Institute of Food and Agricultural Sciences (IFAS) Soil and Water Science Department Baseline Soil Characterization of the Taylor Creek Pilot Stormwater Treatment Area (STA) in the Lake Okeechobee Watershed Final Report Submitted to: South Florida Water Management District 3301 Gun Club Road P.O. Box 24680 West Palm Beach, Florida 33416-4680 By: K. R. Reddy, S. Grunwald, V. D. Nair, and Y. Wang Wetland Biogeochemistry Laboratory Soil and Water Science Department - IFAS University of Florida Gainesville, FL 32611-0510 Table of Contents Table of Contents…………………………………………………… 2 List of Figures ……………………………………………………….. 3 List of Tables ………………………………………………………… 5 Executive Summary………………………………………………….. 7 1. Introduction and Background……………………………………… 9 1.1 1.2 Site description ……………………………………………. Project objectives …………………………………………. 2. Spatial Distribution of Phosphorus in Surface Soils……………… 2.1 2.2 11 11 13 Soil sample and analysis ………………………………… Results and discussion ……………………………………. 13 19 3. Fractionation of Soil Phosphorus ………………………………… 50 3.1 3.2 Materials and methods …………………………………… Results and discussion …………………………………… 50 53 4. Phosphorus Retention Properties of Soils………………………… 64 4.1 4.2 Materials and methods …………………………………… Results and discussion …………………………………… 64 66 5. References ……………………………………………………….. 73 6. Appendix …………… 75 2 List of Figures Figure 1. Map showing landuse within Kissimmee and Taylor Creek hydrologic units of the Okeechobee Drainage Basin Figure 2. Taylor Creek Pilot STA located in north of Okeechobee, Florida. This two-celled STA has a wetted treatment area of 169 acres. Figure 3a. Sampling locations used to determine spatial distribution of soil properties Figure 3b. Sampling locations in north and south sections of the wetland, used to determine spatial distribution of soil properties. Figure 4. Sampling locations of triplicate cores selected for phosphorus fractionation and retention studies. At each location, soils were sampled at the 0-10 cm and 10-30 cm depths. Figure 5. Spatial distribution of total phosphorus of soils collected from Taylor Creek STA Figure 6. Spatial distribution of total inorganic phosphorus of soils collected from Taylor Creek STA. Figure 7. Spatial distribution of bulk density of soils collected from Taylor Creek STA. Figure 8. Spatial distribution of pH of soils collected from Taylor Creek STA. Figure 9. Spatial distribution of loss of ignition of soils collected from Taylor Creek STA. Figure 10. Spatial distribution of total nitrogen of soils collected from Taylor Creek STA. Figure 11. Spatial distribution of total carbon of soils collected from Taylor Creek STA. Figure 12. Spatial distribution of water extractable phosphorus of soils collected from Taylor Creek STA. Figure 13. Spatial distribution of bioavailable phosphorus of soils collected from Taylor Creek STA. Figure 14. Spatial distribution of maximum phosphorus retention capacity of soils collected from Taylor Creek STA, as estimated by the single point isotherm method. Figure 15. Spatial distribution of 1M HCl-extractable calcium of soils collected from Taylor Creek STA. Figure 16. Spatial distribution of 1M HCl-extractable magnesium of soils collected from Taylor Creek STA. 3 Figure 17. Spatial distribution of 1M HCl-extractable iron of soils collected from Taylor Creek STA. Figure 18. Spatial distribution of 1M HCl-extractable aluminum of soils collected from Taylor Creek STA. Figure 19. Phosphorus storage in soils collected from Taylor Creek STA. Stable pools (nonreactive P) was estimated by the difference between total soil phosphorus and inorganic phosphorus extracted using 1 M HCl (Reddy et al., 1998b). Figure 20. Sampling locations used to determine soil phosphorus forms and retention capacities. Stations 20 and 37 were sampled in triplicate to determine the field variability within a sampling location. Figure 21. Soil phosphorus fractionation scheme used to determine labile and stable pools of phosphorus (Reddy et al., 1998b). Figure 22. Total P, inorganic P (measured using single extraction with 1 M HCl), and nonreactive P (not extracted with 1 M HCl) to include organic P and non-reactive inorganic P in soils across the transect at Taylor Creek STA. Figure 23. Distribution of labile P (KCl Pi), Fe/Al-P (NaOH Pi), and Ca/Mg Pi (HCl Pi) fractions in soils collected along a transect in Taylor Creek STA. Figure 24. Distribution of alkali extractable organic P, residual stable P, and total P of soils collected along a transect in Taylor Creek STA. Figure 25. A summary of labile and non-labile pools of phosphorus in soils collected along a transect in Taylor Creek STA. Figure 26. Relationship between Langmuir Smax and P sorbed at 100 mg P L-1 under (a) aerobic and (b) anaerobic conditions. Figure 27. Relationship between Langmuir Smax under aerobic and anaerobic conditions. 4 List of Tables Table. 1. Site identification numbers (ID) of sampling locations with geographic coordinates. Table 2b: Statistical properties of 0-10 cm soils (averaged replicates) [n: 52] Table 2b: Statistical properties of 10-30 cm soils (averaged replicates) [n: 52] Table 3. Range of 1 M HCl extractable metals in soils collected from Taylor Creek STA. Table 4: Cross-validation results interpolations and spline parameters for 0-10 cm depth. Table 5: Cross-validation results interpolations and spline parameters for 10-30 cm depth. Table 6. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Table 7. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Table 8. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Table 9. Correlation matrix for soil variables measured at 0-10 cm and 10 – 30 cm depths. Pearson correlation coefficients are significant at 0.05 level (>0.159) and 0.01 level (>0.208). n =141. BD = Bulk density; LOI = Loss on ignition; TN = Total nitrogen; TC = Total carbon; TPi = Total inorganic P; WEP = Water extractable P; M I-P = Mehlich I –extractable P; SPI = Single point isotherm. Table 10. Storage of labile and non-labile pools of phosphorus in Taylor Creek STA soils. Table 11. Labile and non-labile pools of phosphorus expressed as percent of total phosphorus stored in soils. Table 12. Variability in selected soil properties measured on replicate soil cores from two stations along a transect in Taylor Creek STA. Three cores were taken from each station. Table 13. Total inorganic P recovered during repeated extractions with 1 M HCl. Table 14a. Labile and non-labile pools of phosphorus in soils (0-10 cm depth) collected along a transect in Taylor Creek STA. Table 14b. Labile and non-labile pools of phosphorus in soils (10-30 cm depth) collected along a transect in Taylor Creek STA. 5 Table 15. Variability in soil phosphorus forms measured on replicate soil cores from two stations along a transect in Taylor Creek STA. Three cores were taken from each station. Table 16. Relationship between soil phosphorus forms and total phosphorus in soils collected along a transect in Taylor Creek STA. *Total inorganic P represents sum of inorganic P extracted by alkali and acid. **Pi- [Me-TC] represents inorganic P complexed with metal and organic matter Table 17. Langmuir sorption parameters (P originally sorbed on the solid phase, So; equilibrium P concentrations, EPC; the P retention maximum, Smax and the P bonding energy constant, k) for the Taylor Creek STA soils at the nine selected locations under aerobic conditions. Table 18. Langmuir sorption parameters (P originally sorbed on the solid phase, So; equilibrium P concentrations, EPC; the P retention maximum, Smax and the P bonding energy constant, k) for the Taylor Creek STA soils at the nine selected locations under anaerobic conditions. Table 19. Correlation coefficients of aerobic P sorption parameters† with soil characteristics and P fractionation data. Table 20. Correlation coefficients of anaerobic P sorption parameters† with soil characteristics and P fractionation data. Table 21: Correlation coefficients of Langmuir parameters† under aerobic and anaerobic conditions. 6 Executive Summary Natural and constructed wetlands are used to treat nutrient enriched waters such as agricultural drainage effluents, municipal, urban, and industrial waste waters. Constructed wetlands used as buffers to retain nutrients and other contaminants are usually managed to improve their overall performance, and to maintain expected water quality. The construction and operation of Stormwater Treatment Areas (STAs) in the Lake Okeechobee Watershed (LOW) is a major component of the Lake Okeechobee Protection Plan (LOPP). Required as part of Sec. 373.4595 (F.S.), the plan seeks to restore and protect Lake Okeechobee by achieving and maintaining compliance with water quality standards in the lake and its tributaries, through an innovative restoration program designed to reduce total phosphorus (TP) loads and implement long-term solutions, in accordance to the lake’s Total Maximum Daily Load (TMDL). The Taylor Creek and Nubbin Slough STAs are the first two pilot-scale STAs being implemented north of the lake. Construction of the STAs was completed in July 2005 for Taylor Creek, and October 2005 for Nubbin Slough. These prototype treatment wetlands will be important for demonstrating effectiveness of the STA technology in the LOW area. The overall objective of this work is to document the existing soil and vegetative conditions in the Taylor Creek Pilot STA following construction but prior to operation. This work effort will allow evaluation of changes in the physical, chemical, and biological functions of the STA over time. This project has two main components. (1) collection and characterization of surface and subsurface soils for various physical and chemical properties; and (2) characterization of the existing vegetation and monitoring in the STA. This report focuses on soil characterization. Specific objective of this portion of the study are to: 1. determine the spatial distribution of soil physico-chemical properties of soils. 