Agricultural and Biological Engineering department

contributed to the success of this project. I am sincerely grateful for Billy Duckworth's

help with fieldwork. Ralph Hoffman, Bob Tonkinson, and James Rummell helped with

materials and construction. Thanks to Ms. Yu Wang and the ladies in the lab in the Soil

and Water Science Department for their guidance in the laboratory. Thanks to Dr. Portier

for his assistance with statistical analysis.

I appreciate all the encouragement from my fellow graduate students, professors,

and friends. So many people made this research an experience of a lifetime. This project

would not have been possible without funding from the South Florida Water

Management District, the Florida Department of Environmental Protection, and the

Florida Department of Agriculture and Consumer Services.

And finally, I would especially like to thank my family and Davis whose love and

support have pushed me above and beyond what I thought possible. I could not have

done this without them.















TABLE OF CONTENTS

page

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

LIST OF TABLES ............... ............. ......... ...................... vi

LIST OF FIGURE S ......... ..................................... ........... vii

ABSTRACT .............. .................. .......... .............. ix

CHAPTER

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

1.1 Lake Okeechobee and W ater Quality Issues ........................................ ...............1
1.2 Beef Cattle Ranches and Water Quality Issues ............................................... 1
1.3 Hydrologic Conditions Relative to Florida ......... ......................5
1.4 Phosphorus in W wetlands ................................................ ............................. 6
1.5 Soil/W ater Phosphorus Interactions (P-Cycle) .................................. .............. .8
1.6 M easuring Phosphorus Uptake/Release .............................. ..............................11
1.7 Using Mesocosms for In-Situ Analysis of Phosphorus.............. ...... ........ 12
1.8 G oals and Objectives ............. ........................ .... .... .. ............ 14

2 M E TH O D O L O G Y ...................................................................................... 16

2 .1 Site D description ......................................... ...................16
2.2 Trial Run at Stormwater Ecological Enhancement Project..............................20
2.3 In-Situ W etland M esocosm Study .............................. .................................. 22
H hypothesis ........... ...... ... ...................................... .................. 23
2 .4 W ater Q u ality A naly sis.............................................................. .....................29
2 .5 S o il A n aly sis ................................................. ................ 3 1
2 .6 V egetation A naly sis.......... ............................................................. .... .... .... .. 34
2 .7 Statistical M ethods........... ........................................ ................ .. .... ...... 35

3 RESULTS AND DISCU SSION ........................................... .......................... 36

3.1 W after Level Results.............................. ............ ............. 37
3.2 Water Quality Data and Statistical Results................................................ 38
3.3 Phosphorus Results (Uptake/Release) ...................................... ............... 42
3.4 Soil Results .............................................. ........................ .... 49
3.5 Vegetation Results ......................................... ..................... ........ 50










3.6 B rom ide R esults................................................. 51
S ite 1 C control ................................................................ ............ ...... 54
Site 1 D ilute ................................................................... ......55
Site 1 Spike ............................................................................................... 56
Site 4 Control ............................................................... ..... ............. 57
Site 4 D ilute ........................................................................................... ... ..... 58
Site 4 Spike .................................. .............................. ....... 59
3.7 D term nation of EPCw Sm ax, DPS x .................................................................60
3.8 Langmuir-Hinshelwood Model of Phosphorus .................. .............64

4 C O N C L U S IO N S ................................................................................................... 6 8

5 SUGGESTIONS FOR FUTURE RESEARCH ......................................................72

APPENDIX: TRIAL RUN RESULTS ................................. ...............74

LIST OF REFERENCES ........................ .................. 77

BIOGRAPHICAL SKETCH ................................. ...........................................81




































v
















LIST OF TABLES


Table page

1-1. Mean soluble reactive P (SRP) and total P (TP) concentrations in dairy and beef
cattle m anure (G raetz and N air 1995) .............................................. .................. 4

2-1. Polycarbonate tube dimensions for trial run at Stormwater Ecological
Enhancement (SEEP) site on University of Florida campus...............................20

2-2. Treatments applied at SEEP trial run. ............................................ ............... 21

2-3. Treatments applied to mesocosms in wetlands at Pelaez & Sons Ranch ................23

2-4. Treatments applied at Pelaez Ranch based on water volumes in mesocosms...........28

3-1. Statistical analysis of phosphorus data, Pelaez & Sons Ranch...............................40

3-2. Statistical analysis of nitrogen data, Pelaez & Sons Ranch.................. ............41

3-3. Soil results (0-10 cm depth) for Site 1 and Site 4, Pelaez & Sons Ranch ...............49

3-4. Vegetation results for Site 1 and Site 4, Pelaez & Sons Ranch.............................51

3-5. Illustration of possible leakage underneath mesocosm walls in Site 4 control
m esocosm s. .......................................... ............................ 58

A-1. Trial run results from the Stormwater Ecological Enhancement Project (SEEP)
site, U university of Florida cam pus. ........................................ ....... ............... 74

A-2. Water quality results from trial run at Pelaez & Sons Ranch, Okeechobee County,
F lo rid a ........................................................... ................ 7 5
















LIST OF FIGURES


Figure page

2-1. Map ofPelaez & Sons Ranch, Okeechobee County, Florida, with wetland and
m esocosm locations........... ............................................................ ...... ........ 17

3-1. W after depths at Site 1.......................................... .......................... 38

3-2. W after depths at Site 4 .......................... ...................... ... .. ......... ........... 38

3-3. Mean SRP and standard deviations over time for Site 1. ........................................44

3-4. Mean SRP and standard deviations over time for Site 4..................... ..............45

3-5. M ass versus water depth over time for Site 4.................................. ............... 46

3-6. M ass versus w ater depth over tim e for Site 1....................................... ...................48

3-7. Illustration of poor mixing and ET effects using bromide data ..............................53

3-8. Effects of ET and groundwater loss in control and dilute mesocosms at Site 1.........55

3-9. Effects of ET and groundwater loss in spike mesocosms at Site 1. .........................57

3-10. Effects of ET and groundwater loss for control mesocosms at Site 4....................58

3-11. Effects of ET and groundwater loss for dilute mesocosms at Site 4....................59

3-12. Effects of ET and groundwater loss on spike mesocosms at Site 4.....................60

3-13. Schematic of graph used to determine phosphorus retention and release for
iso lated w etlan d .................................................... ................ 6 1

3-14. EPCw value for Site 1, Pelaez & Sons Ranch ...................................................62

3-15. EPCw graph for Site 4, Pelaez & Sons Ranch. ...................................................... 63

3-16. Predicted vs. measured SRP conc.using Langmuir-Hinshelwood model. ..............67

A-1. Water level changes in Site 1 and Site 4 during trial run .......................................75

A-2. Trial run, Site 1, soluble reactive phosphorus conc. vs. time. ..................................76









A-3. Trial run, Site 4, soluble reactive phosphorus cone. vs. time.................................76















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

PHOSPHORUS RELEASE AND STORAGE BY TWO ISOLATED WETLANDS IN
THE NORTHERN LAKE OKEECHOBEE DRAINAGE BASIN

By

Christy L. Sackfield

August 2005

Chair: Kenneth L. Campbell
Major Department: Agricultural and Biological Engineering

A mesocosm study was conducted to evaluate phosphorus removal potential of two

isolated wetlands located on the Pelaez & Sons beef cattle ranch in Okeechobee County,

Florida. Research has shown that wetlands function as sinks or as sources of nutrients

depending on various properties of the sediment, vegetation, and water column. Best

management practices for beef cattle ranching are currently being implemented in the

Okeechobee basin to reduce P loads to Lake Okeechobee and to help achieve total

maximum daily loads set by the Florida Department of Environmental Protection.

Phosphorus retention and storage by isolated wetlands in the Okeechobee drainage basin

is one of several BMPs that are currently being evaluated on the Pelaez & Sons beef

cattle ranch. The results from the in-situ mesocosms indicated phosphorus retention

under nutrient loading conditions in a native vegetation wetland on the ranch. Little to no

phosphorus retention occurred at an improved, floralta planted wetland. Studying

wetlands in-situ as opposed to conducting sediment core studies in a laboratory can









potentially provide more realistic estimates of P release or retention under varying water

column P concentrations; however, results from this study were limited due to

desiccation of the wetlands.














CHAPTER 1
INTRODUCTION

1.1 Lake Okeechobee and Water Quality Issues

Excessive phosphorus loads to Lake Okeechobee over the past several decades

have led to algal blooms and fish kills, discouraged recreation, and caused taste and odor

problems in the drinking water from the lake (Nordlie 2001). The Florida Department of

Environmental Protection has established a total maximum daily load (TMDL) of 140

metric tons of total phosphorus (TP) per year to help restore the health of the lake. This

translates into a maximum in-lake phosphorus concentration of 40 ppb. Despite land

acquisition and other direct management efforts, the lake is still suffering from high

nutrient inputs from the surrounding watershed indicating that further research is needed

on best management practices (BMPs) and their implementation to improve water

quality.

1.2 Beef Cattle Ranches and Water Quality Issues

Prior to implementation of BMPs in the northern Lake Okeechobee watershed, a

study was conducted from 1985 to 1989 to assess average annual P budgets for each of

25 tributary basins according to their land uses (Fonyo et al. 1991). A follow-up study

was conducted from 1997-2001 to update P budgets based on land management changes

that occurred since the previous study (Hiscock et al. 2003). These two studies were

compared to evaluate effectiveness of the implementation of recent BMPs and

management practices on reducing P loads to Lake Okeechobee. Results indicated that

net P imports to the lake decreased by 28% from the previous study (2380 to 1717 t P),









primarily as a result of changes to four main land uses, dairy (1170 to 458 t P), improved

pasture (1010 to 559 t P), row crops (72 to 545 t P), and sod farms (-70 to -239 t P)

(Hiscock et al. 2003).

Changes in net P imports from dairies were primarily caused by the implementation

of two important programs, the 1987 Florida Department of Environmental Protection

Dairy Rule and the Dairy Buy-Out Program. These programs led to a decrease in the

number of dairies in the northern Lake Okeechobee watershed as well as improved

management practices. Dairy farms only account for 2% of the land use area in the Lake

Okeechobee watershed while improved pasture accounts for 36% (South Florida Water

Management District 2004). Decreases in net phosphorus imports from improved pasture

are the result of lower fertilizer application and improved management practices (Hiscock

et al. 2003).

The significance of dairies in regards to net P imports to Lake Okeechobee are

decreasing. This leaves beef cattle ranches and improved pastures as the current leading

source of net P imports to the Lake. The animal densities and runoff phosphorus

concentrations associated with beef cattle are low compared to dairy cattle; however, the

vast acreage (approximately 470,000 acres) that beef cattle ranches encompass makes

them a major contributor of phosphorus to Lake Okeechobee (SFWMD).

There are 25 drainage basins in the Lake Okeechobee watershed, and of these, four

were identified as priority basins, contributing a disproportionate amount ofP loads to the

lake. These four basins are the lower Kissimmee River Basins (S-65D, S-65E, and S-

154) and the Taylor Creek-Nubbin Slough basin (S-191) (South Florida Water

Management District 2004). The Lake Okeechobee drainage basin consists of









approximately 4,400 square miles, and the four priority basins cover about 450 square

miles of the watershed. These priority regions contribute approximately 35 percent of the

potentially controllable phosphorus load, and account for most of the over-target load to

the lake (SFWMD 2004). Agricultural activity is a major contributor to water quality

problems in these regions. The average annual phosphorus discharge concentration for

improved pastures in the S-154 basin, according to Rules of the SFWMD: Works of the

District Basins Chapter 40E-61, F.A.C is 0.35 mg P/L. Any discharge found to be in

excess of this limit must be reduced to avoid penalty.

According to the U.S. Environmental Protection Agency, runoff from agricultural

activities is considered a nonpoint source of pollution meaning that pollutants are carried

by precipitation over and through the ground as a diffuse source to nearby water bodies.

This process is often expedited on improved pastures due to intensive drainage canals and

high water tables that are common in the central and south Florida region. The most

obvious form of pollution from beef cattle ranches comes from cattle manure, of which a

significant portion is phosphorus attached to manure particles (Reddy et al. 1996). The

amount of manure production varies according to cattle size, age, and productivity of the

animal. The impact of runoff from beef ranches and dairies on water quality can vary

according to cattle manure composition.

Mean soluble reactive phosphorus (SRP) and total phosphorus (TP) concentrations

were found to be higher in dairy manure compared to beef manure (2760 vs. 2100 mg P

kg-1 for SRP and 6500 vs. 5300 mg P kg-1 for TP, respectively (Table 1-1) (Mathews

1992, Graetz and Nair 1995). This is likely due to differences in the diets of beef cattle

and dairy cattle. Beef cattle consume grass with little mineral P supplement while dairy









cattle receive a significant P supplement (Graetz and Nair 1995). However, if you

consider that the amount of land used for improved pasture (36%) now greatly exceeds

the amount of land used for dairy (2%), it becomes evident that the pollution load from

beef cattle ranches can become a serious threat to water quality.

Table 1-1. Mean soluble reactive P (SRP) and total P (TP) concentrations in dairy and
beef cattle manure (Graetz and Nair 1995)
Manure Types SRP (mg P kg-1) TP (mg P kg-1)
Dairy 2760 (1330)a 6500 (2480)
Beef 2100 (880) 5300 (980)
aNumbers in parenthesis are standard deviation values.
Over-fertilization of pastures and direct deposition of cattle manure in waterways

are common problems that can also lead to water quality violations in receiving water

bodies. Results from one study conducted at the MacArthur Agro-ecology Research

Center (MAERC) in 1998 indicated that P loads from improved pastures are often linked

to historical phosphorus fertilizer application, which was applied regularly for 15-20

years prior to 1987 (Bohlen 2003). One case study, conducted in 1997, identified that

bahiagrass roots were capable of penetrating into the subsurface hard pan (Bh horizon).

This suggests that this type of deep-rooted forage may utilize phosphorus located in the

hard pan; therefore, the hard pan can serve as a valuable source of naturally occurring

phosphorus for bahiagrass. Ranchers are able to further reduce their fertilizer

applications if bahiagrass forage is utilized on their ranches and if a substantial pool of

phosphorus is stored in the subsurface hard pan (Bh horizon) from historical P loading.

This information, as well as information from other studies, allowed ranchers to reduce

the amount of phosphorus fertilizer applied to their fields, which saves them money, and

reduces their phosphorus loads in runoff, improving water quality. This study as well as









several other studies provided useful recommendations for the development of a BMP

manual for beef cattle ranches.

In June of 1999, the Florida Cattlemen's Association (1999) published a manual

describing Water Quality Best Management Practices for Cow/Calf Operations in order

to protect water bodies of Florida and to maintain compliance with state water quality

standards. The effectiveness of these BMPs is being evaluated under the Lake

Okeechobee cow-calf BMP research program, which was started by the University of

Florida, Institute of Food and Agricultural Sciences (UF-IFAS). The BMPs

recommended in the cow/calf operations manual are specific to the unique soil and water

conditions of Florida and were developed to help cattlemen meet water quality standards

as well as maintain production and income.

