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Agronomic and environmental characterization of phosphorus in biosolids produced and/or marketed in Florida


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1 AGRONOMIC AND ENVIRONMENTAL CHARAC TERIZATION OF PHOSPHORUS IN BIOSOLIDS PRODUCED AND/OR MARKETED IN FLORIDA By SARAH L. CHINAULT A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2007

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2 2007 Sarah L. Chinault

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3 To Mom, Dad, Amanda, Chris, and Richelle.

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4 ACKNOWLEDGMENTS I would first like to thank Dr. O’Connor, my supervisory committee chair. While there were times of great frustration (for both of us !) I am much better prep ared for a professional career thanks to his teachings. Thanks also go to Drs. Sartain and Elliott for serving on my committee. I must thank Scott Br inton. Without his help, this project would have been beyond my capability. Scott has the ability to handle endl ess interruptions and stupid questions without ever losing patience, for which I am grateful. Sc ott tended to daily green house responsibilities, and provided major help during harvests a nd leachings. Thanks go to Sampson AgyinBirikorang, who helped with the statistical mani pulations of data. Sampson also has endless patience and always made time to assist, even when his own duties were great. When I was swamped with laboratory analyses, Matt Miller was a great help with dishes and other “lab monkey” duties, which helped me maintain my sa nity. Thanks go to Maria Silveria, who helped me learn laboratory procedures when I starte d my working on my degree. Thanks go to the College of Agriculture and Life Science (CALS) for providing a matching assistantship to pay for my tuition. Additional stipend and research support was provided by the Florida Water Environment Association (FWEA )-Utilities Council and Mi lorganite, Inc. Lastly, thanks go to my family and friends, who supported me emoti onally and financially (Dad!) through all my years at UF.

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5 TABLE OF CONTENTS page ACKNOWLEDGEMENTS....4 LIST OF TABLES..7 LIST OF FIGURES. ABSTRACT...12 CHAPTER 1 INTRODUCTION.14 Hypotheses and Research Objectives Study Approach.18 2 MATERIALS AND METHODS..19 Materials Year 1 Glasshouse and St atic Incubation Studies..19 Laboratory Characterization..20 Dynamic Laboratory Incubation Glasshouse Study...26 Statistical Analysis.29 3 RESULTS AND DISCUSSION Laboratory Characterization.. Dynamic Laboratory Incubation....35 Glasshouse Study... Yields.43 Phosphorus Uptake and Re lative Phytoavailability...45 Phosphorus Leaching.49 4 CONCLUSIONS...70 Dynamic Laboratory Incubation Glasshouse Study...72 Land Applying BPR or BPR-like Residuals..74 APPENDIX GLASSHOUSE ANOVA AND CU MULATIVE DATA....................76

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6 LIST OF REFERENCES………………...……………………..…….…………………………82 BIOGRAPHICAL SKETCH…………………………………….……………...…….………...85

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7 LIST OF TABLES Table page 2-1 Selected proper ties of Immokalee fine sand………………………….………………….30 3-1 Materials received for laboratory characterization………………………………...……51 3-2 Selected general ch emical properties of materials………………………………...…….52 3-3 Selected phosphor us properties of materials…………………………………………….53 3-4 Comparison of TP concentrations determined by 3 digestion methods…………...…....54 3-5 Dynamic laboratory incubation: cumulative SRP released and SRP released (% of applied P)…………………………………………………………………………55 3-6 Cumulative Bahiagrass tiss ue P concentrations after 4 harvests……………………..…65 3-7 Relative phosphorus phytoa vailability of biosolids to TSP. …………………………....66 3-8 Various RPP es timate model f it statistics….……………………………...….…………67 3-9 Point estimates of RPP for Milorganite and Lakeland NS biosolids…………………………..……………….……………………………...…….69 A-1 Cumulative Bahiagrass P upt ake after 4 harvests ANOVA...…………...………...…….76 A-2 Cumulative Bahiagrass yield after 4 harvests ANOVA.………………..………………77 A-3 Cumulative P leached in glasshouse experiment ANOVA …………………………….78 A-4 Cumulative Bahiagrass yields after 4 harvests………………………....…………...…..79 A-5 Cumulative P uptake for Bahiagrass after 4 harvests……………….…………………..80 A-6 Cumulative P leached after 4 leachings…………………………………………………81

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8 LIST OF FIGURES Figure page 3-1a P rate: 56 kg P ha-1. Cumulative SRP released (% of applied P) as a function of P source. ...56 3-1b P rate: 224 kg P ha-1. Cumulative SRP released (% of applied P) as a function of P source..56 3-2a P rate: 56 kg P ha-1. Dynamic laboratory incubation: cumu lative P released (% of applied P) as a function of biosolids-PWEP...... 3-2b P rate: 224 kg P ha-1. Dynamic laboratory incubation: cumulative P released (% of applied P) as a function of biosolids-PWEP..57 3-3a P rate: 56 kg P ha-1. Dynamic laboratory incubation: cu mulative P released as a function of biosolids-PSI......58 3-3b P rate: 224 kg P ha-1. Dynamic laboratory in cubation: cumulative P released as a function of biosolids-PSI..58 3-4a P rate: 56 kg P ha-1. Dynamic laboratory incubation: cumula tive P released (% of applied P) per released event..59 3-4b P-Rate: 224 kg P ha-1. Dynamic laboratory inc ubation: cumulative P released (% of applied P) per released event. ......60 3-5a P rate: 56 kg P ha-1. Cumulative Bahiagrass yi elds after 4 harvests......61 3-5b P-rate: 112 kg P ha-1. Cumulative Bahiagrass yiel ds after 4 harvests...61 3-5c P rate: 224 kg P ha-1. Cumulative Bahiagrass yiel ds after 4 harvests........62 3-6 Cumulative Bahiag rass yield-weighted tissue P c oncentrations after 4 harvests...62 3-7 P rate: 224 kg P ha-1. Bahiagrass N tissue concentrations in each harvest.... 3-8 P rate: 224 kg P ha-1. Bahiagrass yield-weighted N co ncentrations after 4 harvests....63 3-9a P rate: 56 kg P ha-1. Cumulative Bahiagrass P upt ake after 4 harvests.........64 3-9b P-rate: 112 kg P ha-1. Cumulative Bahiagrass P uptake after 4 harvests...........64 3-9c P-rate: 224 kg P ha-1. Cumulative Bahiagrass P uptake after 4 harvests.......4 3-1 0 Cumulative Bahiagrass P upt ake as a function of P applied..66

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9 3-11 Plateau model: P uptake from Milorganite treatments as a function of P applied…….....68 3-12 Relative phosphorus phytoav ailability (RPP) as a func tion of biosolids-PWEP……..….69

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10 LIST OF ABBREVIATIONS Al aluminum AN ammonium nitrate ANOVA analysis of variance BAP biologically available phosphorus BPR biological phosphorus removal C carbon Ca calcium DDI distilled, de-ionized water EC electrical conductivity FDEP Florida Department of Environmental Protection Fe iron ICP inductively coupled plasma spectrophotometry K potassium LOI loss on ignition Mg magnesium N nitrogen P phosphorus PSC phosphorus source coefficient PSI phosphorus saturation index PV pore volume PWEP percent water-e xtractable phosphorus RPA relative phosphorus adsorption