2. identify relative partitioning of labile and non-labile pools of P in soils 3. determine the P retention capacity of soils. The first objective was to determine the spatial distribution of soil physico-chemical properties of soils. Spatial distribution of various soil properties showed high degree of variability. Total P in the topsoil was dominant in the southern portion of the STA, whereas only few TP hotspots remained with values > 500 mg kg-1 in 10-30 cm depth. High and low TP values in top and subsoil were found in close proximity to each other. This high variability within the STA in TP was confirmed by large ranges of 955 mg kg-1 (0-10 cm) and 873 mg kg-1 (0-30 cm), respectively, and high standard deviations. Total inorganic P (TPi) hotspots in the topsoil coincided with TP hotspot areas in the southern portion of the STA. Spatial distribution of TPi was similar to the spatial distribution of HCl-extractable Al. Total P storage ranged from 4.3 to 44.7 g m-2 (mean value = 21.1 g m-2) in 0-10 cm soils and 3.1 to 90.3 g m-2 (mean value = 38.4 g m-2) in 10-30 cm soils. Water extractable P, Mehlich 1 extractable P and TPi, respectively, accounted for 0.18%, 4.2%, and 13% of the total P. A large proportion of P was stored in organic P pool and as stable inorganic P. The maximum P retention capacity of the soils was estimated using single point isotherms. This estimate suggests that the soils are capable of adsorbing a maximum of 72 g P m-2. If one 7 assumes that the STA is loaded at a rate of 2 to 5 g P m-2 year-1, these soils potentially function as sorption sinks for 14 to 36 years. Long term P retention in Taylor Creek STA depends not only on soil P sorption capacity, but accretion of organic matter. The second objective of the study was to identify relative partitioning of labile and non-labile pools of P in soils. Labile Pi (as determined by Mehlich-1 extraction) accounted for 0.5% of the total P. Total inorganic P accounted for <12% of the total P. A large proportion of soil phosphorus is present in two major pools: alkali extractable organic P; and residual P stable under both alkali and acid solutions. Approximately 40% of the total P is in stable pool, while another 45% is present in organic P pool. Stability of these two pools under varying hydrologic conditions needs further investigation. The third objective of the study was to determine the P retention capacity soils. The Taylor Creek STA soils exhibited P retention capacity within the top 30 cm. Significant correlation was observed between P retention capacity and extractable Al and Ca. The P retention capacity of the soils will not be adversely impacted during flooding of the soils as indicated by minimal changes in Smax values under aerobic and anaerobic conditions. Soils play a critical role during the initial establishment of STA. Once the STA starts accreting organic matter and other particulate matter, the newly accreted material dictates the exchange of P between soil and the water column. Soils of Taylor Creek STA have relatively high P retention capacities. However, the P retention capacities are highly spatially variable. In certain portions of STA where Al is high, P retention capacity is also high. Additional studies are needed to determine the stability of P stored in these soils and determine how P retention capacities change with period of operation of the STA. 8 1.0 Introduction Natural and constructed wetlands are used to treat nutrient enriched waters such as agricultural drainage effluents, municipal, urban, and industrial waste waters. Constructed wetlands used as buffers to retain nutrients and other contaminants are usually managed to improve their overall performance, and to maintain expected water quality. The extent of management required depends upon the nutrient/contaminant retention capacity of the wetlands and the desired effluent quality. Management scenarios can vary, depending on wetland type and hydraulic loading rate. For example, small-scale wetlands can be managed effectively by altering hydraulic loading rates or integrating them with a conventional treatment system, while large-scale systems can be managed by controlling nutrient/contaminant loads. Several biogeochemical processes regulate the retention of nutrients by wetlands. Some of these processes include: accretion of particulate matter, uptake by vegetation, and chemical and microbiological processes. Phosphorus (P) retention by soils and sediments, which store most of the P relative to other ecosystem parts components include surface adsorption on minerals, precipitation, microbial and immobilization. In treatment wetlands, such as the Stormwater Treatment Areas (STAs) these processes may be combined into two distinct P retention pathways: sorption and burial. Phosphorus sorption in sediments is defined as the removal of phosphate from the soil solution to the solid phase, and includes both adsorption and precipitation reactions. When plants and microbes die off, the P contained in cellular tissue may either recycle within the wetland, or may be buried with refractory organic compounds. The South Florida Water Management District (SFWMD) is using constructed wetlands commonly known as STAs to abate P pollution. The STAs are now considered as key to restoration of the Everglades. The construction and operation of STAs in the Lake Okeechobee Watershed (LOW) is a major component of the Lake Okeechobee Protection Plan (LOPP). Required as part of Sec. 373.4595 (F.S.), the plan seeks to restore and protect Lake Okeechobee by achieving and maintaining compliance with water quality standards in the lake and its tributaries, through an innovative restoration program designed to reduce total phosphorus (TP) loads and implement long-term solutions, in accordance to the lake’s Total Maximum Daily Load (TMDL). 9 Figure 1. Map showing landuse within Kissimmee and Taylor Creek hydrologic units of the Okeechobee Drainage Basin The Taylor Creek and Nubbin Slough STAs are the first two pilot-scale STAs being implemented north of the lake. These prototype treatment wetlands will be important for demonstrating effectiveness of the STA technology in the LOW area. Research and monitoring data from these STAs will provide scientific basis for making management decisions to improve design and operational guidance as additional STAs are planned in the watershed. The design of the pilot STAs was based on TP removal performance data collected on the STAs south of the lake in the Everglades Agricultural Area. Using the Everglades STA design model, the average TP removal for Taylor Creek and Nubbin Slough STAs was estimated at 2.08 and 5.14 metric tons/year, respectively (Stanley Consultants Inc., 2000). There is some concern that the Okeechobee STAs may perform differently from the Everglades STAs because of inherent differences in water chemistry, soil and vegetation types, and expectations of effluent TP concentrations. For this reason, research and management efforts and supplemental monitoring beyond the normal permit monitoring requirements are being planned for these two pilot STAs to optimize their performance. The primary goal of this project is to maximize effective removal of TP in the STAs and minimize operational costs per pound of TP removed. The Research and Management Plan developed in 2004 identified and prioritized thirteen supplemental research and monitoring needs to address this goal (WSI, 2004). 10 The baseline characterization of the pilot STAs following construction but prior to operation is the first project to be implemented under this plan. The current study documents soil and vegetative conditions in the Taylor Creek Pilot STA. 1.1 Site description The Taylor Creek Pilot STA is located about 1.4 miles north of the city of Okeechobee in central Okeechobee County. It is bordered on the east by U.S. 441 and by Taylor Creek on the west. The site is approximately 200 acres in total area and the STA has a treatment area of about 169 acres (Figure 1). The Taylor Creek Pilot STA is divided into two cells in series and is expected to treat about 10% of the water flow rerouted from Taylor Creek. This would be accomplished by allowing water to flow parallel to the creek for about 1.6 miles, before discharging back to Taylor Creek, just upstream of US 441. The goal for water quality improvement is to reduce TP loads to the maximum extent possible, given the limited area of the STA relative to the amount of water in Taylor Creek. The Taylor Creek Pilot STA is expected to have a long-term average TP removal rate of about 2.08 metric tons of TP per year. 1.2 Project objectives The overall objective of this work is to document the existing soil and vegetative conditions in the Taylor Creek Pilot STA following construction but prior to operation. This research effort will allow evaluation of changes in the physical, chemical, and biological functions of the STA over time. This project has two main components. These include: (1) collection and characterization of surface and subsurface soils for various physical and chemical properties; and (2) characterization of the existing vegetation and monitoring in the STA. This report presents the results of baseline characterization of surface and subsurface soils including: (1) spatial distribution of soil phosphorus; (2) determination of labile and stable pools of soil phosphorus; and (3) determination of phosphorus retention capacity. 11 Figure 2. Taylor Creek Pilot STA located in north of Okeechobee, Florida. This twocelled STA has a wetted treatment area of 169 acres. 12 2.0 Spatial Distribution of Phosphorus in Soils The purpose of this task was to determine the spatial distribution of select physico-chemical properties of soils in the STA. 2.1 Soil sampling and analysis Soils are the dominant storage of TP in the STAs. In order to understand how this TP storage changes through time, it is important to establish the baseline conditions for P in the STAs. This task documents how the existing storage of TP in the Taylor Creek STA is partitioned into the various inorganic and organic P forms. Soil samples within the STA footprint were collected using grid sampling prior to system startup and operation (Figure 3). This sampling technique allows for collection of equally spaced samples throughout the field and approximation of true spatial variability of a number of soil nutrient levels. In grid sampling, the field is divided with a grid using a field computer and GPS, with a sample taken from the center of each grid section. A sampling density of one sample per four acres was used. Soil samples were taken from 42 locations within the 169-acre treatment area of the Taylor Creek STA at depth increments of 0-10 and 10-30 cm. Triplicate soil cores were obtained at 9 stations (sampling stations # 9, 14, 17, 20, 34, 37, 42, 46, and 49, see Figure 4) to determine the variability at the sampling station. Ten additional stations were added at random to increase the spatial resolution. Core collection and handling followed the procedures outlined in the FDEP SOPs (DEP-SOP-001/01, Revision Date: February 1, 2004). Soil samples were transported to the UF-Wetland Biogeochemistry Laboratory and stored in a refrigerator at 4 oC until analysis. Subsamples were air-dried for processing and analysis 13 Figure 3a. Sampling locations used to determine spatial distribution of soil properties. 14 Figure 3b. Sampling locations in north and south sections of the wetland, used to determine spatial distribution of soil properties. Northern section Southern section 15 Table. 