Some common BMPs for cow-calf operations include fencing off cattle from

waterbodies, supplying alternate sources of water, providing ample shade for cattle away

from waterbodies, and installing structures that provide transit of livestock across

waterways without causing sedimentation and/or erosion.

1.3 Hydrologic Conditions Relative to Florida

Soils in the northern Lake Okeechobee watershed consist primarily of Spodosols,

which are characterized by three general horizons, the A, E, and Bh horizons (Graetz and

Nair 1995). Spodosols account for approximately 64% of soils in Okeechobee County

(Nair and Graetz 2002). These soils can often be identified by their slightly acidic pH,

sandy composition, and shallow water tables. In general, the soils in the Okeechobee

drainage basin have <4% clay content and slopes that range from 0-2%, so there is little

to no erosion to contribute to water quality issues (Haan 1995). The A horizon is the

uppermost soil layer which contains small amounts of organic matter and is usually 10 to









50 cm thick. The E horizon contains white sand and varies in thickness. The subsurface

hardpan Bh horizon, or spodic layer, has a low permeability and is identified by a buildup

of organic matter and metals; principally, iron (Fe) and aluminum (Al). For much of the

year, the water table exists between the spodic horizon and the soil surface. The A and E

horizons have a low phosphorus retention capacity; however, the spodic horizon is

capable of retaining high levels of P, if water is allowed to infiltrate into this layer.

According to one study (Campbell et al. 1995), a significant improvement in water

quality occurred in soils with a well-defined spodic horizon. Deep, coarse sand soils with

a barely detectable spodic horizon did not show significant improvements in water

quality in this same study (Campbell et al. 1995). Deep percolation of soluble P into the

iron (Fe) and aluminum (Al) rich lower spodic (Bh) horizons is restricted due to low

permeability; therefore, high soluble P concentrations exist in surface flow or lateral

subsurface flow above the spodic layer (Graetz and Nair 1995).

The topography of south Florida is essentially flat with an abundance of streams,

ponds, marshes, and wetlands. Wetlands currently account for approximately 18% of the

land cover in the Lower Kissimmee River region, where this research takes place (Reddy

et al. 1996). Historically, most improved pastures were once swamplands that were

developed using intensive agricultural drainage techniques. Some pastures maintained

low-lying depressions that were more difficult to completely drain, forming small ponds

or wetlands across the landscape. These wetlands have been identified as having a major

role in reducing the amount of nutrients in pasture runoff

1.4 Phosphorus in Wetlands

Phosphorus is an essential nutrient for plant and animal growth; however, excessive

accumulation of nutrients in wetlands or any other waterbody can cause undesirable









environmental and economic consequences. Phosphorus can be found in the soils,

minerals, living organisms, and water columns of lakes and wetlands. Wetlands may act

as sinks, sources, or transformers of nutrients within a watershed. Although wetlands

generally serve as nutrient sinks, changing hydrologic conditions, decaying vegetation,

and animal use can alter the nutrient cycle leading to an export of nutrients from the

wetland (Mitsch and Gosselink 1993).

The biotic and abiotic factors that influence the P cycle in wetlands are dependent

on water levels, amount of available P, soil P adsorption, and seasonal changes in uptake

by microorganisms (Daniel et al. 1998). The phosphorus cycle does not have a

significant gaseous loss mechanism as does the nitrogen cycle, and it occurs primarily in

the sedimentary cycle. The primary storage mechanism for phosphorus in wetlands is

sediment accumulation, accounting for more than 95% of the P in natural wetlands

(Faulkner and Richardson 1989). Vegetation may account for large amounts of

phosphorus storage during the active growing season, but vegetation serves as a relatively

short-term storage mechanism overall because once the plants senesce, some of the

bound nutrients are released back into the soil or water column (Reddy et al. 1996).

Microorganisms and sediments sorptive characteristics control the initial uptake of P in

wetland systems.

Although some wetlands have a short-term ability to remove nutrients, there exists

the possibility that they may become nutrient saturated leading them to release nutrients

to downstream waterbodies. The transport, storage and biological availability of P in a

watershed may be greatly influenced by the cycling of P in wetlands (DeBusk 1999);









therefore, it is necessary to closely examine nutrient dynamics in these systems in relation

to in-situ experimentation to obtain realistic P uptake rates.

1.5 Soil/Water Phosphorus Interactions (P-Cycle)

It is important to understand the phosphorus cycle in wetlands in order to

understand how wetlands may serve to improve water quality for improved pastures, as

identified in the cow-calf BMP manual. Wetlands perform many important

biogeochemical functions in watersheds, which include trapping sediments, storing

nutrients, and transforming inorganic nutrients to organic forms. Some of the major

processes that influence the phosphorus cycle in wetlands are listed as follows: (1)

diffusion, (2) plant uptake, (3) litterfall, (4) sedimentation, (5) decomposition, (6)

sorption, and (7) burial and peat accretion (Debusk 1999). Phosphorus sorption in

wetlands occurs primarily at the oxidized sediment-water interface by diffusive processes

(Reddy et al. 1996).

Diffusion involves concentration gradients that exist between the soil pore water

and the water column. Dissolved forms of P are transferred from regions of high

concentration to regions of lower concentration. For instance, if the P concentration of

the soil porewater is greater than the P concentration of the water column, then

phosphorus will diffuse out of the soil and into the overlying water until equilibrium is

reached and the gradient no longer exists. However, equilibrium is constantly changing

due to several factors such as runoff events carrying nutrients into the wetland or wind

affects re-suspending P-rich sediments into the water column. Diffusion is one of the

primary mechanisms by which phosphorus is transferred between soil and the water

column within a wetland. Phosphorus sorption by wetlands soils can only occur when









inorganic P is in direct contact with sorptive sites. This requires diffusion of water

column P into the underlying soils before phosphorus can be retained (Reddy et al. 1995).

Plants are capable of extracting needed nutrients by their roots either from the soil

or from the water column if roots are located in the water column. However,

macrophytic uptake of nutrients occurs primarily through roots in the soil on a daily to

weekly time scale. Algae grow attached to plant stems, the sediment and litter, or within

the water column. Algal response to nutrient availability can be more rapid, on the order

of hours to days. The form of P taken up by plants and algae is inorganic and is primarily

orthophosphate (HPO42- and H2P04-). If an equilibrium P concentration has been reached

between the soil and water column, and if no new nutrients are added, then the plants will

generally take up phosphorus from the soil, causing a shift in equilibrium concentration.

Plants play a major role in the phosphorus cycle because they can assimilate large

amounts of nutrients into their biomass. However, once the growing season has ended

and the plants begin to senesce, nutrients will continue to be pumped by the plant, but the

nutrients will not necessarily be utilized by the plant and will therefore be quickly cycled

back into the system.

Litterfall contributes to the phosphorus cycle in that once plants die or senesce, the

dead plant tissue will fall to the soil surface releasing a portion of the phosphorus that

was once incorporated in its biomass. Depending on the hydrologic condition, litter

quality and plant productivity, an accumulation of dead biomass will occur. This layer of

detritus will provide nutrients for other living plants and organisms in the wetland once it

has been broken down into a useable form. More readily available forms of nutrients in









the wetland will be consumed first. Therefore, much of the P storage by plants is

transient, returning much of their nutrients back into the nutrient cycle.

Sedimentation often occurs in wetlands because particulate matter that was once

suspended in the water column settles out due to lower velocities. These lower velocities

as well as shallow water depths and emergent vegetation, serve to filter sediments out of

the water column. Erosion is a major contributor of nutrient pollution in many parts of

the United States; however, its role in sandy soils with no clay coatings or soils where

metal oxide associates with parent material is not as profound due to low phosphorus

retention capacities. Low relief topography reduces impacts from erosion in Florida.

Wetlands can "fill-in" over time due to heavy sediment loading from the surrounding

watershed.

Decomposition is the breakdown of organic matter, such as dead plant tissue, by a

variety of microorganisms that utilize organic carbon as an energy source. These organic

compounds must be broken down into smaller components and ultimately into

orthophosphate, which can be utilized as a nutrient or diffused back into the soil or water

column. Temperature, pH, nutrient availability, carbon quality, redox potential, and

availability of electron acceptors including oxygen, nitrate, sulfate, manganese, and iron

influence decomposition rates.

Sorption involves two processes that include the following: 1) adsorption of

orthophosphate by clays and iron or aluminum oxides in the soil, and 2) precipitation of

phosphate with either iron and aluminum oxides or dissolved calcium, to form solid

compounds in the soil or water column. Phosphate minerals are often very stable in the

soil and contribute to the long-term storage of P in wetlands. Soils with high









concentrations of soil-extractable aluminum and soils that are predominantly mineral

soils have shown high phosphate removal rates, due to their sorptive capacities

(Richardson 1985). The phosphorus retention capacity of wetland soils is directly

correlated with the oxalate extractable iron and aluminum content and organic matter

content according to various studies (Reddy and D'Angelo 1994, Reddy et al. 1996).

Burial and peat accretion takes place when organic matter is gradually buried in the

soil profile, making it more resistant to decomposition. Peat accretion occurs when

deposition of organic matter is more rapid than the decomposition rate. Peat accretion is

a very slow process and often does not produce conditions preferable for reducing high P

loading rates to levels that are acceptable for water quality targets.

If a wetland is being used as a BMP to help reduce phosphorus loads in runoff to

downstream waterbodies, then it is important to know exactly how much P is entering the

wetland as compared to how much P is leaving the wetland. If the wetland is not

successful at reducing P loads to acceptable levels, then it is possible that the wetland has

reached its maximum potential for P storage and other means are necessary to further

reduce P loads from that particular site. If high levels of P are released from a wetland,

then the water quality of nearby streams and waterbodies will ultimately suffer. Excess

phosphorus loads can lead to eutrophication and subsequent destruction of ecological

function.

1.6 Measuring Phosphorus Uptake/Release

In order to assess the potential for a wetland to store phosphorus and remove P

from runoff, it is important to determine historical P loading to the wetland and P loading

capacity of the wetland. Analyzing the amount of P in wetland soils can provide great

insight into these types of questions because storage of P in soils is often the primary









means of P storage in wetlands. Common measurement techniques involve taking

several soil cores from the wetland site, storing them on ice, and returning them to the

laboratory for testing. Chemical fractionation schemes are then used to identify forms of

inorganic and organic P (labile and non-labile pools). One such method involves

subsequent extractions of soils with KC1, NaOH, and HC1 (Reddy et al. 1995). The major

inorganic P pools include the following: loosely adsorbed P, Fe- and Al- bound P, and

Ca- and Mg- bound P. The following describes a laboratory procedure performed in the

Soil and Water Science department at the University of Florida:

1. Extraction with KC1 represents the labile pool of inorganic phosphorus,
which is important for plant growth and for controlling P concentrations of
the overlying water. This pool of phosphorus typically ranges from 0.1 to
1.1% of the total P in wetlands.

2. Extraction with NaOH represents the P associated with amorphous
oxyhydroxide surfaces and crystalline Fe and Al oxides. Typical ranges for
this pool are 17-43% of total P.

3. Extractions with HC1 represent the P associated with Ca and Mg minerals.
This pool is essentially unavailable to biological assimilation and is not often
found in the Okeechobee watershed because of low pH.

*Residual P not extracted by KC1, NaOH, and HC1 is considered to be highly
resistant and biologically unavailable. Fulvic acid bound P (NaOH-P) is
biologically reactive and can be 6-57% of total P.

This method is commonly used to develop Phosphorus Sorption Isotherms for

various wetland soils.

1.7 Using Mesocosms for In-Situ Analysis of Phosphorus

The influence of vegetation, organisms, grazing, seasons, etc. are not taken into

account during the phosphorus sorption isotherm method. By removing the soil cores

from their natural environment and testing them in a controlled laboratory environment,

the results are indicative of phosphorus uptake/release by soil only, which may or may









not be useful for real world applications. Phosphorus sorption isotherms are conducted at

a certain controlled temperature and agitation of soil within the solution maximizes

uptake/release of phosphorus by the soil. In the field however, especially in Florida,

environmental conditions are highly variable and extraction results from laboratory

isotherms may not provide the best possible information about phosphorus uptake and

release. The calculation of maximum retention capacity based on isotherms usually

underestimates potential P sorption by soils under field conditions (Reddy et al. 1995)

because in the field there are numerous factors contributing to phosphorus uptake/release

from the water column and soil porewater, for example, vegetation and algae. The

overall P sorption in the field would be higher because there would be more available

sinks for P compared to isotherm studies.

Another approach to measuring P uptake/release in soils is using mesocosm type

structures for an in-situ experiment as opposed to a laboratory type method. Mesocosms

are middle-sized (typical range of m2 to ha), constructed ecosystems that serve as useful

tools for ecological research. They represent extensions of the microcosm method

because their relatively large size allows the incorporation and use of much more

ecological complexity than is possible in conventional microcosms (Kangas and Adey

1996). Another definition of mesocosms is that they are outdoor semi-controlled

ecosystems whose physical dimensions and basic water chemistry are known and

controlled (Boyle and Fairchild 1997). The initial physical, chemical, and biological

conditions within mesocosms will ultimately shape the final results of experiments. In

Florida, mesocosm studies are used to provide the unique soil-type constraints, water

flows, evaporation, rainfall, wind effects, and water chemistry. One study on the "role of









mesocosm studies in ecological risk analysis" recommended that researchers develop

closer working relationships with mathematical modelers in linking computer models to

the outcomes of mesocosm studies (Boyle and Fairchild 1997). By coordinating the

development of models with the formation of tests and validations, the realism and

accuracy of both activities can be improved (Boyle and Fairchild 1997). The results of

this type of collaborative effort could help provide a foundation for the development of

ecological indicators and improve strategies for environmental monitoring and

assessment on the regional level (Boyle and Fairchild 1997).

Unlike microcosm studies, mesocosm studies can be designed to include critical

ecological variables such as site-specific water-quality conditions, native flora and fauna,

and various strengths and complexities of ecological interactions (Boyle and Fairchild

1997). Factors that influence the fate of nutrients, such as phosphorus, within a system

can be broken down into three main components, physical, chemical, and biological.

Some physical differences include solar radiation, temperature, and the transparency of

the water. Chemical factors that might alter the behavior of nutrients in a system include

pH, redox potential, and level of critical inorganic nutrients. Biological factors may

include type of crops, standing versus floating, levels of organic carbon, and rates of

metabolic activity. Differences in these ecological conditions occur regionally, and are

expected to produce differences in the results of mesocosm experiments as well as model

outputs (Boyle and Fairchild 1997).