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11 RPP relative phosphorus phytoavailability SRP soluble reactive phosphorus S sulfur TC total carbon TN total nitrogen TP total phosphorus TRT treatment TSP triple super phosphate UF University of Florida USEPA United States Environmental Protection Agency WEP water-extractable phosphorus WTR water treatment residual WWTP wastewater treatment plant

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12 Abstract of Thesis Presen ted to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Science AGRONOMIC AND ENVIRONMENTAL CHARAC TERIZATION OF PHOSPHORUS IN BIOSOLIDS PRODUCED AND/OR MARKETED IN FLORIDA By Sarah L. Chinault May 2007 Chair: George O’Connor Major Department: Soil and Water Science Land application of biosolids can result in an accumulation of soil phosphorus (P). While excess soil P is typically not harmful to crops, P can migrate offsite and can lead to surface and groundwater impairment. Increased concern over accelerated eutrophication of water bodies has led to heightened scrutiny and regulation of biosolids land app lication. Regulation could include limiting application rates to match crop P requireme nts (P-based rates). If P-based regulations are imposed, it will be critical to understand bios olids P phytoavailability and the potential for surface and groundwater impairment from biosolid s P. We conducted laboratory and glasshouse studies to provide understandi ng. A laboratory incubation wa s conducted using small soil columns to assess P release potential: 11 biosol ids and triple super phosphate (TSP) were individually mixed with 400 g of a typical low-P sorbing Florida soil (Immokalee fine sand) at two rates: 56 and 224 kg P ha-1. Columns were leached bi-week ly for 14 weeks to attain 60 mL of drainage in each leaching. Soluble reactive P (SRP) was dete rmined and summed over the 8 leachings. Cumulative P release (as a percentage of P app lied) was greatest from biological P removal (BPR) and BPR-like biosolids. Phosphorus release from Milorganite, a thermally dried biosolids high in Fe and Al oxides (44 g kg-1), released ~39% of applied P at the 56 kg P ha-1 rate,

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13 indicating that P releas e was limited by association of P with Fe and Al and by heat drying. In contrast to the moderate P rel ease from Milorganite, P release from the Lakeland NS biosolids, a BPR-like product with low percent solids (3 %), and low Fe and Al content (~12 g kg-1), was ~90% of P applied at 56 kg P ha-1. A glasshouse study utilizing la rge soil columns was conducted: 7 biosolids and TSP were individually mixed with 4 kg sample s of Immokalee soil and Bahiagrass ( Paspalum notatum Flugge) was grown. Bahiagrass was harvested monthly for 4 months and tissue total P (TP) was measured. Four of the biosolids chosen for the glasshouse study had high PWEP values ( 15%), and their P was expected be highly plant avai lable. Indeed, the OCUD S, Lakeland NS, GRU, and Boca Raton biosolids fit into the “high” category of relative P phytoavailability (RPP; >75% of TSP). Two biosolids with low P-solubility (PWEP 1.1%) fit into the moderate RPP category (25-75% of TSP): Milorganite, a nd GreenEdge. One biosolids (Dis ney) with a moderate PWEP (8.4%) also fit into the moderate RPP category. Results of the glasshouse study indicate that no change in biosolids application rate is needed (or justified) for BPR and BPR-like biosolids with RPP values in the high RPP category. However, application rates for Disney and GreenEdge could be approximately doubled to meet crop P need s. Phosphorus in Milorganite is only ~1/3 as phytoavailable as P in TSP, indicating that Milorg anite may be applied at P rates as great as 224 kg P ha-1 (based strictly on phytoavailability). Give n the wide range of RPP values and leaching risks of various biosolids, land application of bi osolids should not be regulated en masse. PWEP, and PSI are easily determined and excellent ga uges of both biosolids agronomic value and P leaching hazard. PWEP is a better indication of how a biosolids might affect the environment than biosolids-TP or soil test P.

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14 CHAPTER 1 INTRODUCTION Throughout history, human and anim al wastes have been recycled to agricultural land to supply nutrients for crops. However, the deve lopment of centralized wastewater treatment systems, and an ever-increasing human population has created biosolids di sposal challenges. The U.S. produced an estimated 6.5 X 106 Mg of biosolids in 2000 and approximately 50-60% of biosolids were disposed of via land-based re cycling (USEPA, 1999). Bi osolids production is expected to increase to 7.5 X 106 Mg yr-1 by 2010. The state of Florida produces about 2.7 X 105 dry Mg of biosolids per year; 66 % of the biosolids are land app lied, 17% are land filled, and 17% are marketed and distributed to the public (F DEP, 2005). In addition to biosolids produced within the state of Florida, 9.1 X 104 Mg of class AA pelletized bios olids are imported each year. Given the large quantities of bi osolids produced, land-based recy cling of biosolids becomes a critical disposal route for municipalities. Biosolids land application can also be an environmentally sound and beneficial practice. Biosolids are a source of essent ial plant elements such as N, P, sulfur, and micronutrients. Thus, land-based recycling of biosolids to agricu ltural land can supply farmers with an economic alternative to chemical fertili zers. Biosolids are also high in organic matter, which can be important in Florida, where soil s are typically sandy and low in organic matter. While the land application of biosolids is bene ficial, long-term biosolids appl ication can result in accumulation of soil P (O’Connor et al., 2005). When biosolids ar e applied at an N-based rate to meet crop N requirements, P is typically ove rsupplied due to differences in biosolids N:P than crop needs. The excessive P accumulation it is not harmful to crops (Person et al., 1994), but leads to accumulation of P in amended soils and potential environmental problems. Migration of P offsite to ground and surface waters is a cause for concern as P is generally the limiting nutrient in

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15 fresh water ecosystems for accelerated eutrophicati on (Carpenter et al., 1 998). P can migrate offsite either in dissolved form, as biosolids particles, or attached to soil particles (Elliott et al., 2005). Most soils in the U.S. have sufficient Psorbing capacity (due to Fe and Al oxides) to prevent P leaching. Elliott et al (2002) showed that even sandy Florida soils with moderate Psorbing capacity can prevent P leaching. In soils with adequate P-sorbing capacity, P loss occurs mostly through erosion and runoff, and erosion c ontrol measures can help control P loss in these soils. Atlantic Coastal Plain soils (including most Florida soils), however, ar e naturally low in Fe and Al oxides. In such soils, P leaching and loss of P dissolved in subsurface flow become the dominant P loss mechanism (He et al., 1999). Excess P in water bodies can l ead to accelerated eutrophica tion. Increased concern over water quality has led to amplified scrutiny of biosolids land application programs and recommendations that biosolids application be limited to meet crop P ne eds (P-based). Limiting biosolids land application to P-based rates woul d significantly reduce bioso lids application rates. When application rates are decreas ed, more land area is required fo r disposal, increasing disposal costs. Lower biosolids application rates also m ean additional N fertilizer is required, increasing costs to farmers, and making land-based recyc ling of biosolids for agronomic benefits less attractive. Recent research suggests that limiting biosolids application to P-based rates is probably unnecessary for conventionally pr oduced biosolids (Brandt et al., 2004). Biosolids-P is not necessarily as labile as P in mineral fertilizers or manures, and lability can be greatly influenced by the wastewater treatment process (Maguire et al., 2001). Treatment processes such as thermal drying can significantly reduce P la bility of biosolids compared to conventionally produced cake (Smith et al., 2002). A possible exception may be biological P removal (BPR) biosolids, in