1. Site identification numbers (ID) of sampling locations with geographic coordinates. Site ID 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 Longitude -80.83678 -80.83607 -80.83538 -80.83471 -80.83641 -80.83570 -80.83499 -80.83429 -80.83600 -80.83526 -80.83453 -80.83383 -80.83557 -80.83480 -80.83406 -80.83341 -80.83510 -80.83432 -80.83357 -80.83290 -80.83589 -80.83629 -80.83540 -80.83529 -80.83585 -80.83278 -80.83150 -80.83235 -80.83102 -80.83188 -80.83052 -80.83136 -80.82999 -80.83081 -80.82946 -80.83023 -80.82891 -80.82898 -80.82876 -80.82784 -80.82877 Latitude 27.31282 27.31298 27.31312 27.31329 27.31192 27.31209 27.31226 27.31245 27.31106 27.31125 27.31141 27.31160 27.31017 27.31036 27.31056 27.31074 27.30929 27.30945 27.30967 27.30987 27.31348 27.31281 27.31272 27.31328 27.31247 27.30677 27.30733 27.30581 27.30637 27.30487 27.30541 27.30393 27.30446 27.30297 27.30352 27.30206 27.30259 27.30064 27.30432 27.30361 27.29936 Site ID 41 42 43 44 45 46 47 48 49 50 51 16 Longitude -80.82922 -80.83185 -80.83188 -80.83198 -80.83145 -80.83566 -80.82758 -80.83219 -80.83086 -80.83646 -80.83474 Latitude 27.30177 27.30655 27.30701 27.30562 27.30612 27.31271 27.30458 27.30655 27.30465 27.31239 27.31264 Soil samples were analyzed for pH, loss on ignition (LOI), bulk density, moisture content, and extractable Fe, Al, Ca, and Mg, and total nitrogen. All samples were analyzed according to the Wetland Biogeochemistry Laboratory (WBL) Standard Operational Procedure (SOP). The WBL has NELAP certification E72949 by the Department of Health, Bureau of Laboratories. All metals were analyzed by the UF-IFAS Analytical Research Laboratory, which is also NELAPcertified (E72850). Figure 4. Sampling locations of triplicate cores selected for phosphorus fractionation and retention studies. At each location, soils were sampled at the 0-10 cm and 10-30 cm depths. Page 17 Soil pH: Soil pH was determined using soil:water ratio of 1:1 and glass electrode. Bulk density (BD): A subsample of wet soil was dried at 70oC to determine dry weight and moisture content. The bulk density was determined by calculating the dry weight of the sample and dividing it by the volume of the corer. Loss on ignition (LOI): Loss on ignition was determined by ignition a known amount of (ovendried soil) at 550oC. Loss in weight after ignition corresponds to organic matter content of the soil. Results are expressed on percentage of over-dried basis. Total carbon and nitrogen (TC and TN): Total carbon and nitrogen were determined on dried, ground samples using Flash EA 1112 Elemental Analyzer (CE Instruments, Saddlebrook, NJ). Results are expressed on a over-dried basis. Total phosphorus (TP): Total P represents the amount of organic and inorganic P in soil samples. Total phosphorus was determined by a combination of ignition at 550˚C and acid digestion to dissolution convert organic P into inorganic P, followed by analysis for inorganic P in digests by ascorbic acid techniques using an autoanalyzer (USEPA, 1993; Method 365.1). HCl extractable inorganic phosphorus (HCl-TPi): Total inorganic P in soil was extracted with 1 M HCl (soil to solution ratio = 1:50; 3 hours extraction time). Filtered solutions (0.45 μm filter) are analyzed for P using an autoanalyzer (USEPA, 1993; Method 365.1). Water extractable phosphorus (WEP): Water-soluble P concentrations provide an estimate of the amount of P that is subject to vertical and/or lateral flow within the soil profile. Water extractable phosphorus in soil was extracted with deionized water using soil to water ratio of 1:10). Filtered solutions (0.45 μm filter) were analyzed for P using an autoanalyzer (USEPA, 1993; Method 365.1). . Mehlich 1 extractable phosphorus (Mehlich 1-P): Mehlich 1-P provides an estimate of bioavailable P in the soils (Kuo, 1996). Mehlich I extractable P was extracted with double acid mixture ( 0.05 N HCl + 0.025 N H2SO4) using soil to solution ratio of 1:10. Filtered solutions (0.45 μm filter) were analyzed for P using an autoanalyzer (USEPA, 1993; Method 365.1). Single point phosphorus retention isotherm (SPI): Single point isotherms are used to determine the maximum P retention capacity of soils. This procedure involves equilibrating a known amount of air-dried soil with 0.01 M KCl solution spiked with 100 mg P/L at a 1:20 soil to solution ratio on a mechanical shaker for 24 h at room temperature. The amount of P lost from solution after 24h equilibration was used to determine the maximum P retention capacity of soils. HCl-extractable metals: Extractable metals (Ca, Mg, Fe, and Al) in soils were extracted with 1 M HCl (soil to solution ratio = 1:50; 3 hours extraction time). Filtered solutions were analyzed for metals using inductively coupled argon plasma spectrometry (ICAP) (USEPA, 1993; Method 200.7). krr Page18 6/26/2007 Phosphorus storage in the soil: The mass of total phosphorus in the top 30 cm of the STA soils was calculated using TP concentrations, bulk density, and soil depth. The mass of P that is subject to leaching (water-soluble) and biovailable (Mehlich 1-P) was also calculated. The amount of phosphorus stored was expressed on a mass per unit area basis. Geostatistical analysis: Contour maps depicting spatial variability of the measured parameters within the STA footprint were constructed. We used completely regularized splines to interpolate variables within the STA. Splines are a suite of interpolation methods that predict values using a mathematical function that minimizes overall surface curvature, resulting in a smooth surface that passes exactly through the input points (Burrough and McDonnell, 1998). Splines are piecewise (local) fitting functions (ArcGIS, Environmental Systems Research Institute - ESRI, Redlands, CA). We also explored the option of semivariogram analysis and kriging (weighted interpolations) (Webster and Oliver, 2001). This type of geostatistics assumes that observations measured close to each other are more similar than the observations taken further apart. This can be captured using semivariograms, which have the ability to characterize the spatial autocorrelation structure of a measured property. However, almost all variables showed an erratic spatial structure (fitted model in the semivariogram) or poor nugget effect indicating that not enough samples were collected to derive robust semivariograms. This is consistent with recommendations given in the geostatistical literature. Chilès and Delfiner (1999) recommend to use > 50 and Webster and Oliver (2001) > 100 (better > 144) observations, respectively. Thus, we used splines to interpolate measured variables. The spline parameters, mean error (ME) and root mean square error (RMSE) derived using cross-validation are listed in Table 4. The number of points identifies the number of observations used in the calculation of each interpolated cell. The more input points, the more each cell is influenced by distant points and the smoother the output surface. The spline parameters were optimized using a heuristic approach with the goal to minimize ME and RMSE. Accurate predictions show a small ME and RMSE. 2.2 Results and discussion Spatial distribution of various soil properties are presented in Figures 5 -18 and Tables 1-3. Interpolated maps on the following pages show the spatial distribution patterns of variables. Total P in the topsoil was high in the southern portion of the STA, whereas only few TP hotspots with values > 500 mg kg-1 were identified in the 10-30 cm depth. High and low TP values in top and subsoil were found in close proximity to each other. This high variability within the STA in TP was confirmed by large ranges of 955 mg kg-1 (0-10 cm) and 873 mg kg-1 (10-30 cm), respectively, and high standard deviations. Inorganic P (HCl-extractable P) hotspots in the topsoil coincided with TP hotspot areas in the southern portion of the STA. As expected bulk densities were higher in the subsoil with means and (maximum) of 0.9 (1.54) g cm-3 in 0-10 cm and 1.27 (1.79) g cm-3 in 10-30 cm depth. Interesting to note is that areas high in topsoil TP showed inverse spatial patterns on the bulk density maps with low values of < 0.4 g cm-3 characteristic of wetland soils. This has implications for phosphorus storage assessment across the STA. The pH spatial patterns showed heterogeneous spatial patterns in top and subsoil with means of 6.3 (0-10 cm) and 6.5 (10-30 cm). Total N showed homogeneous patterns in the top and subsoil which was also found in other wetland studies (Bruland et al., 2006; Corstanje et al., krr Page19 6/26/2007 2006). Only few hotspots in topsoil TN were found in the northern part and most southern tip of the STA with maximum of 26.2 g kg-1 (0-10 cm). Those few TN hotspot areas became insignificant in the subsoil with maximum TN of 16.6 g kg-1. The LOI and total C maps showed the same spatial patterns which was confirmatory. Although TC showed a wide range of values from 3.8 to 406.5 g kg-1 (0-10 cm) and 1.9 to 209.3 g kg-1 (10-30 cm) the map was relatively homogeneous with highest values in the southern section. The most contrasting spatial patterns between top and subsoil were found for water extractable inorganic P and Mehlich P. The spatial patterns of Ca, Mg, Fe and Al-bound phosphorus showed similar patterns for HCl-extractable Ca and Mg in top and subsoil. Spatial patterns of Ca and Mg-bound P diverged from those of Fe and Al-bound P. In particular, HCl-extractable Al showed the same spatial patterns as TP within the STA. Soils of STA exhibited a wide range of Ca, Mg, Fe, and Al concentrations (Table 3). Calcium concentrations ranged from 720 to 23,219 mg kg-1 (mean value = 6,064 mg kg-1) in 0-10 cm soils and 123 to 17,873 mg kg-1 (mean value = 4,520 mg kg-1 ) in 10-30 cm soils. High Ca levels were associated with the accumulation of organic matter. South end of STA showed highest Ca levels. Similar trends were observed for Mg and Fe. Extractable Al concentrations ranged from 141 to 5,926 mg kg-1 (mean value = 1,389 mg kg-1) in 0-10 cm soils, and 65 to 8,350 mg kg-1 (mean value = 1,825 mg kg-1) in 10-30 cm soils. High Al levels were associated with the accumulation of organic matter. Maximum P retention capacity of soils was estimated using single point isotherm (Tables 2a and 2b). The maximum P retention capacity values ranged from 21 to 804 mg kg-1 (mean value = 167 mg kg-1) in 0-10 cm soils and 17 to 1,358 mg kg-1 (mean value = 211 mg kg-1) in 10-30 cm soils. Phosphorus retention capacity was significantly correlated with HCl-extractable Al, Fe, Mg, and Ca (Table 9). Approximately, 77% of the variability in SPI was explained by HCl extractable Al. SPI = HCl-Al 0.143 + 41.4 n = 140; R2 = 0.769 Where: SPI represents maximum P retention capacity using single point isotherm. krr Page20 6/26/2007 Table 2a: Statistical properties of 0-10 cm soils (averaged replicates) [n: 52] BD pH -3 LOI TN TC -1 TP -1 HCl-TPi -1 -1 M1-P g cm - % g kg g kg mg kg mg kg mg kg mg kg mg kg-1 Mean 0.90 6.33 16.1 5.84 69.3 311.4 39.0 0.94 13.6 168.6 SE of mean 0.47 0.09 2.07 0.67 10.2 32.8 5.3 0.16 1.5 20.6 Median 0.89 6.24 13.8 5.30 56.2 284.2 31.3 0.42 10.8 123.0 Mode 2.20a 6.52a 14.3a 1.05a 3.8a 47.3a 6.9 0.026a 1.7a 21.0a Std.dev. 0.34 0.68 14.9 4.84 73.63 236.4 38.3 1.16 10.7 146.0 Skewness -0.134 0.61 2.8 2.54 3.0 1.4 4.2 2.03 2.98 3.09 Kurtosis -0.453 0.20 9.5 8.44 11.2 1.8 22.5 4.49 11.26 11.3 Range 1.39 3.01 80.7 25.2 402.7 955.3 254.5 5.08 59.7 782.7 Minimum 0.15 4.98 1.8 1.05 3.8 47.3 6.9 0.03 1.68 21.0 Maximum 1.54 7.99 82.5 26.22 406.5 1002.6 261.4 5.1 61.4 803.6 Page 21 6/26/2007 -1 SPI Units a: Multiple modes exist. The smallest value is shown. krr WEP -1 Table 2b: Statistical properties of 10-30 cm soils (averaged replicates) [n: 52] BD pH LOI TN TC TP HCl-TPi WEP M1-P SPI Units g cm-3 - % g kg-1 g kg-1 mg kg-1 mg kg-1 mg kg-1 mg kg-1 mg kg-1 Mean 1.27 6.47 10.7 3.7 39.3 191.3 25.0 0.24 7.2 224.9 SE of mean 0.05 0.08 1.2 0.4 5.7 23.8 3.4 0.05 1.1 34.1 Median 1.40 6.50 6.9 2.6 21.9 121.2 14.3 0.12 4.0 145.1 Mode 0.14a 5.49a 6.9 0.9a 1.9a 17.2a 2.6a 0.02a 0.9 17.1 Std.dev. 0.36 0.60 9.0 2.9 41.0 171.4 24.8 0.37 7.7 246.0 Skewness -0.98 -0.28 2.1 2.2 2.1 1.9 1.9 3.8 2.3 2.6 Kurtosis 0.62 -0.03 5.1 6.8 5.4 4.6 3.1 15.2 6.1 8.5 Range 1.65 2.82 46.5 15.7 207.3 873.6 105.1 1.94 38.0 1,340.9 Minimum 0.14 4.94 1.5 0.9 1.9 17.2 2.6 0.02 0.9 17.1 Maximum 1.79 7.76 48.0 16.6 209.3 890.7 107.6 1.95 38.9 1,358.0 a :Multiple modes exist. The smallest value is shown krr Page 22 6/26/2007 Table 3. Range of 1 M HCl