1.8 Goals and Objectives

1. Evaluate the influence of nutrient loading on water column nutrient concentrations
in two isolated wetlands by measuring changes in water quality over time with an
in-situ mesocosm approach.






15


2. Compare nutrient uptake/release in floralta planted wetland to native
vegetation wetland.

3. Address seasonal/water level effects on nutrient uptake/release in wetlands.

4. Demonstrate the effectiveness this in-situ mesocosm approach for
determining equilibrium phosphorus concentration (EPC) values for the wetlands.














CHAPTER 2
METHODOLOGY

A mesocosm study was conducted on two isolated wetlands located on Pelaez &

Sons beef cattle ranch in Okeechobee County, Florida (latitude: 270 9' 25.2" N,

longitude: 80 12' 57.6" W). A circular area with a diameter of approximately 68 cm was

enclosed within each mesocosm structure. The area contained the natural soil, water, and

organisms in order to produce in-situ results. Some mesocosms were spiked with a

treatment that represented a typical runoff effect, which would be contaminated with N

and P from cattle manure or fertilizer. Treatments of 0.5 ambient concentration, ambient

concentration, and two times ambient concentration were used to represent a range of

runoff events. The range of treatments was limited by the size of the mesocosms and

wetlands.

2.1 Site Description

This research was conducted on Pelaez & Sons beef cattle ranch located on 128th

Street in Okeechobee County, Florida (Priority Basin S-154). The ranch is approximately

617 hectares and was historically and is currently managed as a cow/calf operation. In

the late 50's and early 60's, however, row crops such as tomatoes were produced on

portions of the property. The property can produce enough forage to support an

estimated 580 animal units; however, the system currently supports an average of 533

cows, with an average weight of 454 kg and 35 bulls with an average weight of 612 kg.

The native cover used for grazing is primarily 'Pensacola' bahiagrass (Paspalum

notatum) with some fields planted with Floralta limpograss (Hemarthria altissima). The









ranch is divided into approximately fifteen separate pastures and is maintained

hydrologically through a series of canals and culverts. Figure 2-1 illustrates locations of

the two wetlands on the ranch as well as approximate locations of the mesocosms within

the wetlands.







S\\Wetland Boundary
SNle;soco.sm location














Figure 2-1. Map ofPelaez & Sons Ranch, Okeechobee County, Florida, with wetland and
mesocosm locations.

The study site is characterized by subtropical climate conditions with distinct wet

and dry seasons. Average annual rainfall is approximately 1160 mm, with most rainfall

occurring during the wet season months of May through October. Four storms directly

affected Florida around the time of this experiment in 2004, Hurricanes Charley, Frances,

Ivan, and Jeanne. Soils are generally Spodosols that are poorly drained fine sands with

neutral to slightly acidic pH. A spodic horizon or hardpan exists at a depth of 50 to 76

cm below the soil surface and a typical soil profile consists of the A, E, Bh, and Bw

horizons. The sandy pasture soils and lateral groundwater movement in the uplands









cause much of the P to be transported to the wetlands or channels that cut through the

ranch rather than being held efficiently on site (Graetz and Nair 1995).

These soil conditions are indicative of high water tables and saturated soil

conditions during the wet season; therefore, there are several depressional wetlands

located on the ranch, covering approximately 7% of the ranch area. Two specific

wetlands on the ranch were chosen for this study. Site 1 has a drainage area of

approximately 58 ha and is characterized by Myakka Fine Sand and Immokalee Fine

Sand. The average elevation at this site is 9.3 meters above mean sea level. The wetland

drains to a flume that connects to a channel that transports water off of the ranch and

eventually towards Lake Okeechobee. Drainage from the watershed eventually ends at

gated control structures leading to Lake Okeechobee (Reddy et al. 1996). Site 4 has a

drainage area of approximately 22 ha and is characterized by Myakka Fine Sand. The

topsoil layer in this wetland is believed to be below the hardpan meaning that the soil is

primarily characterized by coarse, white sand. The average elevation of this wetland is

approximately 9.9 meters above mean sea level and this wetland also drains to a flume

that is connected to a channel. Myakka and Immokalee soils are characterized by their

poor phosphorus retention capacity and high water permeability. These wetlands are

seasonal with periods of standing water in the wet season (May-Oct) and drying out in

the dry season (Nov-Apr).

The wetlands on this ranch provide a variety of ecological functions as well as

hydrologic functions. The wetlands vary in size, shape, and vegetative cover, but they

are similar in that they are both isolated, receiving inputs from surface runoff or

subsurface flow and precipitation only. The wetland at Site 1 is covered with native









vegetation including Panicum hemitomon, Juncus effuses, Pontederia cordata, and

Polygonum hydropiperiodes. The vegetation at Site 4 wetland is dominantly Floralta

limpograss (Hemarthria altissima) with some bahiagrass (Paspalum notatum) and some

Polygonum hydropiperiodes. Research has been conducted on the usefulness of Floralta

for grazing purposes, and the average daily gain (ADG) of cows grazing on Floralta

compared to Bahiagrass was found to be somewhat similar (Sollenberger et al. 1988).

Surface water in the wetlands and ditches on the beef cattle ranch are colored,

indicating humic and fulvic acids within the water column. Organic phosphorus

associated with these acids accounts for greater than 40% of total phosphorus in the water

column. Humic and fulvic acids give the water a tea color and are relatively resistant to

biological degradation (Reddy and D'Angelo 1994).

The wetlands for this study were selected on the basis that they play some role in

improving water quality on the ranch. Restoration of hydrology of isolated wetlands is

expected to reduce phosphorus loads to Lake Okeechobee by storing surface runoff and

assimilating excessive nutrients before they are transported downstream. The

implementation of landowner and typical cost-share Best Management Practices for

addressing nonpoint sources are expected to achieve a significant reduction in TP loading

to the lake. The Best Management Practices that will be implemented at this site include

raising the water level (flashboard risers) to hold water in the wetlands and slowly

releasing it after rains, and restoring a longer hydroperiod in the isolated wetlands.

Reddy et al. (1996) suggested that increasing the hydraulic retention times of a wetland

would serve to improve the overall phosphorus retention capacity of the wetland. Also,

alternative water supplies will be installed on the ranch to help keep cattle out of the









wetlands and canals to prevent direct contamination by cattle manure. This study was

conducted in the pre-BMP phase of the project meaning that water was allowed to flow

from the wetlands to the flumes naturally without implementation of any water control

practices.

2.2 Trial Run at Stormwater Ecological Enhancement Project

A trial run experiment was conducted at the Stormwater Ecological Enhancement

Project (SEEP) site on the University of Florida campus using smaller mesocosm

structures to assess the time frame needed to conduct a complete experiment on the

wetlands at Pelaez & Sons Ranch. Table 2-1 describes the characteristics of the

polycarbonate tubes used for the trial run experiment.

Table 2-1. Polycarbonate tube dimensions for trial run at Stormwater Ecological
Enhancement (SEEP) site on University of Florida campus.
Total Length of Tube = 50.8 cm
Diameter (Outside) =15.2 cm
Wall Thickness = 0.1 cm
Diameter (Inside) 15 cm
Cross-Sectional Area= 176.7 cm2
Total Volume = 5442.8 cm3 (5.4 Liters)

Before the polycarbonate tubes were installed, a composite water sample was taken

from three locations within SEEP. This was conducted before serious disturbance of the

site occurred. The sample was filtered, acidified and placed on ice to be taken back to the

laboratory for analysis of soluble reactive phosphorus (SRP). Comparing ambient water

quality in the SEEP to the water quality inside the small mesocosms provides useful

information on the effect of the mesocosm structure on water quality (ambient vs.

control).

Nine polycarbonate tubes were installed at SEEP on July 15, 2004. Native

vegetation was carefully retained in each tube, and then each tube was pushed









approximately 10 cm into the soil. Care was taken to ensure a proper seal was formed

between the bottom of the mesocosm and the surrounding soil to avoid leakage.

An assumption was made that the ambient soluble reactive phosphorus level in the

SEEP was approximately 1 mg/L. Using this assumption, treatments were applied with

the goal of raising the SRP concentration in the spiked treatment mesocosms to 3 mg/L

and reducing the SRP concentration in the diluted treatment mesocosms to 0.5 mg/L.

Table 2-2 shows the treatments applied to the mesocosms, with triplicates of each

treatment.

Table 2-2. Treatments applied at SEEP trial run.
Mesocosm Treatment
Control (Cl, C2, C3) No treatment applied
Spiked (S1, S2, S3) Added -150 mL of 100 mg/L P solution
Diluted (D1, D2, D3) 50% dilution with deionized water

Treatments were carefully applied; ensuring that water level inside the mesocosms

remained the same as water level outside the mesocosms (1/2" tube used as a siphon).

This was done to prevent porewater exchange with the water column due to a head

pressure differential. After treatments were applied, water samples were taken from each

tube with a syringe, filtered, acidified, and placed on ice for transport to the lab for

analysis of SRP. Water samples were taken again on July 16, 2004 (composite ambient

and samples from each mesocosm). Two more water sampling dates had been set for the

18th and 20th; however, on the 18th, all of the mesocosms had been flooded due to a storm

event raising water levels. Further water sampling would not have provided meaningful

information. Samples taken were refrigerated until analysis, which took place within 28

days of sampling. SRP results from the trial run experiment are listed in Table A-1.









It was noted during the trial run experiment that the water level inside the

mesocosms did not consistently coincide with water levels outside the mesocosms. The

clay content of the soil allowed a strong seal to form between the bottom of the tube and

the soil. Because SEEP site serves as a detention basin, it receives high runoff loads from

the surrounding area during storm events. As the water level at SEEP rose, it did not rise

as quickly inside the tube because the tube only received water input from rainfall and

not from surface runoff The same occurred as the water level dropped after the rainfall

event. The water level dropped much more quickly in SEEP as compared to the water

level inside the mesocosms. This led to the conclusion that future mesocosm designs

may need to be modified to include some type of bladder that allows water level to

equilibrate between the inside and outside of the structure without head differentials

potentially resulting in mass flow of porewater into or out of the mesocosms. In soils

with lower clay content, the differences in water level would possibly not have been as

profound because the levels would have equilibrated naturally through the soil.

2.3 In-Situ Wetland Mesocosm Study

This experiment was conducted to evaluate various phosphorus interactions within

the wetlands. An in-situ experimental design was used so that all factors influencing

phosphorus storage and release in wetlands could be evaluated. The direction of

phosphorus flux is primarily regulated by the concentration gradients across the

soil/water interface; therefore, in-situ mesocosms were subjected to high, low, and

ambient phosphorus levels to compare the flux of phosphorus between the soil and

overlying water column. Changes in water quality concentrations of the water column

were regularly monitored over time in hopes of obtaining phosphorus uptake and release

rates.









Hypothesis

* The spike and dilute treatments will cause a shift in equilibrium between the
phosphorus concentration in the overlying water column and the soil porewater,
leading to a diffusive flux

* SRP concentrations in all mesocosms will converge at an equilibrium phosphorus
concentration where uptake equals release

* The SRP concentration in the water column will decrease over time in the spiked
mesocosms due to uptake by soil, vegetation, algae, etc.

* The SRP concentration in the water column will increase over time in the dilute
mesocosms due to release of phosphorus from the soil, vegetation, algae, etc

The treatments for this experiment are shown in Table 2-3.

Table 2-3. Treatments applied to mesocosms in wetlands at Pelaez & Sons Ranch.
Mesocosm Wetland Phosphorus Treatments
1-3 Floralta Wetland (Site 4) 0.5A
4-6 Floralta Wetland (Site 4) A (control)
7-9 Floralta Wetland (Site 4) 2A
10-12 Native Vegetation (Site 1) 0.5A
13-15 Native Vegetation (Site 1) A (control)
16-18 Native Vegetation (Site 1) 2A
*Each mesocosm will be replicated three times for comparison. A=Ambient.

For the actual experiment, a total of eighteen mesocosms were constructed, nine

mesocosms for Site 1 and nine for Site 4. The mesocosms were constructed out of

Fiberglass Kalwall material (Sun-Lite HP), which was ordered from Solar Components

Corporation. This material was chosen for being lightweight, shatterproof, highly

transmissive of sunlight (85-90%), impact resistant, and easily manageable. The

mesocosms had a wall thickness of 0.1016 cm, were 61-91 cm in height, and

approximately 68 cm in diameter when completed. The circular mesocosms were

constructed from a rectangular sheet; therefore, the edges had to be overlapped and sealed

using a fiberglass epoxy and aluminum tape along the outside wall for additional support.

The original kalwall sheet height was 152 cm and was cut to produce mesocosms at 60









cm and 90 cm heights, to reduce costs. The mesocosms did not have inflows or outflows;

they simply isolated the areas within the mesocosms from the rest of the wetland to

assess effects of various influential factors on phosphorus retention in the soils and

floodwaters. Bladders were not incorporated into the design of these mesocosms, as

suggested from the trial run, to avoid compromising the structural integrity of the

mesocosms. Water level differences between the inside and outside of the mesocosms

during the experiment were not expected to be as significant at Pelaez & Sons due to the

sandy soil conditions. Also, water level fluctuations in the two wetlands were not

expected to be large. The mesocosms were open at the tops and bottoms so that they

could be pushed into the wetland soil as well as exposed to the atmosphere at the top to

maintain field conditions as much as possible. It was assumed that light and temperature

remained similar inside and outside of the mesocosm because of the material chosen for

the mesocosm design.

Once the mesocosms were constructed, solutions for treatments of the mesocosms

were prepared. Water quality results from a trial run experiment at Pelaez & Sons Ranch

were used to design and prepare the treatments for the actual experiment. Results from

this trial run are presented in the appendix, Table A-2, and Figures A-i, A-2, and A-3.

Based on the trial run, ambient soluble reactive phosphorus (SRP) concentration at Site 1

was 0.23 mg/L and the ambient ammonium (NH4+) concentration for this site was 0.20

mg/L. For Site 4, ambient SRP concentration was 1.6 mg/L and ambient NH4

concentration was 0.2 mg/L. The treatments used for the SEEP experiment were

approximately the same treatments used in this experiment, three control mesocosms (no

treatment), three 50% diluted with de-ionized water, and three nutrient enriched (spiked)









mesocosms. The desired concentrations after applying the treatments for the spiked

mesocosms were 3.0 mg/L SRP and 0.40 mg/L NH4+ for Site 1 and 3.2 mg/L SRP and

0.40 mg/L NH4+ for Site 4.

A 500 mg P/L solution was prepared using phosphorus fertilizer (KH2PO4) and a

100 mg N/L solution was prepared using nitrogen fertilizer (NH4C1). These solutions

were prepared in separate six-gallon containers to be carried into the field for treatment

application. A 2000-ppm bromide tracer solution was also prepared to add to each

mesocosm. Bromide was used successfully as a subsurface water-movement tracer in an

experiment conducted on flat, sandy, high water table soils in the Kissimmee River Basin

of Florida, which drains into Lake Okeechobee in a former study (Campbell et al. 1995).