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16 which the wastewater treatment process is engineer ed to promote luxury uptake of P by bacteria. While the BPR process reduces P concentrations in wastewater effluent, the resulting biosolids have a higher concentration of P than conventio nally produced residuals, and labile P in BPR biosolids may be higher than for conventional or h eat-dried biosolids (Ellio tt et al., 2002; Brandt et al., 2004; O’Connor et al., 2004). Total P (TP) concentration of the biosolids is generally a poor indicator of P lability and phytoavailability. Only a small fraction of P fr om most conventionally produced biosolids is soluble, making most biosolids less likely to negatively impact the environment compared to soluble P sources (mineral fertilizer, manures). The water-extractable P (WEP) content of biosolids has been highly correla ted to P lability (Brandt et al., 2004). For typical biosolids, percent water-extractable P (PWEP = WEP/TP *100) is < 5% (Bra ndt et al., 2004), and phytoavailability (plant-available) P is only 4050% of TSP (USEPA, 1995). Biosolids produced using iron (Fe) and aluminum (Al) salts may ha ve even lower P lability and PWEP values (<0.5%) (Corey, 1992; Brandt et al., 2004). BPR biosolids may ha ve much greater soluble P concentrations than conventionally produced bios olids, and greater PWEP (~ 14%) (Brandt et al., 2004). The phosphorus saturation index (PSI) has also been correlated to environmental P leaching risk (Elliott et al., 2002). PS I is calculated as the molar ra tio of oxalate-extractable P to Fe and Al ([Pox]/[Alox + Feox]). When biosolids have PSI values less than 1.1, little P leaching is expected to occur, even in sandy, low P-sorbing soils (Elliott et al., 2002). Both PWEP and PSI can serve as a priori estimates of biosolids-P lability. Bo th measures can better estimate how P in biosolids will affect the environment when la nd applied than biosolids-TP or soil test P measures (Maguire et al., 2001; Elliott et al., 2002; Brandt et al., 2004 ; O’Connor et al., 2004).

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17 Given the nutrient concerns that accompa ny biosolids land applic ation, each state’s Natural Resources Conservation Service (NRCS) is required by the Unified Strategy for Animal Feeding Operations (USDA/USEPA, 1999) to de velop P management strategies. Under code 590, states have three options to manage P: agronomic soil test P recommendations, environmental soil P thresholds, or a P site in dex to evaluate vulnerability to potential P loss (Elliott and O’Connor, 2007). Most st ates have chosen a P-index approach as both P source and transport factors are taken into account. The P-index acknowledges that for negative environmental impacts to occur, both a soluble P source and a transport mechanism are required (Sharpley et al., 2003). The state of Florida is in the midst of de veloping a P-index to manage P nutrient concerns. Hypotheses and Research Objectives A good understanding of biosolids P phytoavailability relative to fertilizer-P is critical to making adjustments to biosolids application rate s should P-based applica tion restrictions be imposed. All biosolids do not have the same pot ential to negatively affect the environment, hence, it is important to know which biosolids-P chemical charac teristics can be used to judge a priori the environmental impact a bioso lids will have once land applied. Hypothesis 1: Relative P phytoavailability is greater for BPR biosolids than conventionally produced biosolids. Hypothesis 2: P leaching is significantly greater fr om (sandy, low P-sorbing) soil amended with BPR residuals than the same soil amende d with conventionally treated biosolids. Hypothesis 3: P lability of all biosolids is less than fertilizer-P (TSP). Objective 1: Characterize the agronomic value of vari ous biosolids important in Florida so adjustments can be made to biosolids applica tion rates if biosolids P-based regulations are imposed.

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18 Objective 2: Develop sufficient data to demonstrate that most biosolids pose less of an environmental hazard (with the possible exceptio n of BPR biosolids) than readily soluble P sources. Objective 3: Expand the database of knowledge to include a wider variety of biosolids production schemes, specifically materials produced or marketed in Florida. Research was focused on materials not previously studied in detail, specifically BPR materials. Study Approach A full laboratory characterization was conducte d on 21 biosolids produced or marketed in Florida to identify materials wa rranting further study in glasshous e and laboratory experiments. Seven residuals were chosen for a glasshouse study to judge agronomic P availability and environmental lability. Eleven biosolids were chosen for a dynamic laboratory incubation, the purpose of which was to quantify water soluble P, examine the kinetics of P release, and determine the leaching hazard of various biosolids materials.

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19 CHAPTER 2 MATERIALS AND METHODS Materials Wastewater treatment plants (WWTPs) through out Florida were invite d to participate in the research effort by completing a survey (d eveloped by Robert Morrell of PBS&J consulting) of plant operations and materials characteris tics. Completed surveys were submitted by 24 WWTPs, representing 22 residuals products, and re sults were forwarded to UF personnel. Based on survey results, 20 Florida products were reque sted from WWTPs for an alysis. A few samples of biosolids produced in other stat es, but marketed in Florida, were also requested. Milorganite, a commercially available biosolids product from Wi sconsin, was chosen to be included in this study. In total, 21 materials were subject ed to laboratory characterization. Year 1 Glasshouse and Static Incubation Studies In 2005, glasshouse and static laboratory incubation studies were conducted with 9 biosolids: Milorganite, GreenE dge, Jacksonville Cake, Tampa, Di sney Compost, Pinellas Cake, Boca Raton, and Orange County Utilities Division (OCUD) east dry and cake materials. The residuals were individually amended to a typical Florida Spodosol (Immokalee fine sand) at 2 Papplication rates: 56 and 224 kg P ha-1 to represent P-based and N-based biosolids application rates, respectively. Most of th e soil was used in the glasshouse study, but some was used in a static laboratory incubation. The glasshouse stud y was intended to provide measures of P leaching risk and relative P phytoavailability to pa sture grass of various biosolids. Amended soils used in the static laboratory incubation were sampled at various times for WEP and TP determination, and the data were intended to yiel d information about the kinetics of biosolids-P release. Both the glasshouse study and the st atic laboratory incuba tion experiments were terminated in December 2005 because of apparent un-equal P loadings in treatments. We have