extractable metals in soils collected from Taylor Creek STA. 0-10 cm depth Ca 10-30 cm depth Mg -1 Fe -1 Al -1 Ca -1 Mg -1 Fe -1 Al Units mg kg mg kg mg kg mg kg mg kg mg kg mg kg mg kg-1 Mean 6,450 550 869 1,500 5,348 426 829 1,828 SE of mean 631 49 63 146 785 40 52 187 Median 5,091 501 761 1,022 3,185 375 750 1,555 Mode 750a 44a 138a 141a 123a 11a 40a 65a Std.dev. 4,639 355 455 1,052 5,711 289 380 1,360 Skewness 1.6 1.5 3.0 2.6 3.2 1.9 1.3 2.5 Kurtosis 3.0 2.7 12.6 8.4 14.3 4.8 2.5 9.7 Range 22,468 1,645 3,007 5.785 35,294 1,505 2,004 8,285 Minimum 750 44 138 141 123 11 40 65 Maximum 23,219 1,689 3,145 5.926 35,417 1,516 2,045 8,350 a :Multiple modes exist. The smallest value is shown krr Page 23 6/26/2007 -1 Results indicate that RMSEs were relatively high for all variables indicating the large uncertainty of predictions. This was due to the limited sampling size of 52. For example, the RMSE for TP (0-10 cm) was relatively high with 239 mg kg-1 given a measured TP range of 955 mg kg-1 and mean of 311 mg kg-1. The ME indicates which variables were under- and which ones were over predicted. Overall, most variables in the topsoil, except for TN, TP, SPI, and HCl-Al, were slightly under predicted (Table 3). The accuracy for all variables in the subsoil (10-30 cm) was higher indicated by a lower RMSE when compared to the topsoil (0-10 cm) except for SPI and HCl-Al (Table 3 and 4). Interestingly, most variables in the subsoil (except for TPi, Mehlich I P, SPI and HCl-Fe) were slightly over predicted (Table 4 and 5). Interpolated maps on the following pages show the spatial distribution patterns of variables. The TP in the topsoil was dominant in the northern part of the STA, whereas these patterns shifted and relatively high rates of TP were found in the subsoil (10-30 cm depth). Total inorganic P in 0-10 cm showed a very uneven spatial distribution that peaked at only few locations up to a value of 1003 mg kg-1. Values jumped from very high TPi to extremely low TPi in the topsoil indicating that soils are extremely variable in inorganic P. krr Page24 6/26/2007 Table 4: Cross-validation results interpolations and spline parameters for 0-10 cm depth. Variable Spline Parameters Mean Error RMSE Moisture (%) 10(4)1 - 0.232 15.53 BD (g/cm3) 10(4)1 - 0.1269 0.3367 - 0.008467 0.6983 1 pH 10(4) LOI (%) 12(7)1 - 0.1552 15.48 TN (g kg-1) 10(4)1 0.04441 7.05 TC (g kg-1) 10(7)1 - 1.132 75.61 TP (mg kg-1) 12(4)1 1.067 239.1 -1 1 - 0.8871 282.2 TPi (mg kg ) 10(7) Water Extractable P (mg) 12(7)1 - 0.00767 1.067 Mehlich I P (mg kg-1) 12(7)1 - 0.01961 10.52 SPI (mg kg-1) 12(7)1 0.2091 149 HCl-Ca (g kg-1) 10(7)1 - 78.45 47.25 HCl-Mg (mg kg-1) 10(7)1 - 4.962 366.5 HCl-Fe (mg kg-1) 10(7)1 -11.4 500.4 HCl-Al (mg kg-1) 10(7)1 1.558 933 1 Neighbors included; in parenthesis: minimum of neighbors krr Page25 6/26/2007 Table 5: Cross-validation results interpolations and spline parameters for 10-30 cm depth. Variable Spline Parameters Mean Error RMSE Moisture (%) 10(4)1 0.04315 10.11 BD (g/cm3) 10(4)1 0.0008794 0.3372 12(7) 1 0.009733 0.5886 12(4) 1 0.06301 7.773 12(4) 1 0.04377 2.29 TC (g kg ) 12(4) 1 0.3908 32.51 TP (mg kg-1) 12(4)1 5.095 148.9 -1 1 - 0.397 20.19 1 pH LOI (%) -1 TN (g kg ) -1 TPi (mg kg ) 10(7) Water Extractable P (mg) 10(4) 0.001243 0.3934 Mehlich I P (mg kg-1) 10(4)1 -0.3392 7.694 12(4) 1 -1.259 234.7 12(4) 1 1.107 30.23 12(4) 1 1.028 287.9 HCl-Fe (mg kg ) 10(7) 1 - 3.001 390.3 HCl-Al (mg kg-1) 12(4)1 2.215 1289 -1 SPI (mg kg ) -1 HCl-Ca (g kg ) -1 HCl-Mg (mg kg ) -1 1 Neighbors included; in parenthesis: minimum of neighbors krr Page26 6/26/2007 Figure 5. Spatial distribution of total phosphorus of soils collected from Taylor Creek STA krr Page 27 6/26/2007 Figure 6. Spatial distribution of total inorganic phosphorus of soils collected from Taylor Creek STA. krr Page 28 6/26/2007 Figure 7. Spatial distribution of bulk density of soils collected from Taylor Creek STA. krr Page 29 6/26/2007 Figure 8. Spatial distribution of pH of soils collected from Taylor Creek STA. krr Page 30 6/26/2007 Figure 9. Spatial distribution of loss of ignition of soils collected from Taylor Creek STA. krr Page 31 6/26/2007 Figure 10. Spatial distribution of total nitrogen of soils collected from Taylor Creek STA. krr Page 32 6/26/2007 Figure krr 11. Spatial distribution Page of total carbon 33 of soils collected 6/26/2007 from Taylor Creek STA. Water extractable inorganic phosphorus (mg/kg) 0-10 cm Water extractable inorganic phosphorus (mg/kg) 10-30 cm Figure 12. Spatial distribution of water extractable phosphorus of soils collected from Taylor Creek STA. krr Page 34 6/26/2007 Figure 13. Spatial distribution of bioavailable phosphorus of soils collected from Taylor Creek STA. krr Page 35 6/26/2007 Figure 14. Spatial distribution of maximum phosphorus retention capacity of soils collected from Taylor Creek STA, as estimated by the single point isotherm method. krr Page 36 6/26/2007 Figure 15. Spatial distribution of 1M HCl-extractable calcium of soils collected from Taylor Creek STA. krr Page 37 6/26/2007 Figure 16. Spatial distribution of 1M HCl-extractable magnesium of soils collected from Taylor Creek STA. krr Page 38 6/26/2007 Figure 17. Spatial distribution of 1M HCl-extractable iron of soils collected from Taylor Creek STA. krr Page 39 6/26/2007 Figure 18. Spatial distribution of 1M HCl-extractable aluminum of soils collected from Taylor Creek STA. krr Page 40 6/26/2007 Table 6. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Site Depth Cm 9 0-10 14 0-10 17 0-10 20 0-10 34 0-10 37 0-10 42 0-10 46 0-10 49 0-10 9 10-30 14 10-30 17 10-30 krr Moisture % BD g cm-3 pH LOI % TN g/kg TC g/kg Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 35.0 0.8 2.4 23.5 1.6 6.7 15.9 1.8 11.6 3.9 0.8 20.8 8.5 1.0 12.1 23.9 1.4 5.7 10.0 2.6 26.3 25.0 10.2 40.8 26.0 0.3 1.0 0.4 0.0 3.1 0.8 0.0 4.2 0.9 0.1 9.2 1.5 0.3 17.9 1.5 0.1 4.1 0.7 0.1 10.0 1.0 0.1 7.8 0.6 0.2 42.6 0.9 0.1 13.7 5.6 0.2 2.9 6.8 0.1 1.5 6.0 0.1 1.7 6.5 0.4 6.2 8.0 0.1 1.4 6.0 0.0 0.4 6.4 0.1 1.3 5.8 0.3 4.9 5.7 0.2 3.6 28.7 3.5 12.2 14.4 1.2 8.3 13.6 2.2 16.0 5.6 0.3 4.9 1.8 0.3 16.6 25.0 3.3 13.2 6.3 1.8 28.2 23.3 8.3 35.7 16.2 1.4 8.8 10.2 1.1 10.4 5.4 0.3 6.3 5.5 1.1 20.0 2.4 0.1 2.4 1.3 0.2 16.7 8.5 1.5 17.4 2.3 0.2 8.0 8.8 3.5 40.5 5.8 0.4 7.0 121.0 11.3 9.4 54.8 0.7 1.3 58.4 11.5 19.7 19.3 0.4 1.8 3.8 2.4 63.3 111.1 20.5 18.4 17.7 4.1 23.3 101.2 49.0 48.4 64.5 7.5 11.7 Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 19.2 3.0 15.9 14.8 1.6 10.7 15.2 0.8 5.4 1.3 0.1 8.7 1.6 0.1 4.0 1.4 0.0 2.6 6.3 0.1 1.8 7.1 0.1 1.8 6.5 0.2 3.8 9.4 1.6 16.9 5.8 0.8 13.1 6.9 1.0 13.9 3.7 0.6 15.3 2.1 0.1 6.5 2.5 0.3 12.0 36.8 6.2 17.0 15.5 3.0 19.3 21.8 2.7 12.5 Page41 6/26/2007 Table 6. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Site Depth Cm 20 10-30 34 10-30 37 10-30 42 10-30 46 10-30 49 10-30 Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Moisture % BD g cm-3 pH LOI % TN g/kg TC g/kg 7.7 0.9 12.0 11.2 0.5 4.5 16.5 1.4 8.7 34.0 4.2 12.5 13.0 0.8 6.1 21.8 2.6 11.7 1.4 0.1 6.8 1.7 0.1 5.4 1.2 0.2 13.5 1.0 0.1 14.2 1.5 0.0 3.1 1.4 0.1 9.0 6.5 0.3 4.5 7.5 0.2 2.3 6.3 0.2 2.5 6.3 0.1 1.8 7.0 0.3 4.7 6.5 0.2 3.1 5.3 0.8 14.4 1.5 0.0 2.1 9.9 1.3 13.1 20.2 2.7 13.4 6.5 0.5 7.5 8.6 2.0 23.4 2.3 0.3 12.6 0.9 0.1 10.7 3.5 0.4 12.2 7.1 1.1 15.9 2.5 0.2 7.3 2.9 0.5 17.1 16.2 2.4 14.9 1.9 0.4 21.8 38.7 7.1 18.3 84.9 16.4 19.3 22.1 1.7 7.5 26.5 6.6 25.0 Data on variability among replicate cores at select stations is shown in Tables 6 and 7. For most of the parameters measured, coefficient of variation was less than 20% among replicate cores. However, for labile pools of phosphorus such as WEP and Mehlich 1- extractable P, a much higher variability was observed. krr Page42 6/26/2007 Table 7. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Site Depth Cm 9 0-10 14 0-10 17 0-10 20 0-10 34 0-10 37 0-10 42 0-10 46 0-10 49 0-10 9 10-30 14 10-30 17 10-30 krr TP mg/kg TPi mg/kg TPo mg/kg WEP-P mg/kg M I-P mg/kg SPI mg/kg Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 536.5 56.7 10.6 239.2 27.3 11.4 284.4 60.5 21.3 130.9 6.4 4.9 47.3 16.6 35.1 563.5 63.4 11.3 107.4 21.6 20.1 521.3 169.3 32.5 300.5 32.8 10.9 47.0 4.2 9.0 27.9 2.9 10.4 20.1 2.9 14.6 16.9 2.5 14.7 6.9 0.7 10.6 31.2 3.7 11.9 13.2 2.6 19.9 37.1 18.3 49.4 24.8 4.6 18.6 489.5 60.5 12.4 211.3 27.2 12.9 264.4 57.6 21.8 114.1 8.2 7.2 40.3 15.9 39.3 532.3 60.1 11.3 94.2 19.0 20.1 484.2 151.2 31.2 275.6 28.7 10.4 2.1 0.4 18.7 0.5 0.3 63.3 0.7 0.2 26.2 0.2 0.0 10.9 0.1 0.0 42.0 3.0 1.7 56.2 0.1 0.0 24.0 0.9 0.6 65.4 0.4 0.1 32.9 17.6 1.6 8.9 16.4 2.5 15.3 9.1 2.3 24.9 4.8 0.5 10.1 2.6 0.7 28.3 10.9 3.3 30.3 5.8 2.0 33.7 12.3 4.8 38.8 7.2 2.4 33.7 191.1 31.0 16.2 192.1 5.6 2.9 158.1 18.8 11.9 183.8 40.5 22.0 51.6 9.9 19.1 215.9 61.7 28.6 130.7 4.0 3.1 112.1 35.1 31.3 329.1 81.2 24.7 Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 186.9 32.5 17.4 84.7 13.5 15.9 111.4 11.2 10.0 17.8 1.0 5.6 9.7 0.8 7.9 8.1 0.5 6.7 169.1 32.0 18.9 75.0 13.6 18.1 103.4 10.7 10.3 0.1 0.0 17.9 0.0 0.0 1.6 0.1 0.0 20.6 5.8 0.3 5.8 3.8 1.1 28.9 1.9 0.3 15.6 145.7 19.4 13.3 121.9 31.6 25.9 143.4 27.0 18.8 Page43 6/26/2007 Table 7. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek . STA Site Depth Cm 20 10-30 34 10-30 37 10-30 42 10-30 46 10-30 49 10-30 krr Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) TP mg/kg TPi mg/kg TPo mg/kg WEP-P mg/kg M I-P mg/kg SPI mg/kg 105.9 17.9 16.9 22.5 3.2 14.4 217.0 26.4 12.2 382.5 52.6 13.8 129.8 13.7 10.6 135.0 39.1 29.0 13.9 2.4 17.4 9.5 1.8 19.2 14.6 2.9 19.7 41.4 4.2 10.2 9.9 2.1 21.6 10.3 1.6 15.7 91.9 18.8 20.5 13.0 2.4 18.2 202.4 23.6 11.6 341.1 49.0 14.4 119.9 11.6 9.7 124.7 37.7 30.2 0.1 0.1 60.6 0.1 0.0 16.5 0.3 0.1 20.5 0.2 0.2 78.9 0.1 0.0 20.3 0.0 0.0 25.1 4.0 1.5 35.9 3.8 2.6 68.8 3.7 1.4 39.2 13.6 4.7 34.8 2.4 0.6 27.0 1.9 0.7 35.8 154.9 37.1 23.9 32.8 11.7 35.7 227.8 25.9 11.4 429.3 106.9 24.9 166.2 5.1 3.1 129.0 44.6 34.6 Page44 6/26/2007 Table 8. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA. Site Depth Cm 9 0-10 14 0-10 17 0-10 20 0-10 34 0-10 37 0-10 42 0-10 46 0-10 49 0-10 9 10-30 14 10-30 17 10-30 krr HCl-Ca mg/kg HCl-Mg mg/kg HCl-Fe mg/kg HCl-Al mg/kg Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 7057 644 9 7074 597 8 4689 579 12 2138 342 16 1150 372 32 9022 981 11 3468 750 22 4256 1170 27 8250 1283 16 1128 278 25 653 117 18 490 38 8 293 4 1 44 17 39 918 50 5 273 25 9 570 178 31 660 47 7 1025 218 21 896 78 9 591 55 9 794 53 7 344 89 26 547 102 19 645 49 8 728 47 6 839 10 1 754 66 9 818 41 5 974 54 6 914 73 8 698 181 26 1584 490 31 1085 145 13 831 52 6 1962 106 5 Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) 3944 555 14 3075 486 16 3101 223 7 459 69 15 296 17 6 372 10 3 750 96 13 684 49 7 620 53 9 957 53 6 1395 325 23 1451 357 25 Page45 6/26/2007 Table 8. Variability in soil properties on triplicate soil cores along a transect in Taylor Creek STA Site Depth Cm 20 10-30 34 10-30 37 10-30 42 10-30 46 10-30 49 10-30 krr Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) Mean SD CV (%) HCl-Ca mg/kg HCl-Mg mg/kg HCl-Fe mg/kg HCl-Al mg/kg 2061 17 1 634 102 16 4224 164 4 9963 1522 15 2776 208 8 4384 704 16 317 25 8 87 8 10 629 24 4 592 51 9 390 19 5 409 60 15 937 123 13 706 63 9 564 123 22 801 99 12 918 43 5 583 38 6 1517 410 27 1834 171 9 2371 148 6 2974 435 15 1358 274 20 1981 72 4 Page46 6/26/2007 Table 9. Correlation matrix for soil variables measured at 0-10 cm and 10 – 30 cm depths. Pearson correlation coefficients are significant at 0.05 level (>0.159) and 0.01 level (>0.208). n =141. BD = Bulk density; LOI = Loss on ignition; TN = Total nitrogen; TC = Total carbon; TPi = Total inorganic P; WEP = Water extractable P; M I-P = Mehlich I –extractable P; SPI = Single point isotherm. pH LOI TN TC TP TPi WEP M I-P SPI HCl-Ca HCl-Mg HCl-Fe HCl-Al krr BD 0.55 0.77 0.79 0.77 0.82 0.52 0.52 0.46 0.35 0.55 0.69 0.45 0.20 pH LOI TN TC TP TPi WEP M I-P SPI HCl- HCl- HClCa Mg Fe -0.51 -0.53 -0.52 -0.51 -0.22 -0.37 -0.09 -0.21 -0.13 -0.45 -0.30 -0.05 0.99 0.99 0.93 0.60 0.60 0.40 0.43 0.70 0.84 0.70 0.32 0.99 0.93 0.57 0.62 0.41 0.37 0.67 0.82 0.66 0.25 0.91 0.57 0.64 0.40 0.36 0.68 0.81 0.67 0.25 0.69 0.55 0.48 0.56 0.65 0.87 0.65 0.44 0.29 0.81 0.58 0.56 0.61 0.65 0.52 0.40 -0.09 0.28 0.44 0.21 -0.19 0.21 0.35 0.35 0.32 0.15 0.48 0.58 0.57 0.88 0.62 0.52 0.42 Page 47 6/26/2007 0.65 0.49 0.47 Phosphorus Storage in Soils Table 10. Storage of labile and non-labile pools of phosphorus in Taylor Creek STA soils. Phosphorus pools Total Phosphorus Average Minimum Maximum HCl-extractable P Average Minimum Maximum Mehlich I- P Average Minimum Maximum Water extractable P Average Minimum Maximum Stable Pool P Average Minimum Maximum SPI-Pmax Average Minimum Maximum 0 – 10 cm g P m-2 10 – 30 cm g P m-2 0 – 30 cm g P m-2 21.1 4.3 44.7 38.4 3.1 90.3 59.5 7.4 135.0 2.67 0.92 14.7 4.82 0.19 17.5 7.49 1.11 32.2 1.01 0.23 6.82 1.49 0.05 9.13 2.50 0.28 16.0 0.06 0.003 0.30 0.05 0.01 0.58 0.11 0.013 0.88 18.5 3.41 37.2 33.5 2.87 81.0 52.0 6.28 118.2 14.0 1.46 43.5 45.4 3.31 196.5 59.4 4.77 240 Table 11. Labile and non-labile pools of phosphorus expressed as percent of total phosphorus stored in soils. Phosphorus pools Water extractable P Mehlich 1-P HCl extractable P Stable P krr 0 – 10 cm % of TP 0.3 5.1 12.7 87.9 10 – 30 cm % of TP 0.13 3.9 12.6 87.2 Page48 0 – 30 cm % of TP 0.18 4.2 12.6 87.4 6/26/2007 Figure 19. Phosphorus storage in soils collected from Taylor Creek STA. Stable pools (nonreactive P) was estimated by the difference between total soil phosphorus and inorganic phosphorus extracted using 1 M HCl (Reddy et al., 1998b). Data on P storage in various pools are presented in Tables 10 and 11 and Fig. 19. Total P storage ranged from 4.3 to 44.7 g m-2 (mean value = 21.1 g m-2) in 0-10 cm soils and 3.1 to 90.3 g m-2 (mean value = 38.4 g m-2) in 10-30 cm soils. Water extractable P accounted for 0.18% of total P storage, while Mehlich 1 -extractable accounted for 4.2% of total P, and total inorganic P accounted for 13% of the total P. A large proportion of P was stored in organic P pool and as stable inorganic P. Stable inorganic P is operationally defined as Fe, Al, Ca, and Mg-bound P not extracted with 1 M HCl. The maximum P retention capacity of soils was estimated using single point isotherm. This estimate suggests that the soils are capable of adsorbing a maximum of 72 g P m-2. If one assumes that the STA is loaded at a rate of 2 to 5 g P m-2 year-1, these soils represent a P retention expectancy of 14 to 36 years. Long term P retention in Taylor Creek STA depends not krr Page49 6/26/2007 only on soil P sorption capacity, but the physico-chemical characteristics of newly accreted organic and mineral matter. 3.0. Fractionation of Soil Phosphorus into Organic (Po) and Inorganic (Pi) Forms Mobility and reactivity of P in wetlands under variable hydrologic conditions are controlled by the chemical composition of P in soil and water, relative sizes of various P pools in the soil, interactions of soluble fractions with solid phases, and decomposition of soil organic matter. Phosphorus is present in both organic and inorganic forms, with organic forms present as the dominant pool in many wetlands. Forms of inorganic P (Pi) in soils are usually determined by sequential extractions with acid and alkaline reagents, as proposed by Chang and Jackson (1957) and later modified by others for soils and sediments (Psenner et al., 1988; Ruttenburg, 1992; Olila et al., 1994). A modification of this scheme has been adopted for wetland soils (Qualls and Richardson, 1995; Reddy et al., 1995, 1998b). These schemes typically identify P in the following groups: (i) labile Pi loosely adsorbed; (ii) Pi associated with Fe and Al; (iii) Pi associated with Ca and Mg; (iv) alkali-extractable organic P (fulvic- and humic-bound P); and (v) residual organic P. In soils with high levels of organic P such as those impacted organic waste loading, neutral salt extractions may include labile organic P. Forms of organic P (Po) have also been distinguished using acid and alkaline extractions of soils. The objective of this study was to quantify the labile and stable pools of phosphorus in soils collected from Taylor Creek STA. 3.1 Materials and methods The forms in which the existing P is held in the soils was evaluated by the Reddy et al., (1998a) procedure. Total inorganic P was determined by extraction with 1.0M HCl and organic P calculated as the difference between total P and inorganic P. Inorganic P was separated sequentially into loosely bound P, Fe/Al-P, and Ca-P by extractions with 1M KCl, 0.1M NaOH and 0.5M HCl . In addition, alkali extractable P was analyzed for organic P. All fractionations were done on 26 samples (13 for each depth, 9 stations and 2 stations with triplicates) at the selected sampling locations (Figure 20). The sampling scheme used is given in Figure 21. Fractionation data for all samples on a weight basis is given in Appendix 1a and on a volume basis in Appendix 1b. Potassium Chloride extractable P (labile P): Phosphorus in field-wet soil (0.2 g dry-weight equivalent) was extracted with 1 M KC1 solutions, with the P extracted representing the readily available pool of P (KCl-Pi). Air-dried soils should not be used to determine labile pools, as drying may affect the lability of P through oxidation of organic P. Soil suspensions were equilibrated for a period of 2 h by continuously shaking on a mechanical shaker, followed by centrifugation at 4066 x g for 10 min. The supernatant solution was filtered through a 0.45 μm membrane filter. Solutions were analyzed for soluble reactive P (SRP) (U.S. EPA, 1993, Method 365.2). The residual soil was used for the following sequential extraction. Alkali (NaOH) extractable P: The residual soil was then treated with 0.1 M NaOH and allowed to equilibrate for a period of 17 h on a mechanical shaker, followed by centrifugation and filtration as described above. Filtered solutions were analyzed for both SRP and a separate krr Page50 6/26/2007 portion extract is digested and for TP (U.S. EPA, 1993, Method 365.1). These fractions are referred to as NaOH-Pi and NaOH-TP, respectively, with NaOH-Pi considered to represent Feand Al-bound P. Extraction with 0.1 M NaOH also removes the P associated with humic and fulvic acids. The difference between NaOH-TP and NaOH-Pi was assumed to be organic P (NaOH-Po ) associated with fulvic and humic acids. Acid (0.5M HCl) extractable P: Residual soil obtained from the above extraction was treated with 0.5 M HCl and allowed to equilibrate for a period of 24 h followed by centrifugation and filtration as described above. The filtered solutions were analyzed for SRP using an autoanalyzer (U.S. EPA, 1993, Method 365.1). The HCl-Pi fraction is assumed to represent Ca- and Mgbound P. Residual P and Total P: The residue from the above extraction was combusted at 550°C for 4 h. The ash was dissolved in 6 M HCl followed by analysis using an autoanalyzer (Andersen, 1976; U.S. EPA, 1993, Method 365.1). A similar method was also used to analyze total P of the original soil. Acid (1 M HCl) extractable P and Cations: Oven-dry soil samples were extracted with 1 M HCl (soil/solution ratio of 1:50, w/v basis) after a 3-h equilibration, followed by centrifugation and filtration, as described above. Filtered solutions were analyzed for P using the procedures described above, and for Ca, Mg, Fe, and Al using inductively coupled argon plasma spectrometry (U.S. EPA, 1993, Method 200.7). All samples were analyzed according to the specifications described in the Wetland Biogeochemistry Laboratory (WBL) Standard Operating Procedures (SOP). The WBL is certified by the Department of Health, Bureau of Laboratories for NELAP certification (E72949). All metals were analyzed by the UF-IFAS Analytical Research Laboratory. This lab is certified by NELAP (E72850). krr Page51 6/26/2007 Figure 20. Sampling locations used to determine soil phosphorus forms and retention capacities. Stations 20 and 37 were sampled in triplicate to determine the field variability within a sampling location. krr Page52 6/26/2007 Soi 1.0 M KCL extraction [2hr] hr] Readily available P [Pi] Residu 0.1 M NaO extraction [17hr] [TP] [SRP Alkali extractable organic P [ Po] [TP-SRP]] Fe/A -bound P [Pi ] Residu 0.5 M HC extraction [24hr] [SRP] Ca/Mg-bound P [Pi ] Residu Ashing [TP] Residual P [Po ] I Figure 21. Soil phosphorus fractionation scheme used to determine labile and stable pools of phosphorus (Reddy et al., 1998b). 3.2 Results and discussion Total Phosphorus concentrations in soil samples across the STA Transect. The total P (TP) concentrations within the STA transect at the 0-10 cm and 10-30 cm depths are given in Figure 22. Stations #20 and 37 were sampled in triplicate. Data for all replicates are plotted in Figure 22 and presented in Table 12. Total P concentrations in surface soils ranged from 28 to 562 mg kg-1 with high values observed in stations at the south end of the transect. The high TP concentrations are a reflection of lower bulk densities. Bulk densities ranged from 0.5 to 1.5 g cm-3. Lowest bulk density values in surface soil was observed at Station # 9, but TP concentrations were not highest at this station. Highest TP concentrations were observed at Station #34, where bulk density of soils was 0.65 g cm-3. Lowest concentrations were observed at Station #34; total P concentrations in subsurface soils ranged from 19 to 242 mg kg-1. Similarly, lowest TP concentrations were noted at Station #34. Total P concentration was higher in surface soils than in subsurface soils. Distribution of inorganic phosphorus across the STA transect: Distribution of inorganic P (as determined by a single extraction with 1.0M HCl) within the STA transect at the 0-10 cm and krr Page53 6/26/2007 700 0 -1 0 c m 600 T o ta l P 10 - 30 cm 500 R e p lic a te c o res 400 300 200 R e p lic a te c o res Phosphorus [mg kg-1] 100 0 60 In o rg a n ic P 50 40 30 R e p lic a te c o res R e p lic a te c o res 20 10 0 700 N o n -r e a c ti v e PR e p lic a te 600 c o res 500 400 300 R e p lic a te c o res 200 100 0 20 20 20 46 9 14 17 42 49 34 37 37 37 S ta tio ns a lo ng the T ra ns e c t Figure 22. Total P, inorganic P (measured using single extraction with 1 M HCl), and nonreactive P (not extracted with 1 M HCl) to include organic P and non-reactive inorganic P in soils across the transect at Taylor Creek STA. 10-30 cm depths are given in Figure 22. Station #34 had lowest TP concentrations, as compared to other stations along the transect. At this station, inorganic P accounted for 21 and 45% of the total P in 0-10 and 10-30 cm depths, respectively. At the remaining stations, inorganic P accounted for 6 to 15% of TP in 0-10 cm soil and 6 to 16% in 10-30 cm soils. Lower percentage of