Other tracers such as chloride and rhodamine tracers did not prove useful in the region of

interest due to high background concentrations and sorption of the tracer to various

elements, making detection and recovery difficult. For these reasons, bromide, a

conservative tracer, was used to raise the bromide concentration in each mesocosm to 5

mg/L to provide some insight into the hydrologic conditions occurring inside the

mesocosms. Evapotranspiration and groundwater losses were estimated using bromide

results.

Once the equipment was prepared and carried into the field, locations for the

mesocosms within the wetlands were identified. General locations for the mesocosms

had been identified during the trial run experiment. An area was chosen within the

wetland that provided similar vegetative cover for all the mesocosms to be placed in the

wetland as well as similar water levels. It was difficult to find locations for all eighteen









mesocosms in the wetlands that provided similar conditions. The area in which the

mesocosms could be placed was limited by water depth.

On October 20, 2004, installation of the mesocosms within the wetlands

commenced. Each mesocosm was carefully placed over the vegetation and lowered

down to the soil. Once soil was encountered, pressure was gently applied by hand to

minimize movement of the mesocosm while a knife was used to cut through vegetative

roots and the soil surrounding the tube. A board was placed on top of the mesocosm so

even pressure could be applied while pushing the structure into the soil. Two people

were required to successfully install the mesocosms in the wetlands. The mesocosms

were pushed approximately 10 cm into the soil. Care was taken to ensure that the

mesocosms were deep enough in the soil to prevent leakage under the bottom walls of the

mesocosm. To test for leaks, water level inside a test mesocosm was lowered below the

outside water level, and a stopwatch was used to determine how long it took the water

level to fill back up (water level would not change or would change very slowly inside

the mesocosm if properly constructed). Installing the structures while attempting to

cause as little disturbance as possible was an important aspect of the experiment. Once

the mesocosms were installed, they were allowed to settle for 24 hours before treatment

application.

After a 24-hour settling period, ambient water samples were taken from each

wetland to establish initial water quality conditions. Water samples were taken from each

mesocosm for the same purpose. Comparing ambient water samples from the wetlands to

initial condition samples from each mesocosm provides an estimate of the degree of

disturbance from installation.









Treatments were then applied on October 21, 2004. The control mesocosms did

not receive any treatment except for the bromide solution. All eighteen tubes received a

bromide addition based on water levels that was expected to raise the concentration to 5

mg Br/L inside each tube. Each Spike mesocosm received additions from the phosphorus

and nitrogen solutions according to their water depths to raise the N and P concentrations

to a predetermined level. Because the amount of solution added to the spike tubes was

minimal compared to the total water volume in the tube, water levels inside and outside

the tube remained the same. For the dilutions, 50% of the water volume within the tube

had to be removed and then replaced with de-ionized water. To do this, a 1 1/2" siphon

tube was used to connect the inside water level to the outside water level while a clear

plastic trash bag placed inside the mesocosm was slowly filled with the appropriate

amount of de-ionized water. The siphon tube allowed water levels to constantly

equilibrate, pushing 50% of the water volume out of the mesocosm and replacing it with

the de-ionized water volume inside the plastic bag. Once water levels were the same

inside and outside the mesocosm, the siphon tube was carefully removed and de-ionized

water inside the trash bag was released into the mesocosm, thus completing the 50%

dilution treatment. The de-ionized water had to be carefully released from the plastic bag

to avoid disturbance. The bromide was added after the dilution so that bromide would

not be lost through the siphon tube. Each tube was very carefully stirred for complete

mixing of the water column following treatment application. Treatments were applied at

random to the mesocosms installed in each wetland, as indicated in Table 2-4.












Table 2-4. Treatments applied at Pelaez Ranch based on water volumes in mesocosms.


Site 1


Control
2


Dilute
2


Spike
2


Circumference (cm) 208.8 214.9 219.5 214.9 208.8 211.8 199.6 210.3 208.8
Radius (cm) 33.2 34.2 34.9 34.2 33.2 33.7 31.8 33.5 33.2
Bromide Addition (mL) 107.0 156.0 108.0 138.0 171.0 112.0 117.0 142.0 95.0
Ammonium Chloride Addition (mL) 95.0 114.0 76.0
Phosphorus Addition (mL) 261.0 313.0 210.0
Water Addition (L) 27.6 34.1 22.5

Control Dilute Spike
Site 4 1 2 3 1 2 3 1 2 3
Circumference (cm) 210.8 210.3 216.4 210.3 210.3 216.4 213.4 210.3 213.4
Radius (cm) 31.5 31.4 32.4 31.4 31.4 32.4 31.9 31.4 31.9
Bromide Addition (mL) 140.0 120.0 137.0 106.0 116.0 163.0 129.0 134.0 132.0
Ammonium Chloride Addition (mL) 103.0 107.0 106.0
Phosphorus Fertilizer Addition (mL) 165.0 172.0 170.0
Water Addition (L) 21.2 23.2 32.6 ---









Water quality sampling was again conducted within each mesocosm immediately

following treatment application to assess effectiveness of the treatments. Water quality

results taken immediately after treatment application and until the end of the experiment

were used to evaluate concentration changes over time. Water levels were also recorded

each time water samples were taken. Water sampling was conducted on day 1, 2, 4, and

8 following treatment application. Details on water sampling techniques and water

quality parameters are discussed later.

Vegetation and soil samples were collected at the end of the experiment.

Vegetation above the water surface was clipped, collected in individual Ziplock bags for

each mesocosm, and then stored on ice for transport back to the lab. Vegetation below

the water surface and above the soil surface was also clipped and stored in a separate

ziplock bag for analysis. Soil cores were taken from within each mesocosm using a

special wetland-coring device. Cores were stored in ziplock bags and placed on ice for

transport to the lab.

2.4 Water Quality Analysis

Water samples were collected and analyzed for soluble reactive phosphorus (SRP),

total phosphorus (TP), nitrate (NO3), ammonium (NH4+), total kjeldahl nitrogen (TKN),

and bromide (Br). The next several paragraphs describe methods used for water quality

analysis.

Water total Kjeldahl nitrogen (TKN) was assessed using a Kjeldahl digestion

method in compliance with EPA Method #351.2. Reagents used include concentrated

sulfuric acid (H2S04) and Kjeldahl salt catalyst (K2SO4 + CuSO4). Samples were taken

in the field with a syringe, acidified with concentrated H2S04, and then stored on ice for

transport to the lab for analysis.









Water total phosphorus was assessed using an autoclave method. Reagents

included 11 N H2SO4 and potassium persulfate. Samples were digested in the autoclave

for 60 minutes at 1210C and 15 psi. Water TP in the sample digests was determined

using a TechniconTM Autoanalyzer, EPA Method 365.1 (EPA 1993). Samples were

taken in the field with a syringe, acidified with concentrated H2SO4, and then stored on

ice for transport to the lab for analysis.

Soluble reactive phosphorus, nitrate, and ammonium concentrations were

determined using a TechniconTM Autoanalyzer. Samples were taken in the field with a

syringe, filtered through 0.45-rm filter paper, acidified with concentrated H2SO4, and

then stored on ice for transport to the lab for analysis.

Bromide was analyzed using a Perkin Elmer Series 200 Auto-sampler and a

RFICTM Ion Pac AS4A-SC Analytical 4x250 mm Ion Exchange Column. A wavelength

of 205 nm and a flow rate of 1 mL/min were used on the water samples to determine

bromide concentrations. The eluent used was 20 mmol sodium borate powder

(Na2B407* 10H20).

The procedures used for collecting water samples in the field were as follows: One

composite sample was taken outside of the mesocosms, and one sample was taken inside

each mesocosm (sampling before treatment application and then Day 1, Day 2, Day 4,

and Day 8 following treatments).

The soluble versus particulate forms of P are useful in quantifying physical

behavior during transport. Transport processes affect the availability of P for

assimilation by biota and retention by soils and sediments (Reddy et al. 2003).









Groundwater monitoring wells were installed around the perimeter of the wetlands

to determine gradients between the surface water in the wetland and groundwater;

however, these data were not available during the time frame of this experiment. The

wells were instrumented with water level recorders to track water level changes. Water

levels were to be measured both above and below the spodic horizon in order to estimate

the flow through this layer.

2.5 Soil Analysis

Soil cores were taken at the end of the experiment with a special coring device that

was developed at the University of Florida Soil and Water Science Department. Soils

were analyzed for bulk density, water content, pH, total phosphorus from ashing, water-

soluble phosphorus, and Fe/Al oxalate bound phosphorus.

To calculate bulk density and water content, the whole wet soil sample was

weighed in the original collection bag, noting the number of soil cores per bag. The

volume of the soil sample was calculated based on the size of the corer used to take the

sample and the number of cores. The corer had a cross sectional area of 38.5 cm2 and a

length of 10 cm. The sample was then homogenized and a 0.28 kg sub-sample was

taken, picking out roots from the sample. A portion of the sub-sample was placed in an

aluminum tin, weighed, and then dried at 700C for a minimum of 72 hours. After drying,

the soil sample and tin were weighed again. This procedure allowed for the calculation

of water content and bulk density of the soil samples. Once the soil sample was dried, it

was hand ground and placed in a scintillation vial for eventual analysis of total

phosphorus from ashing. A portion of the wet, homogenized soil sample was stored for

eventual water extraction to assess water-soluble phosphorus in the soil.









Soil pH was determined using an ORION SA 720, Fisher AR50 pH meter. The

meter was calibrated using a 2-point calibration with buffer solutions pH 7.00 then pH

4.00 to obtain a standard curve. Twenty mL of deionized water were added to 10 mL of

wetland soil sample then stirred and allowed to equilibrate before taking the pH

measurement (Hanlon 1994, Thomas 1996).

Total phosphorus was determined using the ignition or ash method in compliance

with EPA Method 365.1. Soils were dried (at 700C for 72 hours), ground in a ball mill,

and passed through a #40 mesh sieve. Then, 0.2-0.5 g prepared soil as well as an external

QC standard (peach leaves) were placed in a muffle furnace for 30 min. at 2500C then 3-4

hr. at 550C. Weights were determined before and after being placed in the furnace for

loss of ignition (LOI) calculations. The ash was moistened with distilled, de-ionized

water and 20 mL of 6.0 M hydrochloric acid (HC1). Samples were then placed on a hot

plate at 100-1200C until dry, and then an additional 30 minutes on high heat. Samples

were re-moistened with DDI water and 2.25 mL of 6.0 M HC1, and then placed back on

the hot plate to bring to a boil. The samples were filtered with Whatman #41 filter paper,

and then transferred to 20-mL HPDE scintillation vials for TP analysis. The TP

concentrations of digested solutions were determined analytically on a TechniconTM

Autoanalyzer. Calculations were as follows (Anderson 1976, Jackson 1958) (EPA

Method 365.1):

Total Phosphorus (pg g-')= TP conc. (pg mL-1) 50 (mL) / soil wt. (g)

Loss of Ignition (%) (LOI) = 100-[Ash weight (g) / soil wt. (g) 100]

Water-soluble phosphorus was determined using 2.00 g of air-dried soil sieved to

pass a 2-mm sieve into a 50-mL centrifuge tube. 20 mL of de-ionized water was added,









and then the tubes were placed on their sides in a reciprocating shaker at low speed for

one hour. The samples were centrifuged at 6000 rpm for 10 min. A Millipore filtration

apparatus and 0.45-im filters were used to filter the supernatant from the tubes into 20-

mL scintillation vials. The soluble reactive phosphorus concentration in the samples was

determined using the automated ascorbic method (Luscombe et al. 1979).

Soil analysis for oxalate extractable iron and aluminum bound phosphorus was

conducted by preparing a soil:solution ratio of 1:40 (0.5 g dry ground soil and 20 mL

oxalate reagent) (McKeague et al. 1966, Sheldrick 1984). The oxalate reagent was

prepared using 350 mL of ammonium oxalate and 267.5 mL of oxalic acid. Samples

were placed in tubes and shaken in the dark for 4 hours. Then the samples were

centrifuged at 6000 rpm for 10 min, and filtered with 0.45-[im filter paper with the lights

off. The pH of the solution was checked (pH should be 3.0). Filtered samples were sent

to the UF/IFAS Analytical Research Laboratory (ARL) for determination of oxalate

extractable Fe/Al bound phosphorus (EPA Method 200.7). The oxalate extraction was

used to determine the Fe and Al bound P, which is the reactive fraction of amorphous Fe-

Al oxides.

An in-depth soil characterization was not conducted for this experiment due to the

fact that the experiment was conducted in-situ and there were several factors affecting

phosphorus assimilation in the soils. Other research studies involved with phosphorus

assimilation in soils have conducted chemical fractionation schemes as mentioned earlier.

Phosphorus sorption isotherms are then developed based on the results from this

procedure. These isotherms can be used to determine the maximum phosphorus retention

capacity and uptake rates of soils, but again, the calculation of maximum retention









capacity based on isotherms usually underestimates potential P sorption by soils under

field conditions (Reddy et al. 1995). Phosphorus release rates from soils are probably

slower under field conditions compared to rates observed under laboratory conditions

(Reddy et al. 1996). An attempt was made to estimate maximum phosphorus retention

capacity and EPCw values for the wetland soils in this research based on oxalate

extractable Fe/Al results and previous results from soil cores taken within the Lake

Okeechobee drainage basin.

In one experiment, batch incubation studies were conducted on selected wetlands

soils in the Okeechobee Basin to demonstrate their capacity to retain or release P (Reddy

et al. 1995). The average EPCw (threshold P concentration in water column where P

retention = P release) for wetlands soils in the Okeechobee Basin was found to be 0.42

mg P L-1 (Reddy et al. 1995). Soils with strong binding capacities have low EPC values

(Reddy et al. 1996). Chemical fractionation was used in the study to identify forms of

inorganic and organic P (labile and non-labile pools). Other reported results for S-154

Basin (Pelaez Ranch included in this basin) from Reddy et al. (1995) include the

following: pH = 6.21, TOC (mg g-) = 110, Bulk density (g cm-3) = 0.46.

2.6 Vegetation Analysis

Vegetation type and biomass were identified for each wetland site. Above water

vegetation volume and below water, above soil vegetation volume were determined in

each mesocosm.

At the end of each experiment, the vegetation from inside the mesocosms was

clipped at the water surface and then again at the ground surface and brought to the lab

for biomass analysis. The division of vegetative growth above the water surface as






35


compared to below the water surface is often important for data interpretation, especially

if the data can be normalized according to vegetative biomass within each mesocosm.