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20 no explanation for the unequal P loads, but without equal P loadings, conc lusions on relative P phytoavailability and P leaching were not possible. Similar studies were begun anew in 2006. Laboratory Characterization Biosolids percent solids was de termined by drying (105 C) “a s is” materials to constant weight. Biosolids pH and electr ical conductivity (EC) were determined using a 1:10 ratio of biosolids (dry weight equivalent ) to distilled, de-ionized water ( DDI), and equilibrated by static incubation at room temperature for 2 hours. Afte r the 2 hr equilibration, the biosolids-DDI water mixture was stirred and allowed to settle, and pH and EC were determined on the solution. Total carbon/ total nitrogen (TC/TN) was determined on dried, ball-milled biosolids by combustion at 1010 C using a Carlo Erba (Mila n, Italy) NA-1500 CNS analyzer. Loss on ignition (LOI), a measure of biosolid s organic matter content, was determined by measuring 0.2 g of oven-dried and ball-milled bios olids into pre-weighed 50 mL beakers. The materials were ashed at 250C for 30 minutes, followed by ashing at 550C for an additional 4 hours. The samples were allowed to cool, and th e beakers were weighed again. Mass lost during the ash process is a measure of organic matter (Sparks, 1996). To analyze for total phosphorus (TP), samples of biosolids were fi rst oven-dried and ground in a ball mill to a fine powder. The bioso lids (0.2 g) samples were then ashed (250C for 30 minutes and 550C for 4 hours) in a muffle furnace to destroy organic matter. The ashed samples were digested with ~2 mL of DDI wa ter and 20 mL of 6 M HCl. The beakers were placed on a hotplate at 110 C unt il the HCl evaporated, and the residual was dry. The hotplate temperature was then increased to the hottest setting (~300C) for 1 hour. The beakers were allowed to cool, and ~2 mL of DDI and 2.25 mL of 6 M HCl was added to the residual material and the beakers were placed on a hot plate (highe st setting) until small bubbles started to form (solution began to boil). The so lution was removed from the hotplate and allowed to cool. The

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21 solution was transferred quantitatively to a f unnel containing a Whatman #42 filter, and allowed to drain into 50 mL volumetric flasks. The filter paper was rinsed 3 times with DDI and allowed to drain completely between each rinse (Anders en, 1976). The solutions were brought to volume and analyzed for P using the molybdenum blue method (Murphey and Rile y, 1962). Digests from the Andersen (1976) method were also analyzed for total Fe, Al, and Ca via inductively coupled plasma spectroscopy (ICP). We also determined biosolids-TP using EP A method 3050A (USEPA, 1995) to verify TP values determined by the Andersen (1976) me thod were accurate. Method EPA3050A required 2 g (dry weight equivalent) of biosolids. Samp les were pre-digested with 10 mL of 1:1 HNO3, covered with reflux caps, and heated at 110C for 10-15 minutes. After the pre-digestion, an additional 5 mL of HNO3 was added and the samples were refluxed for 30 minutes. This second step was repeated until brown fumes were no longer visible. The reflux caps were removed and the digestion solution was allowed to evaporate (2 -3 h) to a volume of 5 mL. The flasks were removed from the hotplate and allowed to cool Then, 30 mL of 30% hydrogen peroxide and 2 mL of DDI was added and new reflux caps were place on top of the flasks. The samples were returned to the hotplate set at 110C until effe rvescence subsided. Additional 1 mL aliquots of 30% hydrogen peroxide were added (not exceed ing 10 mL) until effervescen ce ceased. After the peroxide reaction, 5 mL of concentrated HNO3 was added and the samples were refluxed for 30 minutes. The samples were then cooled, and fi ltered through a Whatma n #41 filter into 50 mL volumetric flasks. The filters were rinsed 3 tim es with DDI and allowed to drain completely between each rinse. Filtered digests were br ought to volume and analyzed for P via ICP. Biosolids-TP was also determined by an outsi de laboratory via perc hloric acid digestion (Association of Official Analytical Chemists, 1990; The Fertilizer Inst itute, 1982) to further

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22 confirm TP values. One gram of dried and pow dered biosolids were boiled with 30 mL of concentrated HNO3 for ~20 minutes. The samples were cool ed and 20 mL of perchloric acid was added until the solutions were co lorless and started to fume. On ce samples were colorless, and white fumes were noted, the digestion was continued for an additional 20 minutes. Following the second 20-minute digestion, 30 mL of DDI was added and the samples were boiled for 5 minutes. Samples were then cooled and filte red through an Ahlstrom Grade 54, 12.5 cm filter paper into a 100 mL volumetric flask. Samples we re brought to volume and analyzed for P via ICP. Water-extractable P (WEP) was determined using a 1:200 biosolids (dry weight equivalent) to DDI water (Sharpley and Moyer, 2000). The residuals/water mixture was shaken on an orbital shaker at 200 strokes per minut e for 1 hour. A sub-sample of the mixture was centrifuged for 10 minutes at 4000 rpm, and th e supernatant was vac uum-filtered through a 0.45 mfilter. The solution was analyzed for P using the molybdenum blue method (Murphey and Riley, 1962). Percent WEP (PWEP) was calcula ted by dividing WEP by TP and multiplying by 100 (PWEP = WEP/TP*100). Brandt et al. (2004) concluded that PWEP was a good measure of the environmentally relevant portion of total P in biosolids and manures. Oxalate-extractable P, Fe, and Al was determ ined by shaking 0.5 (dry weight equivalent) of biosolids with 30 mL of 0.175 M ammonium oxalate and 0.1 M oxalic acid for 4 hours on an orbital shaker at 200 strokes per minute (Loepp ert and Inskeep, 1997). The samples were shaken in a sealed box to avoid expos ure to light. After shaking, the samples were centrifuged for 10 minutes at 4000 rpm, and vacuum filtered thr ough a Whatman #42 filter. The supernatant was analyzed for P, Fe, and Al via ICP. Moles of oxalate-extractable P, Fe, and Al were used to

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23 calculate PSI, an indication of labile P in residu als [PSI = moles P/ (moles Fe + mole Al)] (Elliott et al., 2002). Fe-oxide extractable P (Fe-strip P) in biosolids was determined using Fe-oxide impregnated strips (Chardon, 1996). Strips were prepared by soaking Whatman #42 filter paper in 0.65 M FeCl36H2O + 0.6 M HCl solution overnight. The st rips were removed and allowed to air dry. The strips were immers ed for 30 seconds in 2.7 M NH4OH, then rinsed twice in DDI water, left to sit in clean DDI water for 1 hour, and then air dried before use. Fe-strip P was determined by shaking the prepared strips with 1 g (dry weight equivalent) of biosolids and 60 mL of 0.01 M CaCl2 in a 120 mL bottle for 16 hours on an orbital shaker at 125 oscillations/minute. The original method was changed from 40 mL CaCl2 to 60 mL CaCl2 to ensure the biosolids were completely covered with solution. During the CaCl2 wash, P is removed from the biosolids and is retained on the Fe-strip. After shak ing, the strips were removed from the glass bottles and rinsed thorou ghly with DDI to remove biosolids particles. The rinsed strips were placed in 125 mL Erlenm eyer flasks and shaken with 40 mL of 0.1 M H2SO4 on an orbital shaker for 1 hour at 125 oscillations/minute. The 0.1 M H2SO4 extracts P from the Fe-strip, and the solutions were then analyzed for P using the molybdenum blue method (Murphey and Riley, 1962). Fe-strip P is measure of biologically available P in soil (Sharpley, 1993a and b). Dynamic Laboratory Incubation Eleven biosolids and TSP were chosen for a dynamic laboratory incubation. Biosolids were mixed at 2 rates, equivalent to 56 and 224 kg P ha-1, with 400 g samples of Immokalee A horizon soil (Immokalee fine sand, sandy, siliceous hyperthermic Arenic Alaquods; Table 2-1) and enough water (40 mL) to reach field capacity The biosolids-amended soil was incubated for 2 weeks in zip-lock plastic bags. The bags of soil were mixed and opened daily during the initial