inorganic P was found in soils with high organic matter content, suggesting P may be present in organic pool. Since the soils in Taylor Creek STA were mineral in nature, we expected higher recovery of TP as inorganic P. Lower inorganic P recovery in 1 M HCl suggests that P may be present in non-reactive, stable pool. Distribution of non-reactive phosphorus across the STA Transect: Non-reactive phosphorus represents P not extracted with 1 M HCl. This may include organic phosphorus and stable inorganic phosphorus complexed with organic matter (Reddy et al., 1998b). Distribution of non-reactive P (as determined by the difference between total P and total inorganic P) within the STA transect at the 0-10 cm and 10-30 cm depths are presented in Figure 22. Station #34 had lowest TP concentrations, as compared to other stations along the transect. At this station, non-reactive P accounted for 79 and 55% of the total P in 0-10 and 10-30 cm depths, respectively. At the remaining stations, non-reactive P accounted for 85 to 94% of TP in 0-10 cm soil and 84 to 94% in 10-30 cm soils, respectively. High percentage of non-reactive P in krr Page54 6/26/2007 these soils was surprising observation and further investigation is needed to determine the forms of P stored in this pool. Table 12. Variability in selected soil properties measured on replicate soil cores from two stations along a transect in Taylor Creek STA. Three cores were taken from each station. Parameter Station Bulk density g cm-3 LOI g kg-1 Total C g kg-1 Total N g kg-1 Total P mg kg-1 Inorganic P mg kg-1 Non-reactive P mg kg-1 20 37 20 37 20 37 20 37 20 37 20 37 20 37 0-10 cm Mean 1.54 0.65 56 250 19 111 2.4 8.5 131 563 17 31 114 532 SD 0.28 0.07 2.7 33.1 0.4 20.5 0.1 1.5 6.4 63.4 2.5 3.7 8.2 63.2 CV (%) 18 11 5 13 2 18 4 18 10 11 15 12 7 12 10-30 cm Mean 1.39 1.19 53 99 16 39 2.3 3.5 106 217 14 15 92 202 SD 0.10 0.16 7.6 12.6 2.4 7.1 0.3 0.4 17.9 26.4 2.4 2.0 18.8 23.6 CV (%) 7 13 14 13 15 18 13 11 17 12 17 13 20 12 Table 13. Total inorganic P recovered during repeated extractions with 1 M HCl Station 23 52 111 128 138 Total 1M HCl-Pi mg kg-1 46.2 10.3 34.6 61.3 103.8 % of Total HCl-Pi recovered during each extraction First Second Third 57.6 73.1 80.0 81.2 81.5 13.2 14.7 9.0 10.8 9.6 26.3 12.1 11.0 8.0 9.0 To determine the efficacy of 1M HCl in extracting inorganic P, we selected soil samples from five stations and subjected them to sequential extractions with the acid. The purpose of this sequential extraction was to determine how reactive is the residual inorganic and organic P. During each extraction, soils were equilibrated with acid for a period of 3 hours. Results are presented in Table 13. With the exception of soil from Station #23, approximately 80% of the TPi was extracted during the first extraction, and the remaining 20% was extracted in the next two extractions. These results suggests that the P not extracted after repeated extractions is either in stable inorganic P pool (stable mineral form) or organic P form. Further analysis of residual organic P (using more modern techniques such NMR spectroscopy) is needed to document the forms of organic P forms. If the residual P contains inorganic P, that can documented by X-ray diffraction. These analysis is beyond the scope of this project. krr Page55 6/26/2007 Labile and Non-labile Pools of Soil Phosphorus The P fractionation scheme used (Figure 21) sequentially separated P into: (i) loosely bound P (ii) Pi associated with Fe and Al ; (iii) Pi associated with Ca and Mg; (iv) alkali-extractable organic P (fulvic- and humic-bound P); and (v) residual organic P. Data are presented in Tables 14 and 15. KCl-extractable P: Inorganic P extracted with salts such as 1 M KC1 represents loosely adsorbed P, which is bioavailable and can be readily released into the water column. Labile Pi content of surface soils (0-10 cm) was in the range of 0.14 to 2.8 mg kg-1, which accounted for 0.12 to 0.54% of total P (Figure 23). At Station #34, a larger proportion of TP (2 to 6%) was labile. On an average, 0.3% of the total P was labile, as estimated by the regression equation presented in Table 16. 3 .0 R e p li c a t e c o r e s 2 .5 0-10 cm 10 - 30 cm 2 .0 E xch -P 1 .5 Phosphorus [mg kg-1] 1 .0 0 .5 0 .0 70 60 50 40 30 20 10 0 30 R e p lic a t e co re s F e - / A l- P R e p l ic a t e co re s C a -/M g -P 25 R e p lic a t e co re s 20 15 10 R e p l ic a t e co re s 5 0 20 20 20 46 9 14 17 42 49 34 37 37 37 S ta tio n s a lo n g th e T ra n s e c t Figure 23. Distribution of labile P (KCl Pi), Fe/Al-P (NaOH Pi), and Ca/Mg Pi (HCl Pi) fractions in soils collected along a transect in Taylor Creek STA. Iron - and Aluminum bound P: Inorganic P extracted with 0.1N NaOH represents Fe-and Albound P. This pool accounted for 8 to 14% of TP in 0-10 cm soils and 7 to 15% in 10-30 cm soils, respectively. There was no distinguishable trend among the stations sampled. On an average, Fe- and Al-bound P accounted for 9% of total P (Table 16). krr Page56 6/26/2007 Calcium and Magnesium bound P: Inorganic P extracted with 0.5M HCl (after alkaline extraction) represents Ca-and Mg-bound P. This pool accounted for 2 to 9% of total P in surface soils and 2 to 13% in soils from 10 -30 cm depth (Figure 25, Tables 14, 15 and 16). krr Page57 6/26/2007 Table 14a. Labile and non-labile pools of phosphorus in soils (0-10 cm depth) collected along a transect in Taylor Creek STA. Site 9-1 14-1 17-1 20-1 20-2 20-3 34-1 37-1 37-2 37-3 42-1 46-2 49-1 krr NaOHNaOHResidual Sum TP HCl-TPi BD KCl Pi Pi HCl-Pi Sum TPi Po P TPo Sum TP -1 -1 -1 -1 -1 -1 -1 -1 -1 mg kg mg kg g cm-3 mg kg mg kg mg kg mg kg mg kg mg kg mg kg mg kg-1 ---------------------------------------------------------Soil Depth 0-10 cm-------------------------------------------------------------507.1 51.1 0.384 2.80 59.4 25.97 88.1 199.8 231.1 430.9 519.0 223.4 24.8 0.843 0.57 22.6 18.75 41.9 56.4 114.4 170.8 212.7 273.2 19.8 0.925 0.31 29.9 6.83 37.0 119.5 115.9 235.4 272.4 123.6 18.6 1.853 0.14 17.2 4.07 21.4 53.6 45.0 98.6 120.0 134.9 14.0 1.338 0.18 16.7 3.08 20.0 66.2 46.6 112.8 132.8 134.3 18.0 1.428 0.35 18.1 3.63 22.0 64.0 44.5 108.5 130.6 28.9 6.1 1.498 0.43 1.6 1.52 3.5 4.4 12.2 16.7 20.2 627.6 35.5 0.628 2.52 50.8 17.03 70.4 314.8 257.8 572.6 643.0 562.1 29.1 0.603 1.17 44.1 12.47 57.7 254.3 233.8 488.1 545.8 500.8 28.9 0.727 2.09 38.8 11.39 52.3 224.2 221.9 446.2 498.5 103.0 13.1 1.017 0.32 6.0 4.94 11.3 22.0 43.9 65.9 77.2 447.9 26.2 0.774 0.47 33.7 9.77 43.9 164.9 161.2 326.1 370.0 266.3 19.5 0.935 0.25 20.5 6.93 27.7 95.8 98.7 194.5 222.2 Page 58 6/26/2007 Table 14b. Labile and non-labile pools of phosphorus in soils (10-30 cm depth) collected along a transect in Taylor Creek STA. Site 9-1 14-1 17-1 20-1 20-2 20-3 34-1 37-1 37-2 37-3 42-1 46-2 49-1 krr NaOHNaOHResidual Sum TP HCl-TPi BD KCl Pi Pi HCl-Pi Sum TPi Po P TPo Sum TP -1 -1 -1 -1 -1 -1 -1 -1 -1 mg kg mg kg g cm-3 mg kg mg kg mg kg mg kg mg kg mg kg mg kg mg kg-1 ---------------------------------------------------- Soil Depth 10-30 cm -------------------------------------------------------151.2 17.6 1.433 0.25 16.2 5.64 22.1 45.1 60.8 105.9 128.1 84.8 8.8 1.596 0.35 5.5 4.29 10.2 17.4 44.1 61.5 71.7 110.4 7.9 1.390 0.15 8.1 3.27 11.5 32.0 55.0 87.0 98.5 86.8 13.7 1.303 0.12 13.0 3.42 16.5 34.3 33.1 67.4 83.9 108.5 16.5 1.492 0.15 15.0 3.86 19.0 43.9 41.9 85.8 104.8 122.3 11.6 1.387 0.14 11.3 2.81 14.3 53.6 44.8 98.4 112.6 18.9 8.5 1.774 0.93 1.5 1.95 4.4 2.1 8.3 10.3 14.7 220.1 15.6 1.277 0.28 23.9 4.68 28.9 137.3 79.7 216.9 245.8 241.6 16.9 1.009 0.35 22.3 4.25 26.9 123.4 82.7 206.2 233.1 189.1 11.4 1.298 0.30 13.4 3.74 17.4 82.2 65.4 147.6 165.1 385.7 44.0 0.938 0.22 33.8 19.40 53.4 121.7 168.5 290.2 343.6 116.1 8.0 1.445 0.27 10.4 3.66 14.3 47.0 60.7 107.7 122.0 89.9 8.6 1.535 0.17 4.4 3.58 8.2 18.3 33.3 51.6 59.7 Page 59 6/26/2007 Table 15. Variability in soil phosphorus forms measured on replicate soil cores from two stations along a transect in Taylor Creek STA. Three cores were taken from each station. Parameter Station Loosely bound P, mg kg-1 Fe-/Al-P, mg kg-1 20 37 20 37 20 37 20 37 20 37 20 37 Ca-/Mg-P, kg kg-1 Organic P, mg kg-1 Residual P, mg kg-1 Sum TP, mg kg-1 krr 0-10 cm Mean 0.23 1.93 17.3 44.6 3.6 13.6 61.3 264 45.4 238 128 562 Page SD 0.11 0.69 0.68 6.0 0.5 3.0 6.7 46.1 1.1 18 6.8 73.7 CV (%) 47 36 4 13 14 22 11 17 2 8 5 13 60 10-30 cm Mean 0.14 0.31 13.1 19.9 3.4 4.2 43.9 114 40.0 75.9 100 215 6/26/2007 SD 0.01 0.04 1.9 5.7 0.53 0.47 9.6 28.6 6.1 28.6 14.8 43 CV (%) 7 13 15 29 16 11 22 25 15 37 15 20 Table 16. Relationship between soil phosphorus forms and total phosphorus in soils collected along a transect in Taylor Creek STA. *Total inorganic P represents sum of inorganic P extracted by alkali and acid. **Pi- [Me-TC] represents inorganic P complexed with metal and organic matter Regression equation: P form = m TP + b R2 n KCl-Pi = 0.0033 TP + 0.124 0.609 26 Fe-/Al-bound P = 0.086 TP + 3.76 0.924 26 Ca-/Mg-bound P = 0.029 TP + 1.22 0.608 26 Total Inorganic P (Pi)* = 0.116 TP + 3.86 0.887 26 Extractable Organic P = 0.463 TP + 6.46 0.963 26 Residual P = 0.421 TP + 2.6 0.976 26 [NaOH-HCl]Pi = 1.802 [HCl]Pi - 5.6 0.907 26 Pi- [Me-TC]** = 0.06 TP - 3.9 0.871 26 Total Inorganic P: Total inorganic P (TPi) is the sum of P extracted with KCl, NaOH, and HCl. Total Pi was also estimated by a single extraction with 1 M HCl. Both methods showed similar trends and were highly correlated (P = 0.0001), but showed varying extraction efficiencies. The following empirical relationship was observed between TPi and Pi extracted with 1 M HCl: TPi = 1.802[HCl-Pi] – 5.6; R2 = 0.907; n = 26 In other studies, Reddy et al., (1998b) showed 1:1 relationship between these extraction methods. Their results suggested that 1 M HCl is strong enough to dissolve mineral and amorphous forms of P bound to iron, aluminum, calcium, and magnesium. For Taylor Creek STA soils, only 55% of the inorganic P was extracted with 1 M HCl, suggesting presence of other forms of P that are resistant to HCl treatment. A sequential extraction with alkali and acid, resulted in solubilization P held in the soil. It is hypothesized that P in the Taylor Creek STA soils was probably bound to metal-organic matter complexes. With this assumption, we estimated P bound to metal-organic matter (Me-TC) as follows: Pi- [Me-TC] = TPi [alkali-acid extraction] – HCl-Pi krr Page61 6/26/2007 Where: Pi- [Me-TC] is the inorganic P bound to metal-organic matter complexes; TPi [alkaliacid extraction] is the total inorganic P extracted during the sequential alkali and acid extraction (Figure 21); HCl-Pi is the single extraction with 1 M HCl (Reddy et al., 1998b). The estimated Pi- [Me-TC] showed strong correlation with total carbon (TC) of soils. Pi- [Me-TC] = 0.282 TC + 2.7; R2 = 0.893; n = 26 This pool accounted for approximately 6% of the total P in both surface and subsurface soils (Table 15). Alkali Extractable Organic Phosphorus: This fraction includes both living and dead sources of organic P associated with humic and fulvic acids. The NaOH-Po, fraction was estimated as the difference between total P of the NaOH extract and SRP concentration in the NaOH extracts. This pool is termed as Organic P. At all locations, organic P was higher in surface layers and decreased with depth (Figure 24 and Tables 14, 15 and 16). Alkali extractable organic P accounted for 22 to 50% in surface layers and 14 to 56% in 10-30 cm soils. 