2.7 Statistical Methods

Water quality data were analyzed using Statistical Analysis Software (SAS, 2003)

version 9.1.0. An analysis of variance (ANOVA) was performed on the data using the

GLM procedure, which uses the method of least squares to fit general linear models. The

Waller-Duncan k-ratio t test was performed on all the main effect means. Significant

differences were determined at the p<0.01 level.
















CHAPTER 3
RESULTS AND DISCUSSION

The native vegetation wetland (Site 1) exhibits lower ambient nutrient

concentrations compared to the improved, floralta planted wetland (Site 4), as a result of

differences in cattle stocking densities in the surrounding pastures, soil characteristics,

and vegetative cover. The wetland at Site 4 receives higher nutrient loading on an annual

basis from higher cattle stocking densities on the surrounding pasture compared to Site 1,

and has a limited phosphorus storage capacity due to low Fe/Al content of the soil within

the wetland. The soil at Site 4 is coarse, white sand, characterized by a low phosphorus

storage capacity and high infiltration rates. At Site 1, lower cattle stocking densities are

evident and the storage capacity of the wetland soil is improved by having higher Fe/Al

content. Organic matter buildup at Site 1 is higher than at Site 4 due to vegetative

densities within the wetlands. The maximum phosphorus storage capacity of the soil was

found to be higher at Site 1 compared to Site 4.

Rapidly decreasing water levels during the time frame of this experiment produced

unfavorable conditions for data collection and analysis. In general, water samples were

taken at the midpoint of the water column. As water levels decreased, the location of

sampling moved closer to the sediment-water interface. Phosphorus gradients within the

water column have been identified in lakes, and it is believed that such gradients also

exist in wetlands. Phosphorus concentrations are generally higher near the sediment-

water interface. It is possible that as the water level declined, changes in water column









phosphorus concentrations were compounded due to a naturally existing gradient within

the water column.

3.1 Water Level Results

Initial water depths were approximately 16 cm above the soil surface and declined

rapidly during the course of the experiment. These low water levels were not ideal for

taking water quality samples. Sediments play a more dominant role in the metabolism of

the water column at shallow water depths. Water levels declined slightly more rapidly at

Site 4 compared to Site 1 (Figs. 3-1 and 3-2). The higher organic matter content of the

soil at Site 1 possibly serves as a "sponge", helping to maintain saturated soil conditions

for longer periods of time under decreasing water level conditions. Infiltration through a

thick organic layer is usually limited.

Three to five water depth measurements were taken at each mesocosm. An average

daily value was determined for each wetland to produce Figs. 3-1 and Fig. 3-2. Water

depths inside the mesocosms were influenced by proximity of the mesocosms to the

canals that run through the wetlands. Slightly higher water depths were measured in

mesocosms located closest to the canals. Average daily water depths were also

determined per treatment for some analyses.










Site 1 Native Vegetation Wetland
20.0 Average Water Depth in Mesocosms

^ 16.0 -- v, y = -1.8611x + 71263
R2 = 0.9659
S12.0

S8.0-

4.0

0.0
10/21/2004 10/23/2004 10/25/2004 10/27/2004 10/29/2004 10/31/2004
Date

Figure 3-1. Water depths at Site 1.

Site 4 Improved Wetland
Average Water Depth in Mesocosms
20.0

-16.0 --T

120 y = -2.0305x + 77743
R2 = 0.9437



4.0-

0.0
10/20/2004 10/22/2004 10/24/2004 10/26/2004 10/28/2004 10/30/2004
Date

Figure 3-2. Water depths at Site 4.

3.2 Water Quality Data and Statistical Results

Water quality results and statistical analyses are presented in Table 3-1 and Table

3-2. The time, 0.5 days, indicates samples that were taken before treatments were

applied. Results from day 1 indicate samples that were taken immediately following

treatment application. The trends over time, which will be discussed in future sections,

were examined from day 1 to the end of the experiment. The wetland at Site 4 was









completely dry by October 29, 2004; therefore, no water quality samples were taken.

Samples were taken on October 29 at Site 1 wetland, but water levels were near zero.

There was no water inside three of the nine mesocosms located in Site 1 wetland

by day 9 (one control, one dilute, and one spike were dry). Results for SRP, TP, NH4+,

NO3-, and TKN on day 9 were determined from water quality samples taken from the

other six mesocosms that were not dry (two replicates of each treatment analyzed).

One control, two dilutes, and one spike mesocosm were dry by October 25 in Site

4 wetland.

Mean concentrations in the same column with the same letter (a, b, or c) in front

indicate values that are not statistically different. For instance, on the first day, before

any treatments were applied (time 0.5), SRP concentrations for all three treatments were

statistically the same. On the second day, after treatment application, the control and

dilute were statistically similar to each other, but different from the spike treatment at

Site 1. At Site 4, SRP concentrations for all three treatments were statistically different

immediately following treatment application. The same occurred for total phosphorus

concentrations.

At both Site 1 and Site 4, ammonium concentrations were only statistically

different immediately following treatment application. Nitrate concentrations remained

statistically similar throughout the time frame of this experiment. No relationships were

determined from the TKN results.










Table 3-1. Statistical analysis of phosphorus data, Pelaez & Sons Ranch.
Soluble Reactive Phosphorus (SRP)


Tie (day) 0.5


Site 1
1 2 3 5 9


Site 4
0.5 1 2


3 5


Root MSE 0.029 0.59 0.284 0.321 0.287 0.086 0.133 0.303 0.102 0.178 0.219
TRTp-value 0.4293 0.0002 0.0002 0.0008 0.0008 0.001 0.31 0.0001 <0001 <0001 0.015
LSrman (std
0.017 0.344 0.164 0.186 0.165 0.061 0.077 0.175 0.059 0.103 0.155
error)
Spike
stdev 0.013 1.032 0.49 0.555 0.494 0.014 0.087 0.517 0.102 0.258 0.204
nman a-0.047 a-4.098 a-2.122 a-1.788 a-1.660 a-1.462 a-1.729 a-3.197 a-3.400 a-3.564 a-3.744
Control
stdev 0.045 0.027 0.026 0.021 0.047 0.126 0.119 0.09 0.128 0.146 0.234
nman a-0.068 b-0.082 b-0.095 b-0.068 b-0.120 b-0.188 a-1.868 b-1.849 b-1.822 b-1.912 b-2.090
Dilute
stdev 0.018 0.006 0.024 0.037 0.017 0.078 0.177 0.033 0.069 0.085 novalue
nman a-0.035 b-0.022 b-0.036 b-0.048 b-0.083 b-0.140 a-1.903 c-0.570 c-0.795 c-0.826 c-0.795

Total Phosphorus (TP)
Site 1 Site 4
Tme(day) 0.5 1 2 3 5 9 0.5 1 2 3 5
RootMSE 0.163 0.403 0.501 0.652 0.425 0.148 0.151 0.228 0.172 0.177 0.346
TRTp-value 0.1634 <0001 0.0006 0.0064 0.0068 0.0024 0.288 <0001 <0001 <0001 0.033
ISrmnan (std
0.094 0.233 0.289 0.377 0.245 0.104 0.087 0.132 0.099 0.102 0.244
error)
Spike
stdev 0.142 0.65 0.796 1.084 0.705 0.085 0.144 0.388 0.256 0.199 0.288
nman a-0.298 a-5.149 a-3.463 a-2.768 a-2.227 a-2.266 a-1.922 a-3.540 a-3.877 a-3.792 a-4.041
Control
stdev 0.158 0.243 0.233 0.161 0.079 0.23 0.066 0.061 0.104 0.192 0.288
nman a-0.546 b-0.478 b-0.831 b-0.435 b-0.836 b-0.718 a-2.060 b-2.019 b-2.038 b-2.088 b-2.237
Dilute
stdev 0.186 0.067 0.253 0.274 0.194 0.071 0.209 0.042 0.11 0.131 novalue
nman a-0.280 b-0.132 b-0.467 b-0.364 b-0.605 b-0.542 a-2.136 c-0.642 c-0.921 c-0.944 b-0.951


*LSMEANs are the same for each treatment.
*All C centrations measured in mg/L


*STDEVaries for each TRT and time step.
*Site 1 Native Vegetatin Wetland, Site 4 Impoved Wetland


Lake Okeechobee has been impacted from phosphorus loading from its

surrounding watershed. Phosphorus trends over time were analyzed in greater detail

because phosphorus is the major nutrient of concern. This in-situ mesocosm experiment

was primarily beneficial in determining phosphorus uptake/release dynamics within the

wetlands. Changes in nitrogen concentrations were not as important in this research.












Table 3-2. Statistical analysis of nitrogen data, Pelaez & Sons Ranch.
Ammonium (NH4)


Time (day) 0.5


Site 1
1 2 3 5 9


Site 4
0.5 1 2


Root MSE 0.016 0.105 0.025 0.092 0.079 0.423 0.049 0.038 0.065 0.066 0.036
TRT p-value 0.381 0.0086 0.28 0.592 0.399 0.718 0.968 <.0001 0.201 0.554 0.582
LSmean (std
error) 0.009 0.061 0.014 0.053 0.046 0.299 0.028 0.022 0.037 0.038 0.025
Spike
stdev 0.025 0.171 0.021 0.144 0.02 0.217 0.064 0.065 0.104 0.024 0.017
mean a-0.046 a-0.392 a-0.037 a-0.141 a-0.043 a-0.399 a-0.091 a-0.570 a-0.175 a-0.098 a-0.059
Control
stdev 0.005 0.061 0.032 0.059 0.134 0.665 0.053 0.011 0.013 0.041 0.047
mean a-0.026 b-0.058 a-0.057 a-0.112 a-0.126 a-0.585 a-0.082 b-0.041 a-0.122 a-0.160 a-0.092
Dilute
stdev 0.01 0.012 0.019 0.038 0.022 0.218 0.018 0.008 0.039 0.105 no value
mean a-0.034 b-0.014 a-0.021 a-0.061 a-0.045 a-0.221 a-0.083 b-0.029 a-0.067 a-0.136 a-0.045

Nitrate (NO3)
Site 1 Site 4
Time (day) 0.5 1 2 3 5 9 0.5 1 2 3 5
Root MSE 0.003 0.018 0.005 0.002 0.002 0.015 0.016 0.019 0.005 0.005 0
TRT p-value 0.037 0.961 0.152 0.079 0.422 0.318 0.682 0.246 0.63 0.593 no value
LSmean (std
error) 0.001 0.01 0.003 0.001 0.001 0.01 0.009 0.011 0.003 0.003 0
Spike
stdev 0.003 0.019 0.003 0 0 0.023 0.012 0.033 0.006 0.003 0
mean b-0.007 a-0.022 a-0.009 a-0.011 a-0.011 a-0.027 a-0.018 a-0.038 a-0.015 a-0.009 a-0.011
Control
stdev 0 0.019 0.005 0.003 0.003 0.011 0.023 0.003 0.006 0.005 0
mean a-0.011 a-0.022 a-0.016 a-0.007 a-0.009 a-0.019 a-0.027 a-0.013 a-0.015 a-0.006 a-0.011
Dilute
stdev 0.003 0.016 0.006 0 0 0.004 0.005 0 0 0.005 no value
mean a-0.015 a-0.025 a-0.007 a-0.011 a-0.011 a-0.046 a-0.016 a-0.011 a-0.011 a-0.006 a-0.011

Total Kjeldahl Nitrogen (TKN)
Site 1 Site 4
Time (day) 0.5 1 2 3 5 9 0.5 1 2 3 5
Root MSE 2.928 2.439 3.92 4.079 7.736 14.851 0.723 0.218 8.037 0.426 4.872
TRT p-value 0.862 0.02 0.174 0.347 0.832 0.994 0.394 <.0001 0.349 0.0006 0.546
LSmean (std
error) 1.691 1.408 2.263 2.355 4.466 10.501 0.417 0.126 4.64 0.246 no value


Spike
stdev
mean
Control
stdev
mean
Dilute
stdev
mean


4.47 3.66 5.657 6.942 3.567 3.642 0.349 0.347 13.868 0.476 6.867
a-6.969 a-9.92 a-11.729 a-10.396 a-15.918 a-30.56 a-5.217 a-5.826 a-13.404 b-5.008 a-10.568

1.783 1.761 2.68 1.015 8.494 2.221 0.151 0.066 1.204 0.446 0.565
a-6.417 a-7.235 a-8.378 a-6.740 a-17.651 a-29.56 a-5.427 b-5.389 a-6.378 a-5.884 a-5.883

1.602 1.159 2.63 0.828 9.73 25.367 1.193 0.132 0.144 0.344 no value
a-5.655 b-2.057 a-4.760 a-5.236 a-13.767 a-31.19 a-6.055 c-2.133 a-3.218 c-3.161 a-3.542


*LSMEANs are the same for each treatment.
*All Concentrations measured in mg/L


*STDEV varies for each TRT and time step.
*Site 1 Native Vegetation Wetland, Site 4 Improved Wetland


3 5









3.3 Phosphorus Results (Uptake/Release)

Assuming that soluble reactive phosphorus concentrations in the soil porewater and

water column were already at equilibrium prior to the experiment, it was expected that

the system would show a net decrease in water column SRP concentration in the spiked

mesocosms over time as a new equilibrium was established in response to the nutrient

load. The SRP concentration in the spiked water column was expected to be greater than

the SRP concentration in the soil porewater, causing a net flux of SRP from the water

column into the sediment through diffusive processes. Results indicated a decrease in

SRP concentration over time at Site 1 as expected, but not at Site 4. Site 1 wetland

showed a typical two-part response to the nutrient loading, a quick, initial SRP uptake

followed by a slower, more drawn out uptake rate (see Fig. 3-3). Site 4 wetland showed

an increase in SRP concentration over time in the spiked mesocosms, possibly due to

evapotranspiration loss and lack of adsorptive sites in the soil in this wetland. As water

levels dropped at Site 4, the concentration of SRP in the mesocosms increased (see

Figure 3-4). Obtaining an equilibrium phosphorus concentration value was difficult for

the time frame of the experiment due to water levels decreasing to zero; however, SRP

concentrations in the spiked mesocosms at Site 1 appear to be decreasing towards a

minimum value or equilibrium.

The dilute treatment was expected to result in a net flux of phosphorus from the soil

into the overlying water column. Site 1 showed an increasing trend in SRP concentration

in the water column over time. Dilute mesocosms at Site 4 showed increasing SRP

concentrations from Oct 21 through Oct 23 followed by leveling off of the SRP

concentration from Oct 23 through Oct 25. The dissolved phosphorus concentration in

the soil porewater tends to be naturally higher than the phosphorus concentration in the









overlying water column in many wetlands, causing a flux from the soil to the water

column (Reddy and D'Angelo 1994). This could explain some of the increases in the

SRP concentration in the water column in the control mesocosms over time.

Changes in soluble reactive phosphorus concentrations were primarily linear for

most treatments, increasing over time. The graphs in Figs. 3-3 and 3-4 demonstrate the

mean daily SRP concentrations as well as standard deviations for each treatment over

time.