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24 incubation to avoid anaerobic conditions. As in the glasshouse study (below), ammonium nitrate was added to the soil to supply additional N. Orig inally, we intended to equalize varying N levels among the materials at both P rates to 300 kg N ha-1 plant available N (PAN). We initially applied 75 kg N ha-1 to the biosolids-amended soil at the st art of the 2-week equilibration, with the intention of split applying the remaining N after leachings. However, the columns of soil were near field capacity for the duration of th e experiment, and applying AN in solution would have induced unintentional leaching; applying AN in crystalline form would not allow for N distribution throughout the soil colum n. Thus, the remaining 225 kg N ha-1 was not applied. Incubation columns were constructed of 17 cm x 5 cm sections of polyvinyl chloride (PVC) tubing with screening in the bottom to prev ent soil loss. At the end of the initial 2-week bag incubation, 400 g biosolids-amended soils were packed into the in cubation columns to a depth of 13 cm and a bulk density of 1.51 g cm-3. A total of 75 columns was used (12 materials x 2 rates x 3 reps + 3 controls = 75). The column s were positioned vertically in wooden racks for leaching events. Preliminary experiments were conducted to determine a representative column pore volume (PV). Two methods were used to determ ine PV, gradual wetting and flood wetting. Four incubation columns were filled with 400 g of dry soil and weighed. Tap water was gradually added to two of the columns until 1 or 2 drops of water exited the bottom (gradual wetting). The retained water volume (~118 mL) was assumed to be 1 PV. The other two columns were flooded with 250 mL of tap water and allowed to drain overnight. When drainage was complete, the columns were re-weighed and the difference in weight (~120 g) was assumed to be 1 PV. One PV was taken to be 120 mL.

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25 Every 2 weeks, sufficient tap water (adjuste d to pH 5.0) was added to the columns to result in 60 mL (1/2 PV) of drainage. We adjusted the pH of the water to 5.0 to simulate the pH of rainfall in south Florida. La boratory tap water was analyzed fo r soluble reactive (inorganic) P (below detection limit; 0.001 ppm). Fo r the first 2 leachings, P analys is of the leachates included total phosphorus (TP), total di ssolved phosphorus (TDP) and sol uble reactive phosphorus (SRP); pH and EC was also determined. Total P in th e leachate was determined by digesting 5 mL of unfiltered leachate with 0.35 g of potassi um persulfate and 1 mL of 5.5 M H2SO4 on a digestion block at 125 C until only 5 mL of solution re mained (USEPA, 1993). The temperature was then increased to 150 C until 0.5 mL of solution remained. Refl ux caps were placed on top, and the temperature was further increased to 380 C and digestion continue d until the solution was clear. TDP was determined in the same way, however the leachates were vacuum filtered through a 0.45 mfilter to remove particulates before dige stion. The digested leachate was analyzed for P via the molybdenum blue method (Murphey and Riley, 1962). SRP was determined by vacuum filtering leachate through a 0.45 mfilter. The fi ltered leachate (undigested) was analyzed for P using the molybdenum blue method. Organic P wa s determined by subtracting SRP from TDP. Results from the first 2 leachings, revealed that the SRP represented the majority (>80%) of the total P leached from the amended soils, and that organic P was minimal (<10% of TP). Thus in subsequent leaching events, TP and TDP were m easured only for select (highly colored or cloudy) samples: Lakeland NS, OCUD S, OCUD E cake and OCUD E dry. TDP and TP values were determined on these samples to ensure orga nic P and particulate P was minimal. Leachate pH and EC was measured directly on unfiltered/undigested leachate.

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26 Glasshouse Study Seven biosolids and TSP were chosen for th e glasshouse experiment for a total of 8 materials. Two biosolids were selected to re present (expected) low-P availability biosolids: Milorganite, and GreenEdge (PWEP 1.1%). Four biosolids were se lected as high P-availability biosolids (Boca Raton, GRU, Lakeland NS, and OC UD S), which are BPR or BPR-like residuals (PWEP 15%). One biosolids selected (Disney) ha d a moderate PWEP (8.4%) and biosolids-P was expected to be moderately plant available. Biosolids were also selected based on PSI and PWEP values. BPR and BPR-like biosolids typica lly have PSI and PWEP values greater than traditionally produced residuals. We chose biosolids with high PSI and PWEP values to expand the existing relative P phytoavailability da tabase. Much work has been done on the phytoavailability and lability of conventionally produced biosolids, including some Florida materials, and some BPR materials (O’Connor et al., 2004; Elliott et al., 2002), but the database is limited. Materials were mixed with 4 kg of A horizon Immokalee soil (Table 2-1) at 3 rates: 56, 112, and 224 kg P ha-1. The 56 and 224 kg P ha-1 rates represent P-based and N-based application rates, respectively. The 112 kg P ha-1 rate was added to better define the relative P phytoavailability response curve of the materials. Immokalee fine sand was chosen to represent a typical, P-deficient, low-P sorbing Florida soil. A P-deficient and low P-so rbing soil is necessary to represent a “worstcase” scenario of biosolids land a pplication, and to maximize plant response to P additions. The Immokalee soil does not retain P and can allow P movement to ground and surface waters. The biosolids-amended soils were equilibrated (at field capacity) in zip-lock plastic bags for 2 weeks in the laboratory prio r to use in the glasshouse. A mmonium nitrate (AN) was added to the amended soils to equalize varying amounts of N supplied by the biosolids. N was applied at an equivalent rate of 300 kg ha-1 plant available nitrogen (PAN). The GreenEdge material

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27 supplied the most PAN (240 kg ha-1) at the high P rate. We opted to supply an additional 60 kg ha-1 of N to ensure N limitations would not affect P release or uptake. This rate is excessive for Bahiagrass (179 kg N ha-1 recommended; Kidder et al., 1998), but could not be avoided due to the N:P ratio of the materials and the high targeted P rate of 224 kg ha-1. N mineralization was assumed to be 40% of the total N in all of the biosolids, based on previo us experience (O’Connor and Sarkar, 1999). The total supplemental AN needed was split-applied, with applied prior to incubation, and the remaining split applications added throughout the growing season (following the first 3 leaching events). AN is fully soluble in water and therefore is immediately available for plant uptake. Thus, AN was split-applied to ensure sufficient N was available for uptake throughout the growing season. A bl end of potassium-magnesium sulfate (“sul-po-mag”; 22% S, 18% K, 11% Mg) was added ( 0.91 g, equivalent to ~444 kg ha-1) to supply adequate and uniform S, K, and Mg. Containers for the glasshouse study were c onstructed of 15 cm diameter X 45 cm long sections of polyvinyl chloride (PVC) tubing. A screen was fitted to the bottom to prevent soil loss. A PVC cap fitted with plastic tubing was a ttached to the bottom of the column to allow leachate collection. A total of 100 columns was used (8 materials X 4 replicates X 3 rates + 4 controls = 100). The columns were arranged in a randomized complete block design in wooden racks holding 6 columns each. The experiment was blocked to minimize glasshouse positioning effects. The columns were rotated one position within each block weekly to further minimize glasshouse effects on grass growth. O’Connor et al. (2004) used the same container and experimental design to quantify P uptake and leaching for 12 biosolid s products in the same soil. Thirty cm of sand (~8.5 kg) was packed into the columns as a s upport layer (TP = 12 g kg-1, WEP = 0.12 mg kg-1, pH = 5.1, RPA = 8.6%). The sand wa s included to provide additional