350 300 0-10 cm 10 - 30 cm 250 200 R e p lic a t e co re s R e p lic a t e co re s 150 100 Phosphorus [mg kg-1] O r g a n ic P 50 0 700 R e s id u e P 600 500 400 300 R e p lic a t e co re s R e p lic a t e co re s 200 100 0 300 R e p lic a t e co re s 250 T o tal P 200 150 R e p lic a t e co re s 100 50 0 20 20 20 46 9 14 17 42 49 34 37 37 37 S ta tio n s a lo n g th e T ra n s e c t Figure 24. Distribution of alkali extractable organic P, residual stable P, and total P of soils collected along a transect in Taylor Creek STA. Results suggest that a major proportion of P is stored in the organic pool (22-56% of the total P in surface soils). Similarly, 14 to 56% of the total P was present in alkali extractable organic P in subsurface soils (10-30 cm depth). Alkali solutions are used to extract humic and fulvic acids krr Page62 6/26/2007 and organic P recovered in such extracts is considered to have been bound to humic substances. However, the relative stability of organically bound P is unknown. Residual Non-reactive P: Residual P is highly refractory and may not be bioavailable. This pool is not soluble either in alkali or acid. Residual stable P accounted for 34 to 60% of total P in 0-10 cm soil and 32 to 62% in the 10 -30 cm soil (Figure 24; Tables 14, 15 and 16). Stability of residual P under different hydrologic conditions is unknown and needs further investigation. 0 – 10 cm depth Residual P 44.6% Exch- P 0.4% Fe-/Al-P 10.1% Ca-/Mg- P 4.0% Organic P 40.9% 10 – 30 cm depth Residual P 46.3% Exch- P 0.7% Fe-/Al-P 10.1% Ca-/Mg- P 4.5% Organic P 38.4% Figure 25. A summary of labile and non-labile pools of phosphorus in soils collected along a transect in Taylor Creek STA. In conclusion, a large proportion of soil phosphorus is present in two major pools: alkali extractable organic P; and residual P stable in both alkali and acid solutions (Fig. 25). Approximately 40% of the total P is in stable pool, while another 45% is present in organic P pool. Stability of these two pools under varying hydrologic conditions needs further investigation. krr Page63 6/26/2007 4.0 Phosphorus Retention Properties of Soils Phosphorus (P) sorption/desorption reactions in wetland soils are important because they buffer soil porewater P concentrations and regulate P availability to plants, microorganisms and overlying waters (Axt and Walbridge, 1999). Phosphorus sorption is often characterized by an initial rapid P uptake by solid from solution (processes such as ion exchange, ligand exchange) followed by a slower P uptake, which is governed by diffusion and precipitation processes (Reddy et al. 2004). The objectives of this study were to: (1) describe P sorption parameters of soils in the proposed STA under aerobic and anaerobic conditions; and (2) determine the maximum P retention capacity of soils using adsorption isotherms. 4.1 Materials and methods To evaluate the P retention properties of the soils, batch incubation studies were conducted on selected soils at the 9 locations (18 soils at two depths; Figure 21) and single-point isotherms were performed at all 42 locations (Figure 3). The batch incubation studies were conducted under aerobic and anaerobic conditions. Batch incubation under aerobic conditions Phosphate sorption was measured using one gram of an air-dried, homogenized soil treated with 10 mL of 0.01M KCl solution containing various levels of P (ranging from 0 to 100 mg P L-1) in 50 mL centrifuge tubes. The tubes were placed on a mechanical shaker for a 24-hour equilibration period. At the end of the period, the soil samples were centrifuged at 6000 rpm for 10 min and the supernatant filtered through a 0.45 µm membrane filter and the filtrate analyzed for soluble reactive P (Murphy and Riley, 1962) using a TechniconTM Autoanalyzer (EPA 365.1). All extractions and determinations were at room temperature. Batch incubation under anaerobic conditions One gram each of soil samples were pre-incubated anaerobically with 5 mL of deionized water for four weeks and the samples were purged with N2 weekly to maintain anaerobic conditions. At the end of incubation, 5 mL of graded series of P solutions in 0.02M KCl from 0 to 200 mg P L-1 was added so the final concentrations were the same as for the aerobic studies. The samples were equilibrated on a mechanical shaker for 24 hours at room temperature. The amount of P that disappeared from solution after 24-h equilibration represents the fraction of P sorbed by the soil. Single point isotherms Single point isotherms (SPI) were determined for the surface and subsurface soils collected in this study (Figure 3). The procedure involves equilibrating a known amount of air-dried soil with deionized water spiked with 100 mg P L-1 at a 1:20 soil to solution ratio on a mechanical shaker for 24h at room temperature. The amount of P lost from solution after 24h equilibration was used to determine the maximum P retention capacity of the soils. krr Page64 6/26/2007 Calculations The total amount of P adsorbed on sediments can be calculated as follows: [1] S = S’ + So Where, S = total adsorbed P in sediment (mg kg-1), S’ = amount of added P retained by sediment (mg kg-1), and So = initial or native sorbed P in sediment (mg kg-1). Since at low equilibrium concentrations the relationship between S’ and C (equilibrium concentrations) is typically linear (Rao and Davidson 1979), the So can be estimated by a least square fit using the following equation (Reddy et al., 1998): S’ = Kd*Ct – So [2] Where, Ct = solution P concentration measured after 24-h equilibration (mg L-1). By plotting the linear form of equation [2], i.e., S’ vs. Ct, the intercept is equal to So and slope is equal to Kd, a linear adsorption coefficient (L kg-1) estimated without taking into account initially sorbed P (So). So was estimated using a least square fit of S' measured at low (< 10 mg P L-1) equilibrium concentrations, C. At these concentrations, the linear relationship between S' and C can be described by S' = bC - So where b is the linear adsorption coefficient (Gale et al., 1994; Graetz and Nair, 1995; Reddy et al., 1998a). The linear portion of the graph used in the calculations had r2 values of at least 0.95. The method used for calculations of So using actual data points was illustrated by Graetz and Nair (1995). A frequently used term in P sorption phenomena, EPCo, an equilibrium P concentration (mg L-1), can be defined as the concentration of P in solution where no net adsorption or desorption of P occurs, i.e., S’ = 0. Thus, by substituting the values of S’ and Ct in equation [2], EPCo can be calculated as follows: EPCo = So/Kd [3] The P sorption parameters, sorption maxima (Smax) and bonding energy constant (k) were estimated using Langmuir equation: Ct/S = 1/k*Smax + Ct/Smax [4] where: S = S' + So, the total amount of P sorbed, mg kg-1 S' = P sorbed by the solid phase, mg kg-1 So = P originally sorbed on the solid phase, mg kg-1 C = concentration of P after 24 h equilibration, mg L-1 Smax = P sorption maximum, mg kg-1 k = a constant related to the bonding energy, L mg-1 P krr Page65 6/26/2007 4.2 Results and discussion Langmuir Sorption Parameters under Aerobic and Anaerobic Conditions The Langmuir sorption parameters for the nine selected soils for the two depths (0-10 cm and 1030 cm) are provided; Table 17 for aerobic conditions and Table 18 for anaerobic conditions. Details of the calculations are given in Appendix 3 (aerobic conditions) and Appendix 4 (anaerobic conditions). Other pertinent information including replications can be found in Appendix 5 for aerobic conditions and in Appendix 6 for anaerobic conditions. Correlation coefficients of aerobic P sorption parameters with soil characteristics and P fractionation data are given in Table 19 for aerobic conditions and Table 20 for anaerobic conditions. Smax-aero (mg/kg) 500 y = 1.1143x + 4.5232 2 R = 0.8881 400 a 300 200 100 0 0 100 200 300 400 500 P100 Sorbed-aero (mg/kg) Smax-anaero (mg/kg) 600 y = 0.9304x + 1.1784 500 2 R = 0.9265 400 b 300 200 100 0 0 100 200 300 400 500 600 P100 Sorbed-anaero (mg/kg) Figure 26. Relationship between Langmuir Smax and P sorbed at 100 mg P L-1 under (a) aerobic and (b) anaerobic conditions. krr Page66 6/26/2007 Relationships for Smax with P sorption as determined by the single point isotherm procedure indicate that Smax can be predicted with reasonable accuracy under aerobic and anaerobic conditions using single-point isotherms (Figure 26). This relationship is well documented for upland soils (Nair et al., 1998) as well as wetland soils and stream sediments (Reddy et al., 1998a). Relationships for other Langmuir sorption parameters under aerobic and anaerobic conditions are provided in Table 21. The P sorption maximum (Smax) values under aerobic conditions (Table 17) for both the 0-10 cm depth and the 10-30 cm depth do not show a definite trend from the inflow to the outflow. Values of Smax under aerobic conditions range from approximately 400 mg kg-1 at the 10-30 cm depth at the beginning of Cell 2 (Site 42) to <20 mg kg-1 at both soil depths at Site 34 in the same Cell. Based on the retention capacity parameters of the STA soils, it appears likely that a part of the surface horizons may have been removed during the STA construction, and the present “surface” 0-10 and 10-30 cm soils could be a mixture of A, E, and Bh horizon soils with properties that are not typical of surface horizons of other upland soils within the Basin. It is assumed that the STA was constructed on Spodosols, which is the predominant soil order in the Lake Okeechobee Basin. Stepwise regression of Smax with HCl-Ca, Mg, Fe, Al and TC under aerobic conditions gave the following: Smax-aero (mg/kg) = 0.026*[HCl-Ca] + 0.111*[HCl-Fe] + 0.025*[HCl-Al] - 58.82 (R2 =0.82, p<0.0001, n=26) Smax values for soils and sediments of the Lake Okeechobee Basin are usually associated with Fe, Al and organic matter (Nair et al., 1999; Reddy e al., 1998a). The STA stepwise regression equation suggests Ca as a contributor to Smax as well. Definite trends from inflow to outflow were not found for the other Langmuir parameters, So, EPC or k. The situation was similar under anaerobic conditions (Table 18). So and EPC were correlated to both HCl-extractable Ca and Mg under aerobic conditions (Table 19). Under anaerobic conditions, EPC values were correlated to Ca and Mg; there were no significant correlations of So to any of the metals. The presence of Ca and Mg reduces k, the bonding capacity of the soil as noted by negative significant correlations (Table 19). Previous studies on Spodosols of the Lake Okeechobee Basin (Nair et al. 1998) showed that So was significantly correlated to Mehlich 1 extractable Mg, particularly for soils of the spodic (Bh) horizon. The study also showed that k was significantly correlated to Mehlich 1-extractable Ca in the surface A and E horizons, and negatively to Mg concentrations in the Bh horizons. Smax appeared to change minimally under anaerobic conditions (Figure 27). The retention capacity of the STA soils will therefore be little affected by flooded conditions. krr Page67 6/26/2007 Table 17. Langmuir sorption parameters (P originally sorbed on the solid phase, So; equilibrium P concentrations, EPC; the P retention maximum, Smax and the P bonding energy constant, k) for