Because changes in concentrations over time are affected by the changing water

level, it is useful to look at water column phosphorus mass over time. An increase in the

mass of phosphorus in the water column within a mesocosm would potentially reflect a

release of phosphorus from the soil. The factors influencing water depth within the

mesocosms include groundwater loss and evapotranspiration. As evapotranspiration

leaves the mesocosm, nutrients such as phosphorus remain in the water column causing

an increase in phosphorus concentration; however, the mass of phosphorus within the

water column would remain the same. If only groundwater loss takes place (no

evapotranspiration), the phosphorus concentration of the water column within the

mesocosm would not change because phosphorus and groundwater would be leaving at

the same rate; however the mass of P would decrease. Looking at the mass of P within

the water column can help determine the dominant process for water loss from the

mesocosms and help identify when uptake/release of phosphorus from the soil takes

place.












Site 1 Native Vegetation Wetland Control Mesocosms
(with Standard Deviations)


10/21/04 10/23/04 10/25/04 10/27/04 10/29/04 10/31/04
Time


10/21/04


4.00

3.00

2.00

1 (W


0.00 !
10/21/04


Site 1 Native Vegetation Wetland Dilute Mesocosms
(with standard deviations)


10/23/04 10/25/04 10/27/04 10/29/04
Time

Site 1 Native Vegetation Wetland Spike Mesocosms
(with standard deviations)


10/31/04


10/23/04 10/25/04 10/27/04 10/29/04 10/31/04
Time


Figure 3-3. Mean SRP and standard deviations over time for Site 1.


0.40

0.35

0.30

,0.25

0.20

0.15

0.10

0.05
0.00


y = 0.0141x 539.72
2
R = 0.8951
--


0.20

-0.15


'0.10

0.05


00n ff


y = 0.015x 573.77
R2 = 0.9964
















2.00

-1.50

'1.00

0.50


0 00


10/21/04


0.80

0.60

0.40

0.20


0.00 -
10/21/04


4.50
4.00
3.50
3.00
22.50
12.00
1.50
1.00
0.50
0.00
10/21


/04


Site 4 Floralta Wetland Control Mesocosms
(with standard deviations)




y = 0.0569x 2177.3
R = 0.8067


10/22/04 10/23/04 10/24/04 10/25/04 10/26/04


Time

Site 4 Floralta Wetland Dilute Mesocosms
(with standard deviations)





-


10/22/04 10/23/04 10/24/04 10/25/04 10/26/04
Time


Site 4 Floralta Wetland Spike Mesocosms
(with standant deviations)


Figure 3-4. Mean SRP and standard deviations over time for Site 4.


y = 0.1344x 5142
R2 = 0.9596


10/22/04 10/23/04 10/24/04 10/25/04
Time


10/26/04


(,"ith standard deviations)










The control treatments at Site 4 showed a linearly decreasing mass of P with

decreasing water depth, as expected (Fig. 3-5). Significant uptake/release was not

expected in the control treatments because it was assumed that the water column and soil

porewater were already at equilibrium. Phosphorus moved out of the mesocosm with

groundwater loss over time and was possibly adsorbed to soil particles. The dilute

treatments at Site 4 showed an initial release of phosphorus due to diffusion of P from a

higher concentration within the soil porewater moving to a lower P concentration within

the water column (Fig. 3-5). After this initial release, groundwater loss was the dominant

factor influencing the mass of P within the mesocosms. The spike treatments at Site 4

demonstrate some release of P from the sediment may have occurred because the mass

did not decrease as expected from 10/22 to 10/23 but rather stayed relatively constant

(Fig. 3-5). As P mass was lost through groundwater, it was initially replaced by P release

from the sediment. This release of P from the sediment in the spike treatment was not

expected, but is supported by soil data indicating low P storage capacity of this improved,

non-native wetland. Phosphorus mass decreased with time due to groundwater loss.


Site 4 Floralta Wetland Control Mesocosms
100 18
16
80 y = -12.491x + 478274 14 "

S2 = 0.9732 12 "
Sy = -2.6162x + 100170 10 g.
2 8
40 R 0663 8
6 *6
20 4
2
0 0
10/21/04 10/22/04 10/23/04 10/24/04 10/25/04 10/26/04
Time
Mass P m Water Depth
Linear (Mass P) Linear (Water Depth)

Figure 3-5. Mass versus water depth over time for Site 4.











Site 4 Floralta Wetland Dilute Mesocosms
18.0
16.0
14.0'
12.0
10.0
8.0
y =-3.0087x + 11519^^^^ ^ 8.0 Q
R2 = 0.8935 6.0
-4.0
2.0
0.0
21/04 10/22/04 10 23 4 10 24 4 1 25 114 10/26/04


Time
+ Mass P m Water Depth Linear (Water Depth)

e tiS 4 Floralta Wetland Spike Mesocosms


21/04


18.0
S t 16.0
14.0
S12. 0-
10.0t
y = -2.6541x + 101619 8.0
8.0
R2 = 0.9538 6.0
6.0 S
4.0
2.0
0.0
10/22/04 10/23/04 1024 04 1025 04 10/26/04


Time

Mass P Water Depth Linear (Water Depth)


Figure 3-5. Continued.

The control treatment at Site 1 shows an initial rapid decrease in P mass followed

by a slightly increasing P mass within the mesocosms (Fig. 3-6). The initial rapid drop

could be due to either P uptake possibly by the soil, algae, or macrophytes or could be the

result of settling following disturbance from installation of the mesocosm. Higher levels

of Fe/Al content of the soil support adsorption on sediment at this site. ET contributed to

some increase in P concentration in the control mesocosms. Convective circulation could


40
,35
g 30
S25
20
1
10
5
0
10/


180
160
E 140
120




S40
20
0
10/







48


have caused mixing of sediments within the water column leading to an increase in P


mass within the mesocosms. The dilute treatments showed a release of P into the water


column at Site 1 (Fig. 3-6). Adsorption of P occurred in the spike treatments at Site 1 due


to diffusion of P from the higher concentration in the water column to lower


concentration in the soil porewater.


7.0
6.0
5.0
4.0
33.0
2.0
1.0
0.0
10/


3.5
3.0

, 2.5
2.0

Q 1.5
1.0

0.5
0.0
10


Site 1 Native Vegetation Wetland Control Mesocosms


y = -1.8389x + 70414
R2 = 0.9036



21/04 10/23/04 10/25/04 10/27/04 10/29/04 10/31
Time

Mass P m Water Depth Linear (Water Depth)


Site 1 Native Vegetation Wetland Dilute Mesocosms






y = -2.0275x + 77636
R2 = 0.9935


/21/04


10/23/04 10/25/04 10/27/04 10/29/04


10/31
10/31


20
18
16
14
12 t
10
8 /
6 I
4
2
0
/04


18
16
14 j
12
10
8
6
4
2
0
/04


Time

-- Mass P m Water Depth -- Linear (Water Depth)

Figure 3-6. Mass versus water depth over time for Site 1.










Site 1 Native Vegetation Wetland Spike Mesocosms
140 18
120 16
14
100 14
1 y = -1.637x + 62685 12
80 10
S80 = 0.9133 0
S608
40
20 2
0 0
10/21/04 10/23/04 10/25/04 10/27/04 10/29/04 10/31/04
Time
Mass P Water Depth Linear (Water Depth)

Figure 3-6. Continued.

3.4 Soil Results

Soil cores were taken within each mesocosm at the end of the experiment at

depths of 0 to 10 cm below the ground surface. The coring device allowed surface water

to be removed as well as coarse litter on the soil surface. The soil results in Table 3-3

were determined from a composite soil sample from each wetland because soil results

were not expected to be significantly different among treatments.

Table 3-3. Soil results (0-10 cm depth) for Site 1 and Site 4, Pelaez & Sons Ranch.
Water Water Soil Bulk Oxalate Extractions
Content Extractable TP Density P Fe Al
Soil Data pH bywt.(%) P (mg/kg) (mg/kg) (g/cm") (mg/kg) (mg/kg) (mg/kg)
Site 1 Wetland (NV) 5.07 78 1.690 644.72 0.258 149.68 4,296 2,772
Site 4 Wetland (IMP) 6.20 24 6.030 37.44 1.401 8.316 36.96 47.04

NV = Native Vegetation Wetland, IMP = Improved Wetland

The improved wetland (Site 4) showed higher concentrations of water extractable P

compared to the native vegetation wetland at Site 1. Water-soluble P has been used to

indicate the potential for P to be released from manure-impacted soils (Nair et al. 1999).

This would indicate that there is a higher potential for P release from Site 4.









Concentrations of water soluble phosphorus and oxalate extractable P have been found to

decrease with depth in the soil profile (Nair et al. 2004). Soil total phosphorus

concentrations were higher at the native vegetation wetland compared to the improved

wetland. Soil total phosphorus concentrations in the A horizon of manure-impacted

spodosols in Nair and Graetz (2002) were in the range of 25 mg P/kg to 2300 mg P/kg.

The study by Nair and Graetz (2002) was conducted on dairy farms; however, total

phosphorus concentrations in the soils presented here fall within that range.

3.5 Vegetation Results

This experiment took place late in the growing season; therefore, vegetation did

not play a significant role in nutrient uptake within the mesocosms. A limited amount of

vegetation was observed inside each mesocom (Table 3-4) due to limited vegetative

growth in desired water depths. Nutrient results were not normalized according to

vegetative biomass within each mesocosm for this reason.

Emergent macrophytes such as Polygonum sp. and Panicum sp. exhibited lower

storage of phosphorus than other macrophytes such as Hydrocotyle sp. in one study by

Reddy et al. 1996.

There was higher vegetative growth in the spike mesocosms at Site 1 compared to

Site 4. Epiphytic algal growth would have contributed to rapid phosphorus uptake within

the mesocosms. The initial rapid SRP uptake in spiked treatment mesocosms at Site 1 is

potentially explained by higher algae growth within the mesocosms due to higher

vegetative volumes.









Table 3-4. Vegetation results for Site 1 and Site 4, Pelaez & Sons Ranch.
Volmeofwgtaticn Beow
(dbow sil/bowwate) Wter/Abo Ab )eW ter
Site 1 VegAtatimType (nL) Soil BHam s (g) mass (g)
Ctoil- 1 Pdygiznh J #dtippeq i s 40 4.899 1.449
Ctoil -2 Pdjygzmunhtdtnpetis 35 4.500 1.253
ratod-3 Pcnactmh~ n toma 8 1.169 0.289
Iihte- 1 PdygiJunth#dppets 50 6.894 2123
Ilkte- 2 PdjygznzmJth d petds 45 5.918 0.454
Ilkte- 3 PdjygiJMn tdppeks 100 14.936 2245
Sike- 1 Dilr#nii-Rttitkin 55 11.589 3.059
Spke-2 Pcnarcmhitc n 40 5.273 0.73
Spike-3 Pcnacnmh~ntomam 50 8.910 32539


VegiatiknTpe
Pdjygmnit#dtrpexiies
PdjygmunJdtppetvixds
PdjygmunJdtppetvixds
PRnamhimtcnrn
PdjygmunJdtppet#iUds
PdjygmunJdtppetvixds
PdjygimnuJndtrpetixs
Pdjygundtppetvicks
MI"'f #1#/1&R#1k7#/1E~s


Vom-e ofwgetatimc
(dboe i/belowwter)
(nL)
25
20
15
30
20
12
5
1
30


Bkow
Wted/Abow
SoilLHaiis (g)
5.839
4078
3.525
6.179
3.347
2563
0.984
0.571
5.464


3.6 Bromide Results

Bromide data were used to estimate the amount of ET occurring within the

mesocosms. According to data collected at the Florida ONA weather station, the

average ET during the time frame of this experiment (Oct 21-29, 2004) was

approximately 0.25 cm/day. ET was calculated using the Penman calculation method.

Data were also collected at Buck Island Ranch in Highlands County, FL in 2003. These

data indicated an ET rate of 0.31 cm/day. An average daily ET rate was calculated for


Site4
CaQtrl-l
Crtai-2
rCati-3
Dlut-e-1
IlDte-2
IlDte-3
Spike- 1
Spike-2
Spike-3


Abne Wter
imrss (g)
0.309
0.164
0.199
0.068
0.528
0.149
NA
NA
0.055









each wetland on Pelaez & Sons beef cattle ranch using bromide tracer data. The average

daily ET obtained for Site 1 was 0.31 cm/day, and the average ET for Site 4 was 0.36

cm/day. Differences in ET rates for the two wetlands were possibly due to vegetative

cover, root-zone water levels, and soil properties (Hunt and Hunt 2001).

Bromide results from all three treatments at Site 4 and the dilute treatment at Site 1

indicated that there was poor mixing of the bromide solution within the water column in

the first sample taken for analysis. Bromide levels were above the desired target level on

the first sampling date and dropped to the target level of approximately 5-6 mg/L by the

second sampling date. From the second sampling date onward, the bromide

concentration, in general, showed an increasing trend due to ET loss (Fig. 3-7).

Increases in SRP concentrations in all three treatments at Site 4 from the second

sampling date until the end of the experiment were potentially explained by ET loss.

Minor uptake/release from the sediment occurred; however, the changes in SRP

concentration were predominantly explained by the bromide results and ET loss at this

site.

The diagram in Figure 3-7 illustrates initial poor mixing of the bromide solution

within the water column followed by increasing bromide concentration due to ET loss.










_11.0 Bromide Concentrations at Site 1 Wetland

10.0

SPoor Mixing of Bromide Solution
9.0
Within water column

8.0
SIncreasing Br Cone. Due to ET Loss
o 7.0

6.0 Mf


Target Bromide Concentration

4.0
10/20/2004 10/22/2004 10/24/2004 10/26/2004 10/28/2004 10/30/2004
Date
--Control *- Dilute -- Spike

Figure 3-7. Illustration of poor mixing and ET effects using bromide data.

Changes in SRP mass over time within the mesocosms were predicted using a

simple water balance approach. The water volume inside the mesocosms decreased

linearly each day as a result of evapotranspiration and groundwater loss. No rainfall

occurred during the time frame of this experiment. Surface flow was restricted by the

mesocosms, and groundwater flow into the mesocosms was not likely, as water levels

were dropping rapidly. The initial water depth was determined from daily water depth

measurements taken in the field. A decreasing, linear relationship was determined for

water depth over time in both wetlands. An average initial water volume inside the

mesocosms was then determined by multiplying the initial water depth by the average

surface area. An average initial SRP concentration was determined for each treatment

from water quality results and was then used to estimate the mass of SRP within the

mesocosms. For calculation purposes, water loss through ET was calculated first,









followed by water loss through groundwater. As ET occurred within the mesocosms,

SRP concentrations increased, and the mass of SRP remained constant. SRP is removed

at the same rate as groundwater; therefore, ET is the only factor affecting the increase in

SRP concentration.