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28 rooting depth for the grass. The sand was flooded and allowed to freely drain to wet the layer to field capacity and to remove soluble constituen ts. Following the 2-week laboratory incubation, 4 kg of biosolids-amended soil was placed on top of the sand layer in each column, and 5 g of Bahiagrass seed was planted. Five grams of Bahiag rass seed per pot is a s eeding rate equivalent to ~28.6 Mg ha-1, the recommended seeding rate is ~10.9 Mg ha-1 (Chambliss et al., 2001). We increased the seeding rate to ensure sufficient and rapid soil surface coverage. The seeds were covered with a layer of sand (~0.5 cm) and misted every 3-4 hours until ge rmination. The grass was allowed to grow for approximately 7 weeks be fore the first harvest. Subsequent harvests occurred at approximately 4-week intervals. The Bahiagrass was harvested to a height of 3.8 cm using scissors. The wet clippings were placed in pre-weighed paper bags and dried at 68 C to cons tant weight to represent grass yields. The dried tissue was ground to pass a #20 sieve with a Wiley mill, digested (Andersen, 1976) and analyzed for P via the molybdenum blue method (Murphey and Riley, 1962). Phosphorus uptake was calculated as yiel d times tissue P con centration. Individual harvest P uptake masses were summed to give cumulative P uptake mass. Tissue N content of plants from the 224 kg P ha-1 rate for all treatments was also measured for all 4 harvests. Tissue N was determined by grinding the tissue to a fine powder, and analyzing for N by combustion at 1010 C using a Carlo Erba (Mila n, Italy) NA-1500 CNS analyzer. Following each harvest, sufficient tap water (adjusted to pH 5.0) was applied to each column to yield ~500 mL (~0.25 pore volume) of leachate. Soluble reactive (inorganic) P (SRP) of glasshouse tap water was measured (below detection limit; 0.001 ppm) via the molybdenum blue method (Murphey and Riley, 1962). Leachate was analyzed for SRP using the molybdenum blue method. Leachate volume times leachate P concentration yielded mass of P leached.

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29 Leachates from the Lakeland NS material (high P rate) were highly colored. TP was determined on the leachates to ensure organic P loss from the material was not significant. Statistical Analysis Cumulative P leached from the laboratory in cubation was subjected to a time-series analysis (SAS Institute, 1989). Data were te sted for normality using PROC UNIVARIATE. To normalize yield and P uptake data logarithmic transformations were needed. P leaching data were normalized with a square transformation. Transformed cumulative yield, P uptake, and P leached from the glasshouse study were statis tically analyzed using PROC GLM. Means separation of treatment differe nces was by Tukey test (p 0.05) on transformed data. Relative phytoavailability was calculated by fitting a line ar regression to P uptake as a function of P applied data using a sloperatio ap proach. All P sources were regressed through a common intercept of 8.48 mg, the average value of P upt ake for the control, resulting in a response proportional to the rate of P application.

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30 Table 2-1. Selected properti es of Immokalee fine sand. Parameter, units Value Sand, % 95a pH 4.8 Organic matter, g kg-1 7.0 a Oxalate-extractable P, mg kg-1 13.1 a Oxalate-extractable Fe, mg kg-1 85.6 a Oxalate-extractable Al, mg kg-1 40.1 a PSIc 0.14 a RPAd, % 2.0 Total P, mg kg-1 15.5 Mehlich 1-extractable P, mg kg-1 1.47 KCL-extractable P, mg kg-1 1.9 a NaOH-extractable P, mg kg-1 3.3 a HCl-extractable P, mg kg-1 0.9 a Sequenced sum, mg kg-1 6.1 a aData from O’Connor et al. (2004). cPhosphorus Saturation Index. dRelative phosphorus adsorption [fraction of 400 mg P kg-1 soil load sorbed (H arris et al., 1996)].

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31 CHAPTER 3 RESULTS AND DISCUSSION Laboratory Characterization The laboratory characterization was key to de termining which materials warranted further study in the dynamic laboratory incubation and gl asshouse studies. Twenty-one biosolids were received and analyzed (Table 3-1). As detaile d below, both basic chem ical properties and P characteristics were important for material se lection. Recall that a goa l of both the glasshouse and dynamic laboratory incubation experiments was to include materials not previously studied, specifically BPR and BPR-like products. Total nitrogen (TN) concentra tions ranged from 16 to 70 g kg-1 (1.6 to 7%). Biosolids C:N ratios were generally low (6-15), with th e exception of the West Palm Beach Compost material (C:N of 26) (Table 3-2). The TN and C:N ratios are typical of U.S. produced biosolids (USEPA, 1995). C:N ratios are important for pred icting N mineralization from biosolids. In general, when the C:N ratio of an organic material is less than 20:1, N will be released into the soil. If the C:N ratio exceeds 30:1, N can be i mmobilized by soil microbes, and unavailable for plant uptake. Thus, we selected materials with C:N ratios below 20:1. The Disney material was chosen as the representative compost resi dual to avoid possible complications with N immobilization from high C:N ratio of the West Palm Beach biosolids. Biosolids pH varied with source and produc t form (Table 3-2). Cakes were circumneutral to alkaline, and thermally dried products were slightly acidic. Lime stabilized products had the highest pH values, as lime stabilization increases the pH of th e final product (pH > 12). We excluded materials with pH values > 9 from the glasshouse study as Bahiagrass prefers an acidic environment (pH ~5.0; Chambliss and Ad jei, 2006). O’Connor et al. (2004) reported

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32 severely limited growth of Bahiagrass when bios olids with high pH (>12) values were applied to the Immokalee soil at N-based rates. TP concentrations of biosolids (Table 3-3) ranged from 7.9 to 33 g kg-1 (0.79 to 3.3%), typical of TP concentrations of biosolids produced conventi onally nationwide (~20 to 40 g kg-1), and 40 g kg-1 for BPR materials (USEPA, 1995). The diffe rence in TP values results from the differences in wastewater characteristics and treatment practices (B randt et al., 2004). TP concentrations were not used to include/excl ude materials, but TP concentration was an important measurement, as the laboratory determin ed TP values were used to calculate the mass of biosolids needed to attain selected P application rates. TP values for the materials were determ ined using 3 methods: Andersen (Andersen, 1976), EPA 3050A (USEPA, 1995) and perchloric ac id (Association of Official Analytical Chemists, 1990; The Fertilizer Institute, 1982) (Table 3-4). The Andersen and EPA 3050A analyses were performed at UF. The perchloric acid analysis was conduc ted at an independent laboratory for additional TP verification. The abil ity to recover P from the biosolids differs among the techniques, which is reflected in the va riability of the reported TP concentrations. UF researchers were not provided information on how the individual WWTPs analyzed materials for TP, which could explain the variability between determined and producer-supplied P values. A standard reference biosolids material (National Institute of Standards and Technology, Standard 2781: Domestic Sludge) was used to gauge the ability of diges tion methods to recover P. All three methods had excellent P r ecovery percentages (88-96%). Researchers chose to use the TP values de termined by the Andersen (1976) method for this study, primarily because of its ease of use. The EPA 3050A method is tedious and time consuming, making the method impractical for the large number of samples involved in this