the Taylor Creek STA soils at the nine selected locations under aerobic conditions. Cell # Site From inflow outflow Depth So EPC to Smax k cm mg kg-1 mg -1 L mg kg-1 L mg P-1 1 20† 0-10 5.0 0.04 160 0.22 1 10-30 5.6 0.03 135 0.30 1 46 0-10 12.1 2.32 141 0.05 1 10-30 2.8 0.02 101 0.42 1 9 0-10 17.1 1.47 267 0.04 1 10-30 2.7 0.04 88 0.50 1 14 0-10 1.1 0.05 263 0.06 1 10-30 3.4 0.02 89 0.85 1 17 0-10 4.2 0.36 221 0.04 1 10-30 1.6 0.02 109 0.22 2 42 0-10 3.2 0.02 107 0.23 2 10-30 16.1 0.04 407 0.25 2 49 0-10 6.3 0.07 221 0.15 2 10-30 4.0 0.02 152 0.21 2 34 0-10 0.1 0.01 18 0.18 2 10-30 0.0 0.00 12 1.06 2 37 0-10 18.9 2.56 252 0.03 10-30 4.2 0.07 204 0.15 † Mean of triplicates ‡ SPI = P sorption as measured by the single-point isotherm method krr Page68 SPI‡ mg kg-1 158 129 101 96 196 81 239 83 182 104 101 388 209 149 22 9 162 192 6/26/2007 Table 18. Langmuir sorption parameters (P originally sorbed on the solid phase, So; equilibrium P concentrations, EPC; the P retention maximum, Smax and the P bonding energy constant, k) for the Taylor Creek STA soils at the nine selected locations under anaerobic conditions. Cell # Site From inflow to outflow Depth cm So mg kg-1 EPC mg -1 L Smax mg kg-1 k L mg P-1 1 20† 0-10 14.6 0.02 239 0.35 1 10-30 5.3 0.01 210 0.29 1 46 0-10 1 10-30 9.1 0.02 184 1.21 1 9 0-10 10.9 0.20 368 0.05 1 10-30 2.0 0.02 148 0.30 1 14 0-10 8.3 0.14 326 0.16 1 10-30 8.1 0.01 105 0.39 1 17 0-10 7.2 0.26 263 0.08 1 10-30 3.0 0.01 59 -0.67 2 42 0-10 1.3 0.01 100 0.24 2 10-30 39.7 0.15 519 0.10 2 49 0-10 1.9 0.02 225 0.15 2 10-30 0.2 0.00 70 0.96 2 34 0-10 2 10-30 2 37† 0-10 2 10-30 1.7 0.09 180 0.10 † Mean of triplicates ‡ SPI = P sorption as measured by the single-point isotherm method SPI‡ mg kg-1 208 182 173 332 150 299 100 232 54 96 488 280 67 180 Note: Data are not provided for some of the samples since it was not possible to obtain Langmuir isotherms for some soils under anaerobic conditions. These soils are likely P sources and not P sinks. krr Page69 6/26/2007 Table 19. Correlation coefficients of aerobic P sorption parameters† with soil characteristics and P fractionation data. n So EPC Smax k SPI pH 1M HCl-Ca 1MHCl-Mg 1MHCl-Fe !MHCl-Al Loss on ignition Total N Total C Total P Total inorganic P Water soluble P Mehlich 1-P KCl Pi‡ NaOH Pi‡ HCl Pi‡ Sum TPi‡ NaOH Po‡ Residue P‡ Sum TPo‡ So 26 1 0.803 0.686 -0.412 0.509 -0.571 0.794 0.774 0.085 0.149 0.881 0.870 0.889 0.894 0.825 0.851 0.738 0.738 0.862 0.717 0.851 0.877 0.885 0.894 EPC 26 Smax 26 k 26 SPI 26 1 0.334 -0.429 0.055 -0.466 0.609 0.691 -0.163 -0.143 0.800 0.778 0.800 0.854 0.591 0.857 0.511 0.785 0.754 0.535 0.722 0.851 0.843 0.860 1 -0.572 0.883 -0.648 0.862 0.769 0.191 0.411 0.763 0.776 0.774 0.723 0.794 0.486 0.786 0.363 0.751 0.761 0.772 0.678 0.722 0.709 1 -0.417 0.536 -0.506 -0.592 0.066 0.091 -0.560 -0.566 -0.559 -0.580 -0.454 -0.402 -0.397 -0.252 -0.583 -0.414 -0.546 -0.578 -0.548 -0.572 1 -0.531 0.713 0.588 0.181 0.570 0.531 0.532 0.537 0.497 0.627 0.184 0.578 0.081 0.515 0.541 0.530 0.447 0.486 0.472 correlation coefficient: r=0.381 at α=0.05 correlation coefficient: r=0.487 at α=0.01 † So= Native Sorbed P; k=constant related to bonding energy; Smax=P sorption maximum; SPI=Single Point P Isotherm (100 mg L-1) ‡ Parameters from the fractionation studies (see Task 3.0) krr Page70 6/26/2007 Table 20. Correlation coefficients of anaerobic P sorption parameters† with soil characteristics and P fractionation data. n So EPC Smax k SPI pH 1M HCl-Ca 1M HCl-Mg 1M HCl-Fe !M HCl-Al Loss on ignition Total N Total C Total P Total inorganic P Water soluble P Mehlich 1-P KCl Pi‡ NaOH Pi‡ HCl Pi‡ Sum TPi‡ NaOH Po‡ Residue P‡ Sum TPo‡ So 22 1 0.267 0.708 0.022 0.570 -0.037 0.402 0.064 0.269 0.147 0.326 0.328 0.335 0.343 0.552 0.067 0.566 0.088 0.358 0.423 0.389 0.220 0.363 0.306 EPC 22 1 0.565 -0.284 0.360 -0.471 0.602 0.609 0.203 0.052 0.709 0.732 0.748 0.729 0.617 0.582 0.625 0.452 0.750 0.620 0.731 0.744 0.741 0.774 Smax 22 1 -0.112 0.765 -0.404 0.686 0.493 0.529 0.156 0.702 0.729 0.728 0.737 0.860 0.407 0.860 0.361 0.757 0.750 0.779 0.619 0.735 0.708 k 22 SPI 28 1 -0.099 0.302 -0.266 -0.308 0.163 -0.026 -0.288 -0.298 -0.301 -0.310 -0.254 -0.185 -0.266 -0.132 -0.295 -0.214 -0.276 -0.307 -0.289 -0.310 correlation coefficient: r=0.413 at α=0.05 correlation coefficient: r=0.526 at α=0.01 † So= Native Sorbed P; k=constant related to bonding energy; Smax=P sorption maximum; SPI=Single Point Isotherm (100 mg/L) (1:20) ‡Parameters from the fractionation studies (see Task 3.0) krr Page71 6/26/2007 1 -0.531 0.713 0.588 0.181 0.570 0.531 0.532 0.537 0.497 0.627 0.184 0.578 0.081 0.515 0.541 0.530 0.447 0.486 0.472 Smax-anaero (mg/kg) 600 y = 1.1835x + 4.1579 2 R = 0.7188 500 400 1:1 300 200 100 0 0 100 200 300 400 500 600 Smax-aero (mg/kg) Figure 27. Relationship between Langmuir Smax under aerobic and anaerobic conditions. Table 21: Correlation coefficients of Langmuir parameters† under aerobic conditions. n SPI‡ So (aerobic) Smax (aerobic) 28 28 28 n So (aerobic) 28 1 0.506 EPC (aerobic) 28 0.055 0.804 Smax (aerobic) 28 1 0.881 0.688 k (aerobic) 28 -0.417 -0.409 -0.569 So (anaerobic) 22 0.568 0.544 0.571 0.423 EPC (anaerobic) 22 0.362 0.665 Smax (anaerobic) 22 0.731 0.713 0.816 k (anaerobic) 22 -0.026 -0.006 -0.069 and anaerobic k (aerobic) 28 1 0.037 -0.440 -0.321 0.169 † So=native sorbed P; k=constant related to bonding energy; Smax=P sorption maximum; SPI=single point isotherm. n=28 r=0.367 at α=0.05 r=0.470 at α=0.01 krr n=22 r=0.413 at α=0.05 r=0.526 at α=0.01 Page72 6/26/2007 Results of this study show that the physico-chemical properties of Taylor Creek STA soils exhibit significant P retention capacity within the top 30 cm. Low EPC values suggest that these soils potentially function as sinks for P at relatively low concentrations. The P retention capacity of these soils was not be adversely impacted by flooding as indicated by minimal differences in Smax values under aerobic and anaerobic conditions. Long-term effectiveness of STA soils depends on P loading and contact of water column P with underlying soils. In addition several other factors such as vegetation and extent of particulate matter accretion can also affect the overall capacity of soils to retain P. The biogeochemical processes occurring in a wetland soil are dependent on its chemical composition, mineral components, and physicochemical and biological factors. Phosphorus reactivity in soils, for example, changes drastically, depending on whether the soil is calcareous or non calcareous, as moisture regime and hydrology shifts from unsaturated to saturated and prolonged submerged conditions. The complexity of P biogeochemistry in wetlands is compounded by the presence of high organic matter. Hence, chemical characterization and quantification of soil P fractions (organic and inorganic) and other components in wetlands, such as those in STAs, constitute an important component in understanding P dynamics and the effects of hydroperiod on P stability in accreted material. Burial or accretion of organic matter has been reported as a major mechanistic long-term sink for P in wetlands. Wetland soils tend to accumulate organic matter due to the production of detrital material from biota and the suppressed rates of decomposition. Soil accretion rates for constructed wetlands can range between a few millimeters to more than one centimeter per year. Accretion rates in productive natural wetland systems such as the Everglades have been reported as high as one centimeter or more per year. The genesis of this new material is a relatively slow process, which may affect the nutrient retention characteristics of the wetland. With time, productive wetland systems will accrete organic matter that has different physical and biological characteristics than the underlying soil. Management of newly accreted material by consolidation, hydrologic manipulation (water level drawdown), application of soil amendments and/or soil removal can improve the overall longevity of STAs to maintain water quality. Phosphorus management in STAs has been a major focus of the SFWMD. In wetlands, P cycling is tightly coupled to organic matter turnover and cycling of other nutrients such as nitrogen and sulfur. A recent series of papers on STA-1W published in a special issue of Ecological Engineering (Reddy et al., 2006) indicates the importance of hydrology, vegetation, periphyton, and biogeochemical processes regulating long-term retention of P in wetlands. However, to understand the long-term performance of STAs it is critical to determine the fundamental processes and the linkages between those processes for effective long-term P management. 5.0 References Axt, J. R., and M. R. Walbridge. 1999. Phosphate removal capacity of palustrine forested wetlands and adjacent uplands in Virginia. Soil Sci. Soc. Am. J. 63:1019-1031. krr Page73 6/26/2007 Campbell, K. 1999. A written summary report on the use of New Palm Dairy as a site for STA development. Chang, S.C., and M.L. Jackson. 1957. Fractionation of soil phosphorus. J. Soil. Sci. 84:133144. Gale, P.M., KR. Reddy, and D.A. Graetz. 1994. Phosphorus retention by wetland soils used for treated wastewater disposal. J. Environ. Qual. 23:370-377. Graetz, D.A., and V.D. Nair. 1995. Fate of phosphorus in Florida Spodosols contaminated with cattle manure. Ecol. Eng. 5:163-181. Nair, V.D., D.A. Graetz, and K.M. Portier. 1995. Forms of phosphorus in soil profiles from dairies of south Florida. Soil Sci. Soc. Am. J. 59:1244-1249. Nair, V. D., D. A. Graetz and K. R. Reddy. 1998. Dairy manure influences on phosphorus retention capacity of Spodosols. J. Environ. Qual. 27:522-527. Olila, O.G., K.R. Reddy, and W.G. Harris, Jr. 1995. Forms and distribution of inorganic phosphorus in sediments of two shallow eutrophic lakes in Florida. Hydrobiologia. 302:147-161. Psenner, R., B. Bostrom, M. Dinka, K. Pettersson, R.Pucsko, and M. Sager. 1988. Fractionation of phosphorus in suspended matter and sediment. Arch. Hydrobiol. Beih. Ergebn. Limnol. 30:98-103. Reddy, K.R. 1999. A written evaluation and recommendations on the efficacy of New Palm Dairy as a site for STA development. Reddy, K. R., O. A. Diaz, L. J. Scinto, and M. Agami. 1995. Phosphorus dynamics in selected wetlands and streams of the Lake Okeechobee Basin. Ecol. Eng. 5:183-208. Reddy, K.R., G.A. O’Connor, and P.M. Gale. 1998a. Phosphorus sorption capacities of wetland soils and stream sediments impacted by dairy effluent. J. Environ. Qual. 27:438-117. Reddy, K.R., Y. Wang, W.F. Debusk, M.M. Fisher, and S. Newman. 1998b. Forms of soil phosphorus in selected hydrologic units of the Florida Everglades. Soil Sci. Soc. Am. J. 62:1134-1147. Reddy, K.R., R.H. Kadlec and M.J. Chimney. 2006. Editorial: the Everglades Nutrient Removal Project. Ecological Engineering 27(4): 265-267. Ruttenberg, K. C. 1992. Development of sequential extraction method for different forms of phosphorus in marine sediments. Limnol. Oceanogr. 37:1460-1482. Stanley Consultants, Inc. 2002. Lake Okeechobee Water Retention/Phosphorus Removal Project. Design Analysis Report. Final Submittal. Volume I. August krr Page74 6/26/2007 9, 2002. Wetland Solutions, Inc. 2004. Okeechobee Stormwater Treatment Areas (STAs) Research and Management Plan for Performance Optimization. January 2004. krr Page75 6/26/2007
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