Differences between the predicted SRP mass over time and the measured SRP

mass over time should indicate uptake or release that may be occurring within the system.

Site 1 Control

The bromide concentrations within the control mesocosms increased linearly from

day 1 to day 9 as a result of ET loss. ET rates were determined as the amount of water

that had to be extracted from the mesocosm in order to produce the measured increase in

bromide concentration. Comparing the measured SRP mass to the predicted SRP mass

due to ET and groundwater loss proved useful in determining the actual rates of retention

and release of SRP within the mesocosms.

Figure 3-8 shows that the mass of SRP in the control mesocosms decreased as

predicted due to ET and groundwater losses. SRP concentrations increased linearly with

time, as discussed previously, due to ET loss. The dominant factor influencing the loss of

SRP mass over time was groundwater loss and almost no uptake/release of SRP occurred

within the control treatment mesocosms at Site 1. Minor release of SRP possibly

occurred due to diffusive gradients between the soil porewater and the overlying water

column.











Site 1 Native Wetland Control Treatment
Predicted vs. Measured SRP Mass
8.0

S6.0--

4.0

2.0

0.0
10/20/2004 10/22/2004 10/24/2004 10/26/2004 10/28/2004 10/30/2004
Date

-*- Predicted from ET and G Loss Measured Value

Site 1 Native Wetland Dilute Treatment
Predicted vs Measured SRP Mass
5.0

4.0

3.0 -

2.0 _



0.0
10/20/2004 10/22/2004 10/24/2004 10/26/2004 10/28/2004 10/30/2004
Date
Predicted fromET and G Loss --Measured Value

Figure 3-8. Effects of ET and groundwater loss in control and dilute mesocosms at Site 1.

Site 1 Dilute

Bromide concentrations increased linearly in the dilute mesocosms, similar to the

control mesocosms, as a result of ET loss. The rate of increase in SRP concentrations

was slightly higher for the dilute treatments compared to the control treatments because

of SRP release from the sediment, whereas the control treatments were mainly affected

by ET loss.









The measured SRP masses in the dilute treatment mesocosms at Site 1 were not

predicted by ET and groundwater loss calculations (Fig. 3-8). The mass of SRP

increased from day 1 to day 5 as a result of release of SRP from a source such as the

sediment. The mass of SRP in the water column should have decreased due to

groundwater loss; however, as release of SRP occurred, the mass in the water column

increased. A total average release of 0.084 mg SRP/L occurred for the dilute treatment

mesocosms. This release was expected because the SRP concentration of the water

column was lowered by 50% on day 1 causing a shift in equilibrium between the soil

porewater and the overlying water column. Release slowed or stopped by day 5 and

groundwater loss controlled the loss of SRP mass.

Site 1 Spike

Bromide concentrations in the spike treatment mesocosms at Site 1 increased,

similar to the control and dilute treatment mesocosms. The SRP concentration dropped

rapidly, as discussed previously, and was followed by a slower decrease with time. The

mass of SRP was not predicted by ET and groundwater calculations (Fig. 3-9). The

measured mass of P was lower than the predicted mass, indicating uptake of SRP in the

mesocosms.

The decrease in measured SRP mass in the mesocosm is not believed to be the

result of dilution (leakage) with outside water (which had a lower SRP concentration)

because an increase was seen in the bromide concentration. The bromide concentration

would have decreased as well as the SRP concentration had dilution been the major factor

affecting concentration changes in the mesocosms. Total uptake in the spike mesocosms

averaged 0.735 mg SRP/ L.










Site 1 Native Wetland- Spike Treatment
Predicted vs. Measured SRP Mass
350
300 -
3 250
I 200
E 150
S100

50
10/20/2004 10/22/2004 10/24/2004 10/26/2004 10/28/2004 10/30/2004
Date
--- Predicted from ET and G Loss Measured Value

Figure 3-9. Effects of ET and groundwater loss in spike mesocosms at Site 1.

The desired SRP concentration for the spike mesocosms was 3.0 mg/L. However,

measured concentrations indicated an initial SRP concentration of 4.1 mg/L (See Fig. 3-

3). This is possibly the result of poor mixing of the spike solution within the water

column, which was also evident in the bromide results.

The rate of uptake is higher than rate of release at Site 1. The rate of adsorption is

generally faster than the rate of desorption according to numerous soil phosphorus

models such as the Langmuir-Hinshelwood model (Overman et al. 1999).

Site 4 Control

Bromide concentrations in the control treatment mesocosms increased non-linearly

at Site 4 as a result of ET loss and SRP concentrations increased linearly with time.

Changes in SRP mass were predicted very well by ET and groundwater loss calculations

indicating that no uptake or release of SRP occurred in the control mesocosms. Figure 3-

10 illustrates the effect of ET and groundwater loss on SRP mass in the control

treatments at Site 4.










Site 4 Improved Wetland Control Treatment
Predicted vs. Measured SRP Mass
120
100
8 80
~ 60
4 40
20 -
0
0 ---------------------------
10/20/2004 10/21/2004 10/22/2004 10/23/2004 10/24/2004 10/25/2004 10/26/2004
Date
-*- Predicted from ET and G Loss -- Measured Value

Figure 3-10. Effects of ET and groundwater loss for control mesocosms at Site 4.

A very minor dilution of 0.142 L possibly occurred from 10/21 to 10/22 in the

control mesocosms causing both the bromide concentration and the SRP concentration to

decrease slightly (Table 3-5).

Table 3-5. Illustration of possible leakage underneath mesocosm walls in Site 4 control
mesocosms.
SRP Conc. (mg/L) Bromide Conc. (mg/L) Water Volume (L)
10/21/04 1.868 6.858 49.00
10/22/04 1.849 6.840 46.88
Difference 0.019 0.018 2.12

Site 4 Dilute

Bromide concentrations in the dilute treatment mesocosms at Site 4 increased from

day 2 to day 5 due to ET loss. There was some indication of poor mixing of the bromide

solution within the water column in the dilute treatments as indicated by a dramatic drop

in bromide concentration from 10/21 to 10/22. SRP concentrations increased from day 1

to approximately day 3 and then leveled off as a result of ET loss and SRP release from

the sediment. The measured mass of SRP was slightly above the predicted mass due to










release of SRP from the sediment, as expected in the dilute treatments (Fig. 3-11) due to

diffusive processes.


Site 4 Improved Wetland Dilute Treatment
Predicted vs. Measured SRP Mass
35
30
25
S20
15
9 10
5
0
10/20/2004 1(I 21 211114 1(I 22 21114 1(I 23 21114 10/24/2004 1(I 25 2'1114 10/26/2004
Date
-- Predicted from ET and G Loss -- Measured Value

Figure 3-11. Effects of ET and groundwater loss for dilute mesocosms at Site 4.

SRP release slowed or stopped by day 2 of the experiment and began to follow the

trend predicted by groundwater and ET loss from day 2 to day 5. The soil at Site 4 has a

poor phosphorus retention capacity and the release of SRP from the sediment was

possibly caused by naturally occurring gradients between the soil porewater and the

overlying water column in wetlands.

Site 4 Spike

Bromide concentrations in the spike treatment mesocosms increased non-linearly

from day 1 to day 5 due to ET loss. SRP concentrations increased linearly, as discussed

previously, as a result of ET loss. The increases in SRP concentration in the spiked

mesocosms also resulted from the low phosphorus sorption capacity of the soil in this

wetland. Phosphorus can be released from the sediment at this site even at very low

concentrations. The rate of loss of SRP mass from the spiked mesocosms was predicted










accurately by groundwater and ET loss calculations indicating little to no SRP uptake

(Fig. 3-12), compared to Site 1 spike mesocosms which did show SRP uptake.

Site 4 Improved Wetland Spike Treatment
Predicted vs. Measured SRP Mass
200



S 150 -----------------------



50

10/20/2004 10/21/2004 10/22/2004 10/23/2004 10/24/2004 10/25/2004 10/26/2004
Date
Predicted fromET and G Loss --Measured Value

Figure 3-12. Effects of ET and groundwater loss on spike mesocosms at Site 4.

Slight fluctuations of uptake/release of SRP between the sediment and water

column occurred in these mesocosms as a result of natural processes in which

equilibrium will eventually become established.

Total average release for the spike mesocosms at Site 4 was 0.247 mg SRP/L.

Total average uptake for the spike mesocosms at Site 4 was 0.306 mg SRP/L. The

resulting difference is an uptake of 0.059 mg SRP/L for this improved wetland site.

The desired SRP concentration for the spike mesocosms was 3.2 mg/L. This

concentration was achieved successfully within the spike treatment mesocosms at Site 4.

3.7 Determination of EPCw, Smax, DPSox

A typical graph used to determine phosphorus (P) retention and release for soil

core studies conducted in isolated wetlands is shown in Figure 3-13.

























Water Column P concentration

Figure 3-13. Schematic of graph used to determine phosphorus retention and release for
isolated wetland.

Water column P concentration (mg/L), cumulative P flux (release/retention) = mg

m-2, (Pk) represents initial desorbed P per unit surface area of soils (mg P m-2), slope (Ka)

is the P assimilation or soil buffering capacity coefficient (L m-2), and equilibrium P

concentration (EPCw) is the water column concentration where retention equals release

(mg/L).

An attempt was made to determine EPCw values for the two isolated wetlands on

Pelaez & Sons ranch using this approach. An EPCw value of approximately 1.6 was

determined for the wetland at Site 1, as shown in Fig. 3-14, using only the results from

the spike treatment mesocosms. This is supported by SRP concentrations in the spiked

mesocosms at Site 1 decreasing to a value of around 1.6 mg/L. However, the data do not

indicate a release of phosphorus from the soil at concentrations below the EPCw value,

possibly due to phosphorus being tightly bound by the soil due to high iron and

aluminum content of the soil. Using data from all three treatments gives a much lower










EPCw value (approximately 0.35); however, if the EPCw value were this low, then SRP

concentrations in the spiked mesocosms would have continued to decrease to 0.35 rather

than 1.6 mg/L.


Site 1 Native Vegetation Wetland All Treatments
350EPCw = X Intercept = 1.6 (0.35 all data)
350
300 y= 133.88x 219.31
3 250 R2 = 0.9984
e 200
a y = 64.253x 22.355
150
SR2 = 0.7549
100
S50


-50
4.5 4 3.5 3 2.5 2 1.5 1 0.5 0
Water Column P Concentration

Figure 3-14. EPCw value for Site 1, Pelaez & Sons Ranch.

Data from Site 4 were inconclusive and did not provide useful information for

determining an EPCw value for this wetland, as shown in Fig. 3-15. Possible errors in

the data could have been caused by poor mixing of treatments within the water column

within the mesocosms. The low iron/aluminum content of the soil at this site indicates

that release could occur at very low phosphorus concentrations because there are no

strong binding sites for phosphorus in the soil matrix.










Site 4 Improved Wetland
EPC cannot be determined
20.0

10.0 -

0 .0 -,,,,,,
-10.0

s y = 1.6669x 9.8696
S-20.0 -
1 R2 = 0.0167
-30.0 -

-40.0
4 3.5 3 2.5 2 1.5 1 0.5 0
Water Column P Concentration

Figure 3-15. EPCw graph for Site 4, Pelaez & Sons Ranch.

Reddy et al. (1995) used the following relationship to determine the maximum

sorption capacity of soil in the Lake Okeechobee drainage basin: Smax = 1.74 + 0.172

[Fe + Al], r2=0.78, n=285. Smax was calculated for the two isolated wetlands on Pelaez

& Sons Ranch using this relationship and the Fe/Al soil data collected from the wetlands.

Smax was calculated as 2.15 mmoles P/kg at Site 4 and 32.64 mmoles P/kg at Site 1.

The oxalate extractable Fe/Al bound P was found to be 0.27 and 4.83 mmoles P/kg at Site

4 and Site 1 respectively. This method has been primarily applied to uplands in past

experiments and is usually dependent on agitation (shaking) of a soil sample within a

water column. These relationships were used here for illustrative purposes.

Nair and Graetz (2002) suggested that management recommendations for reducing

P loss through subsurface drainage should consider the degree of phosphorus saturation

(DPS) and water-soluble P. The DPS relates a measure of P already adsorbed by soil to

its P adsorption capacity. It has been indicated as a good measure of a soil's P release

capacity (Nair et al. 2004). DPS values can be used to predict P loss from a soil

irrespective of the depth of the soil within a profile. The following relationship was









described in Nair et al. (2004): DPSox= [(Ox-P)/a(Ox-Fe + Ox-Al)] *100, where alpha is

an empirical factor that compares different soils with respect to P saturation and

concentrations are in mmoles/kg. A value of 0.55 was developed for spodosols in the

Lake Okeechobee drainage basin in Nair and Graetz (2002). This relationship was used

to calculate the DPS for the wetlands in this research.

DPS (Site 1) = [(4.83)/(0.55*(76.92+102.74))] *100 = 4.89%

DPS (Site 4) = [(0.27)/(0.55*(0.66+1.74))]*100 = 20.3%

Low DPS values do not necessarily indicate that a soil is suitable for further P

loading (Nair and Graetz 2002). Consideration of the capacity of a soil to retain P should

be made for management purposes. The sorption capacity of a soil is influenced by soil

properties such as clay content and Al and Fe concentrations (Nair and Graetz 2002). A

change point or value above which there is a rapid increase in water-soluble P and

therefore a likelihood of a negative impact of P in the soil on water quality was identified

in Nair et al. (2004). The change point of DPSox is approximately 20%. This would

mean that the wetland at Site 4 has a higher potential to negatively impact water quality

compared to Site 1. This is also supported by the higher concentrations of water-soluble

P at Site 4 compared to Site 1.

3.8 Langmuir-Hinshelwood Model of Phosphorus

A mathematical model is needed to describe the dynamics of phosphorus uptake in

isolated wetland environments. Water quality results from this in-situ wetland mesocosm

approach indicated a rapid initial uptake of water column P concentration (for nutrient

enriched treatments) followed by a gradual decline at the native vegetation wetland at

Site 1. Similar trends for phosphorus were described in a batch reactor study using the

Langmuir-Hinshelwood Model (Overman and Scholtz 1999). The Langmuir-









Hinshelwood model was used in batch reactor studies to relate soil phosphorus chemistry

to the soil/solution ratio and to initial P in the reactor. Although phosphorus uptake in

wetlands is much more complicated than phosphorus uptake in a controlled batch reactor

study, the trend for phosphorus removal from the water column in-situ could be described

using the Langmuir-Hinshelwood model. The Langmuir-Hinshelwood model for

phosphorus can be described by the following scheme (Overman and Scholtz 1999):

ka kr
P + S -- A F + S
kd

where P = concentration of solution P, mg/L; S = concentration of available sites

for P adsorption, mg/L, A = concentration of adsorbed P, mg/L; F = concentration of

fixed P, mg/L; ka = rate coefficient for adsorption, L mg-1 h-1; kd = rate coefficient for

desorption, h-1; and kr = rate coefficient for reaction, h-1.