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33 study. The perchloric acid analysis requires special facilities to handle the explosive nature of perchloric acid, which were not available in the UF laboratory. In contrast, the Andersen (1976) and EPA 3050A methods use hydrochloric and nitr ic acid, respectively, which are much safer to handle. In a preliminary experiment, the Andersen -TP concentrations were used to calculate the quantity of biosolids necessary to reach a target P rate of 224 kg P ha-1. A small quantity (200g) of Immokalee soil was amended with the calcul ated masses of biosolids. When the biosolidsamended soils were analyzed for TP using the Andersen (1976) method, the target P rate was reached, indicating that the TP values obtained from the Andersen (1976) method were adequate measures of the total P in the biosolids. Total Fe, Al, and Ca concentrations were m easured on the Andersen-TP extracts via ICP (Table 3-2). Total metal concentrations were re presentative of biosolids produced nationally and reflected the individual bioso lids treatment processes. Tota l Fe ranged from 2.2 to 60 g kg-1 (0.2 to 6%), Al ranged from 1.7 to 24 g kg-1 (0.17 to 2.4%) and Ca ranged from 13 to 310 g kg-1 (1.3 to 31%). The Lakeland Glendale ma terial is lime stabilized, whic h is reflected in the high total Ca (310 g kg-1). The greater a residual’s Fe and Al cont ent, the better the material is able to retain P, leading to lower phyt oavailability and lower leaching risks (Elliott et al., 2002). As discussed below, Milorganite (41 g kg-1 Fe, 2.7 g kg-1 Al) has relatively high amounts of Fe and Al, and resulted in decreased P release and P phytoavailability. Water-extractable P (WEP) ranged from 0.04 to 14 g kg-1 (Table 3-3). Brandt et al. (2004) demonstrated that WEP is a good measure of the environmentally relevant portion of P in biosolids. WEP is used to calculate percent water-extractable P (PWE P = WEP/ TP*100). Most of the non-BPR materials analyzed had PWEP values < 5%, which is typical of non-BPR biosolids produced in the U.S. (Brandt et al ., 2004). BPR materials, (Boca Raton, OCUD E cake

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34 and dry) had PWEP values 11%. Brandt et al. (2004) determined the average PWEP for various BPR biosolids sampled nationwide to be 14%. PWEP was high for both Lakeland NS (47%) and GRU (26%). These materials are not produced via BPR processes, but personal communication with plant operators suggests that P removal is likely occurring in both systems. We have categorized these materials as “BPR-like”. Both the Lakeland NS and GRU materials are low percent solids (3 and 5%, respectively, Table 3-2), and we decided to an alyze the liquid and solid phases of both materials to determine the concentration of TP. Phosphorus in the liquid phase would be e xpected to be highly labile, and we suspected that the high PWEP values were due in part to high con centrations of P in the liquid phase. To determine the TP concentrations in the separated liquid and solid phases of each residual, we centrifuged sub-samples at 12,000 rpm for 15 minutes to separate the liquid phase from the solid phase. The separated phases were then analyzed for TP, the solid phase via the Andersen (1976) method, and the liquid phase via persulfate digestion (USEPA, 1993). Analysis showed that 50% and 20% of TP was in th e liquid phase for the Lakeland NS and GRU materials, respectively. The smaller concentrat ion of P in the liquid phase for GRU than Lakeland NS is reflected in the smaller PWEP va lue for GRU (26%) versus Lakeland NS (47%). Disney is a BPR biosolids, however the PWEP (8.4%) is below average for a BPR residual. The Disney material is a composted mixture of biosolid s, food, and yard waste. Brandt et al. (2004) reported that compos ting an anaerobically digested cake decreased WEP by 10-fold. The yard waste itself could d ecrease PWEP; the Disney compost was sieved to pass through a 2 mm sieve prior to analysis, however small pieces of wood were obvious. The yard waste composted with the Disney biosolids decrease s the mass of biosolids per kg of land applied finished product (composted biosolids + yard waste, even after sieving), th us reducing labile P.

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35 Oxalate-extractable Fe, Al, and P concentrations (Table 3-3) were used to calculate PSI values for the materials. PSI can be used a priori to gauge the lability of P in many biosolids in sandy soils (Elliott et al., 2002). PSI relates the mo les of oxalate-extractable P to the moles of extractable Fe and Al (PSI = moles P / [m oles Fe + moles Al]). Biosolids with high concentrations of Fe and Al tend to have less la bile P. PSI has no meaning for biosolids whose P chemistry is controlled by Ca (lime stabilized mate rials). Elliott et al. (20 02) suggested a critical PSI value of 1.1 for non-lime stabilized materials. That is, if the PSI of a material exceeds the critical value, appreciable P leaching may occur from amended, sandy soils with limited P retention capacity. Biosolids with PSI values 1.1 resulted in minimal P leaching in the Elliott et al. (2002) study. Most of the samples analyzed in the current study were BPR or BPR-like materials, and the PSI values exceed the critical value propos ed by Elliott et al. (2002). We would expect significant leaching when these mate rials were land applied to Immokalee soil that retains P poorly. Dynamic Laboratory Incubation Eleven biosolids and TSP were individuall y mixed with 13 cm (400 g) samples of Immokalee soil for the dynamic incubation study. Soil columns were leached a total of 8 times (~4 total PV) over 5.5 months. The first 7 leachings were conducted bi-weekly to attain ~60 mL (1/2 PV) of drainage each time. Significant P release (leaching) ceased after 5 leachings (2.5 months). A time-series analysis (SAS Institut e, 1989) showed no difference in cumulative P released for leachings 5-7. We waited 2 additional months to conduct the final leaching to allow for P dissolution and distribution through the individual co lumns of soil and to confirm P release from all materials was maximized. Indeed, P loss from all materials during leaching 8 was minimal (< 1mg). Data from the final leaching wa s added to the time-series analysis and, again, showed no change in cumulative P released between leachings 5-8. Three months passed

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36 between leachings 5 and 8. Because cumulative P release did not change over the 3-month time frame, we assumed that P release from the materials had ceased, and the experiment was terminated. SRP in leachate was taken to represent total P released, as SRP constituted the majority (>85% of TP) of P lost to leaching. To ca lculate P released as a percentage of applied P, the mean mass of P released from the control treatment was subtracted from the mass of P released for all other treatments, and the di fference divided by the appropriate mass of P originally applied. One objective of the study was to quantify wa ter soluble P (mass of P released) from various biosolids representing a range of chemical character istics. Biosolids with lower quantities of water soluble P are less likely to nega tively affect the environment. The quantity of water soluble P is governed by several factor s, including biosolids treatment processes [especially heat drying (Smith et al., 2002; Maguire et al., 20 01)], and biosolids chemical composition (especially the quantity of Fe and Al oxides in the material). Residuals high in Fe and Al oxides retain P, and result in less P l eaching (Brandt et al., 2004). Thus, we expected significantly more P release from BPR biosolids low in Fe and Al oxides than thermally dried residuals high in Fe and Al. ANOVA showed significant source (P-source), rate (P-rate) and source by rate interactions. As a result, comparisons of cumula tive P released and cumulative P leached as a percent of applied P are discusse d within each P application ra te and not across P application rates. Cumulative P release was greatest from BPR and BPR-like materials (Lakeland NS, GRU, Boca Raton, and OCUD E dry and cake) (Table 35). Figures 3-1a and b show cumulative P release (percentage of ap plied P) in bar graph form for the 56 and 224 kg P ha-1 rates, respectively. P release from Lakeland NS, GRU, Boca Raton, and OCUD E cake biosolids was