This model is separated into two components, the reversible adsorption of P from

solution to the colloidal surface (Langmuir component) and the irreversible reaction of

the surface species (Hinshelwood component). The rate of adsorption of P to soil

particles is dependent on the number of sites available at which adsorption can take place,

the initial concentration of P, and the equilibrium process of adsorption.

Differences between batch reactor studies and the study conducted in this research

include the following:

1. Various environmental factors were allowed to influence the rate of P adsorption and
uptake in the wetland opposed to only soil adsorption occurring in batch reactor
studies

2. Mixing of water column P concentration and soil porewater occurred naturally,
through groundwater loss, diffusion, or convective circulation rather than applied
agitation









Using the Langmuir-Hinshelwood model to describe results from this in-situ

mesocosm approach requires making the following assumptions:

1. Phosphorus uptake is primarily influenced by soil uptake/release in the two wetland
systems addressed in this research rather than other available uptake sites such as
plants, algae, micro invertebrates, etc.

2. Mixing between solution P concentration and the soil porewater occurred within the
mesocosms due to convectional circulation, diffusion or rapid groundwater loss (as
opposed to direct agitation as in the batch reactor study).

The Langmuir-Hinshelwood model adequately describes results from a batch

reactor study because the process of P adsorption is driven by kinetics and complete

mixing of the system; however, in low flow velocities, as seen in wetland environments,

transfer of P from solution to particle surface is more often driven by diffusion. The

interaction between solution P concentration and available sites for adsorption is limited

in wetland environments. Although the Langmuir-Hinshelwood model describes the

kinetics of phosphorus, it fails to identify the mechanisms of soil P chemistry.

Figure 3-16 shows measured SRP values from the in-situ mesocosm approach (Site

1 Spiked Mesocosms) compared to predicted SRP concentrations using the Langmuir-

Hinshelwood model. Initial SRP concentration used in the model was taken from

measured data from Site 1 wetland. The value for Smax was determined to be 1,300

mg/L for Myakka soil under water saturated conditions in Overman and Scholtz (1999).

Values for ka, kd, and kr were determined using a transient analysis and visual

inspection.










Measured vs Predicted SRP
(Langmuir Hinshelwood Model)
5.00

4.00

3.00

S2.00

1.00

0.00
0 24 48 72 96
Time (hrs)
ka=.0004,kd=.55,k1.01 --- Measured SRP

Figure 3-16. Predicted vs. measured SRP conc.using Langmuir-Hinshelwood model.

In the batch reactor study analyzed by Overman and Scholtz (1999), values for ka,

kd, and kr were determined to be 0.05 L mg-1 h-1, 0.25 h-1, and 0.005 h-1 respectively with

an Smax value of 47 mg/L for the Bh horizon of Myakka soil (unsaturated). The rate

coefficient, ka, is lower for the wetlands compared to the batch reactor study because in

the batch reactor study, the soil is completely mixed within a phosphorus solution;

therefore, there is a greater chance that all of the adsorption sites in the soil will come in

contact with phosphorus in the solution. In the wetland soil, only the top layer of the soil

will be in direct contact with the phosphorus in the water column above, and diffusion

must occur before phosphorus can be adsorbed to sorption sites lower in the soil profile.














CHAPTER 4
CONCLUSIONS

The objective of this research was not to identify the individual processes affecting

phosphorus chemistry in wetlands but rather to obtain general information about

uptake/release rates for each wetland system as a whole. The in-situ mesocosm approach

has the potential to provide valuable information for assessing the capability of wetlands

to improve water quality in agricultural settings. This method also shows potential for

improving modeling efforts of wetlands.

The spike and dilute treatments did cause a shift in equilibrium phosphorus

concentrations between the overlying water column and the soil porewater; however,

SRP concentrations did not converge at an equilibrium concentration during the time

frame of this study. Phosphorus uptake occurred as expected in the spike mesocosms at

Site 1, but not at Site 4. Phosphorus release from soil porewater into the overlying water

column occurred at Site 1 as expected, but it was difficult to determine if release occurred

at Site 4 because the data were explained almost entirely by ET effects.

Soluble reactive phosphorus was analyzed in greater detail than other water quality

parameters because phosphorus is the nutrient of concern in the Lake Okeechobee

drainage basin. This parameter is believed to provide the most insight into uptake/release

capabilities of the wetlands on the ranch. Phosphorus is often the primary target element

of nutrient removal systems because of its critical role in limitation of algal growth in

lakes (Elder et al. 1997). Changes in ammonium and nitrate within the mesocosms over









time were not significant. No significant differences in TKN concentrations were

observed between sampling dates.

Isolated wetlands do not receive hydrologic inputs from streams or other direct

supplies; therefore, they rely on rainwater, surface runoff, or groundwater to supply

hydrologic conditions conducive to a wetland environment. The wetlands studied in this

experiment are constantly exposed to highly variable hydrologic conditions. The

wetlands were more often exposed as compared to flooded; however, wetland vegetation

was prominent in the areas, especially at Site 1. Because the experiment had to be

conducted while the wetlands were flooded rather than exposed, the experiment was

limited due to the short flooding duration of the wetlands. The experiment took place in

the middle of a very active 2004 hurricane season; however, water control techniques had

not been implemented on the ranch at the time of the experiment. This research was

conducted in the pre-BMP phase of the overall project, and water control techniques were

not to be implemented until 2005. Flood control practices were implemented near Lake

Okeechobee to prevent severe flood damage to farms in the drainage basin from the

hurricanes. The floodgates near the lake were opened to allow rapid drainage of the

watershed. This, along with no rainfall in the week of the experiment, possibly

contributed to the rapid water level decline in the wetlands during the course of the

experiment, which took place in October 2004.

The mesocosm structure itself did not significantly affect the results of the

experiment. The Kalwall fiberglass material used was effective for the purposes of this

research.









Because this experiment was conducted near the end of the growing season,

vegetation did not contribute significantly to nutrient uptake within the wetlands.

Minimal amounts of vegetation were incorporated inside each mesocosm. This was due

in part to the fact that areas with deep enough water for the experiment did not contain

much vegetation, possibly due to cattle or higher soil elevations around root systems.

Therefore, vegetation data were not used to normalize nutrient concentrations within the

mesocosms.

When considering these isolated wetlands as a means to improve water quality in

the Okeechobee drainage basin, it is important to keep in mind that some studies have

indicated a net release of nutrients from sediments that had been exposed to air and were

subsequently rewetted (Baldwin 1996). This is an important consideration for these

wetlands because they are so often exposed, instead of flooded. After a long period of

exposure, these wetlands have the potential to contribute high phosphorus loads upon

initial rewetting, especially at Site 4 where phosphorus is not held tightly in the soil

matrix.

Results from this study indicate that a lower residence time may be required to

improve water quality leaving the ranch. Treatment in the spike mesocosms at Site 1

occurred within the first 48 hours. Treatment continued after 48 hours but at a much

slower rate.

The two wetlands on Pelaez & Sons beef cattle ranch are quite different. The

wetland at Site 4 has undergone numerous improvement techniques and is less natural

than the wetland at Site 1. Site 4 wetland is drained more often, has a higher pH, is

planted with Floralta limpograss rather than native vegetative cover, and generally









supports more cattle on an annual basis than Site 1 wetland. Differences in initial

ambient conditions could be attributed to these factors. Differences in oxalate extractable

Fe/Al bound P play a significant role on phosphorus adsorption by the soils in each

wetland. Site 1 exhibited a higher phosphorus adsorption capacity compared to Site 4,

and is most likely the result of Fe/Al content of the soils. Site 4 contained coarse, sandy,

white soils compared to darker, mineral soils at Site 1. The higher level of water

extractable P found in the soil at Site 4 compared to Site 1 was likely the result of higher

nutrient loads in runoff from the surrounding pastures.

When taking water quality samples to assess the nutrient removal potential of these

wetlands, it is important to keep in mind the overall results, on an annual basis, rather

than a single measurement.














CHAPTER 5
SUGGESTIONS FOR FUTURE RESEARCH

Installing the mesocosms by hand within the wetlands proved to be an arduous,

time-consuming task. Most of the time was spent cutting through vegetative roots that

would have prevented an adequate seal from forming between the bottom of the

mesocosm wall and the sediment. The mesocosms were constructed of a fairly flexible

Kalwall fiberglass material. Pressure had to be applied gently to the top of the mesocosm

as the roots were cut to avoid buckling of the mesocosm walls. To improve the strength

of the material during installation, a metal collar could have been designed to fit around

the bottom of the mesocosm with a sharpened edge that would aid in cutting through the

roots. Potentially, the collar could be designed so that it could be easily detached and re-

attached between experiments. This would reduce installation time between experiments

if multiple tests were to be performed, reduce disturbance to the wetland, and allow

recovery of the system between experiments once the mesocosm was removed from the

collar.

Another issue involved the amount of time required for taking water samples.

Water samples were taken individually by hand, meaning that only one sample could be

taken from each mesocosm per day. Multiple people would have been required to obtain

more than one sample per day from all of the mesocosms. Setting up an automatic

sampler with multiple sampling lines could have reduced water sampling labor and

allowed more time to collect information such as dissolved oxygen levels, temperature,

and pH. A platform would need to be constructed to house the sampling device, and the









samples could be collected from the sampler at regularly scheduled times. An automatic

sampler would increase the accuracy of the sampling technique and potentially reduce

error. Samples are more easily filtered and acidified within a laboratory environment as

compared to in the field. Walking in the wetland from mesocosm to mesocosm to take

water samples each day caused degradation of the wetland environment around the

mesocosms. This would have had an effect on future experiments conducted in the same

wetland.

In order to avoid water level problems, a minimum water depth of 15 cm should be

maintained during the course of the experiment when possible. Using this minimum

water depth should hopefully prevent sediment control over the water column and

desiccation problems. Installing water level recorders in the wetlands with real-time data

applications would have been useful in planning times to conduct the experiment to avoid

water level issues.

Tracking temperature, dissolved oxygen levels, and pH in the water column

throughout the experiment would have been useful in characterizing the system and

potentially explaining some of the results. Numerous models dealing with phosphorus

sorption require a maximum sorption value, which is often dependent on dissolved

oxygen levels. Also, dissolved oxygen, temperature, and pH have direct effects on

nutrient dynamics within wetlands.
















APPENDIX
TRIAL RUN RESULTS


Table A-i. Trial run results from the Stormwater Ecological Enhancement Project
(SEEP) site, University of Florida campus.
FIRST SAMPLE DATE SECOND SAMPLE DATE THIRD SAMPLE DATE
7/15/2004 7/16/2004 7/18/2004
*Water Depth was 8.25" *Water Depth was 24"
SRP mg/1 SRP mg/1
Ambient AB1 0.0583 Ambient AB11 0.0383

C1 AB2 0.0615 C1 AB12 0.1284
C2 AB3 0.0324 C2 AB13 0.0469 MESOCOSMS FLOODED
C3 AB4 0.0673 C3 AB14 0.0698
NO DATA AVAILABLE
D1 AB5 0.0364 D1 AB15 0.0720
D2 AB6 0.0475 D2 AB16 0.0641
D3 AB7 0.0201 D3 AB17 0.0264

S1 AB8 3.1040 S1 AB18 1.7334
S2 AB9 7.2234 S2 AB19 2.3195
S3 AB10 1.0287 S3 AB20 1.6091
*C = Control, D = 50% diluted with H20, S = Spiked with 100mg/1 P solution.










Table A-2. Water quality results from trial run at Pelaez & Sons Ranch, Okeechobee
County, Florida.
Water TKN NH4 SRP N03
Sample Depth Cone Cone Conc TP Cone
Date Site # Type (m) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
09/18/04 1 Ambient 0.28 3.910 0.144 0.143 0.304 0.017
09/19/04 1 Ambient 0.21 6.254 0.160 0.124 0.492 0.017
09/18/04 1 BS1T1 0.28 4.730 0.299 0.421 0.534 0.115
09/18/04 1 S1T1 0.28 5.726 0.216 3.803 4.142 3.901
09/19/04 1 S1T2 0.21 4.847 0.420 3.256 3.387 1.646
09/19/04 1 S1T3 0.21 4.965 0.339 3.196 3.389 1.537
09/19/04 1 S1T4 0.21 4.378 0.153 2.951 3.304 1.265
09/18/04 4 Ambient 0.27 5.902 0.186 1.594 1.907 0.017
09/19/04 4 Ambient 0.22 5.551 0.237 1.611 1.745 0.072
09/18/04 4 C4T1 0.25 5.316 0.161 1.656 1.921 0.028
09/19/04 4 C4T2 0.20 5.726 0.137 1.668 1.872 0.017
09/19/04 4 C4T3 0.20 5.316 0.092 1.617 1.930 0.017
09/19/04 4 C4T4 0.20 5.316 0.121 1.668 1.918 0.012
09/18/04 4 BS4T1 0.28 5.668 0.191 1.820 1.867 0.213
09/18/04 4 S4T1 0.28 6.195 0.108 3.679 4.090 2.399
09/19/04 4 S4T2 0.26 6.019 0.256 4.211 4.480 2.454
09/19/04 4 S4T3 0.26 5.844 0.289 4.339 4.498 2.535
09/19/04 4 S4T4 0.26 5.785 0.205 4.354 4.523 2.535

*BS=before spike, S=Spike, C=Control, T=time
*No replicates for Trial Run Experiment

Site 1 and Site 4 Water Depths
30.0

27.0

S24.0

21.0

18.0
09/17/04 09/18/04 09/19/04 09/20/04
Date
-- Site 1 -A- Site 4 Linear (Site 1) Linear (Site 4)

Figure A-1. Water level changes in Site 1 and Site 4 during trial run















S3.0


S2.0


o .
0-
U 1.0

VI


Site 1 Trial Run Experiment








_________ ______________________


Date

S Spike


A- Before Spike


-- Ambient


Figure A-2. Trial run, Site 1, soluble reactive phosphorus cone. vs. time.


Site 4 Trial Run Experiment
5.0

.0 4.0






S 1.0

0.0
0 1 2 3 4 5

Time

-- Ambient Spike -A- Before Spike --- Control

Figure A-3. Trial run, Site 4, soluble reactive phosphorus conc. vs. time.















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BIOGRAPHICAL SKETCH

Christy L. Sackfield was born in Reidsville, North Carolina, in 1981. After

graduating high school in 1999, she moved to Raleigh, NC, to attend North Carolina

State University. She graduated with a degree in biological and agricultural engineering

in May 2003. After graduation she entered the master's program in water resources with

the Agricultural and Biological Engineering department in August 2003 to work on water

quality in the Lake Okeechobee drainage basin.