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37 equal to TSP at both the 56 and 224 kg P ha-1 application rates (Figures 3-1a and b). The OCUD E dry material was produced by thermally dryi ng the OCUD E cake material. The OCUD E cake is undigested biosolids and is not lawfully land applied, but was included fo r scientific interest. Heat drying the OCUD E cake create d a class AA material that may be land applied. Heat drying typically decreases labile P (Smith et al., 2002 ), and P release was less for the OCUD E dry biosolids than for the OCUD E cake biosolids. However, P release from the OCUD E dry biosolids at the 56 kg P ha-1 application rate was equal to th at from TSP, indicating the OCUD E dry biosolids still had high quantities of labile P. P release from the Disney biosolids was less than TSP and most BPR and BPR-like biosolids at both the 56 and 224 kg P ha-1 rates. At the 56 kg P ha-1 rate, P release from Disney was equal to GRU. As previously mentioned, Disn ey is a composted mix of biosolids, yard, and food waste, which results in a PWEP (8.4%) le ss than the other BPR and BPR-like biosolids ( 15%) in this study. The PSI (0.45) of Disney refl ects relatively large quan tities of Fe and Al, which likely reduced P release. At 56 kg P ha-1, P release from Milorganite and GreenEdge was significantly lower than from TSP. Both Milorganite and GreenEdge are thermally dried. Thermal drying typically lowers quantities of labile P. Milorganite also ha s relatively high total Fe + Al concentrations (44 g kg-1) compared to typical biosolids tota l Fe + Al concentrations (20 g kg-1), which we expected to further reduce P lability. P release from Milorganite and Gr eenEdge was not significantly different, suggesting that P re lease from Milorganite and GreenEdge could be controlled by physical properties (pellet dissolution). When the laboratory incubation was dismantled, pellets of Milorganite and GreenEdge were still apparent, suggesting that even though the columns were near field capacity for the durat ion of the experiment, the length of time was not sufficient for

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38 complete pellet dissolution. Milorganite Gree ns Grade, which is the same product as Milorganite, but passed through a sm aller sieve, has a slightly gr eater PWEP value (0.85%) than Milorganite (0.58%). We delayed the final leaching for 2 months following leaching 7 to allow dissolved P to diffuse through soil pores (a time limited reaction), and the columns of soil were maintained near field capacity during the 2-m onth break. Despite the elapsed time and sufficient moisture, P release from all materials was < 1 mg in leaching 8. Time series analysis also indicated that P release was minimal over the la st 3-month period (leachings 5-8), suggesting that P release from the P sources was maximized. We expected GreenEdge to release a greater qu antity of P than Milorganite based on the biosolids PSI values, total Fe and Al concentr ations, and PWEP values GreenEdge has greater PSI (1.0) and PWEP (1.1%) values than Milo rganite, (PWEP: 0.58%, PSI: 0.55) and Milorganite has greater Fe and Al (44 g kg-1) concentrations than GreenEdge (Fe + Al = 23 g kg-1). Based on the P chemistry, we expected a greater quantity of P release from GreenEdge, however the data did not support our a priori assumption. We hypothesized th at calcium was influencing P lability, however the Ca concentr ation of GreenEdge is not great enough to suggest that Ca is controlling P solubility. We then ground a sample of GreenEdge with a mortar and pestle and determined PWEP on the finely ground biosolid s. The PWEP of GreenE dge did not increase after grinding, (1.3%, compared to 1.1% on un-ground biosolids) i ndicating that pe llet size was not influencing P solubility. We currently have no explanation for the equal quantities of P released from GreenEdge and Milorganite. Butkes et al. (1998) studied P retention of water treatment residuals (WTRs) and suggested th at cationic polymers added during the water treatment processes can retain P. During the dewatering of GreenEdge, a polymer (Ciba Zetag

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39 8849FS) is added, and it is possible that the dewate ring polymer has the capacity to sorb P, thus reducing P lability. Cumulative mass of P released from the OCUD S material was equal to TSP at the 56 kg P ha-1 application rate and greater than TSP at the 224 kg P ha-1 rate (Figures 3-1a and b). The OCUD S material is a conven tionally produced biosolids; how ever, the PWEP (21%) and the PSI (2.9) values of the OCUD S material are high, and consiste nt with the high quantity of P leached. Given the treatment process of the OC UD S biosolids (anaerobically digested) we would not expect PWEP and PSI values to be so high. However the total Fe + Al concentrations of the OCUD S material are low (11g kg-1), resulting in the high PSI value and quantities of P released equal to TSP. As previously mentioned, biosolids-TP is not a good indication of P lability. However, PWEP can be used to gauge the environmental impact a residual will have once land-applied. A logarithmic relationship exists between cumulativ e P released (% of applied P) and biosolidsPWEP at both rates (Figures 3-2a and b). The correlation was similar for the 56 kg P ha-1 rate (r2 = 0.65) and the 224 kg P ha-1 application rate (r2 = 0.69). The correlation between cumulative P released (% of applied P) and biosolids-PWEP was not strong e nough to indicate that PWEP can be used to predict the amount of P release th at will occur when a biosolids is land applied. However, Brandt et al. (2004) demonstrated that PWEP is a superior measure of the environmentally relevant portion of P in biosolids and manures than biosolids-TP or soil test P. Biosolids-PWEP can be used a priori to gauge the potential of a residual to negatively affect the environment. PWEP is a measure of the water-sol uble P in biosolids, thus materials with PWEP values 14% (vertical line in Figure s 3-2a and b) should be assume d to have a larger negative environmental impact than biosolids with PWEP va lues < 14%. Recall that Brandt et al. (2004)

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40 reported an average PWEP value for BP R biosolids sampled nationwide to be 14%. Given the ease with which WEP/PWEP can be determined, PWEP can be used as a quick and efficient gauge of a residual’s potential to negatively imp act the environment once land applied. Elliott et al. (2006) used source WEP to improve P s ource coefficient assignments (PSC = 0.102 x WEP0.99) for state P-indices, and runoff dissolved P was well correlated (r2 = 0.80) with sourceWEP. Figures 3-3a and b show P released (% of a pplied P) as a function of PSI for the 56 and 224 kg P ha-1 rates, respectively. Elliott et al. (2002) demonstrated that fo r biosolids with PSI values 1.1, no appreciable leaching occurred from another sample of the Immokalee soil amended with biosolids. Several materials used in this study had PSI values above the suggested critical point of 1.1, which would portend signifi cant P losses measured from the BPR and BPRlike materials. Data from the current study indi cate that a critical PSI value of ~2.0 better separates biosolids where leaching was greatest, s uggesting that the critical PSI value be raised from 1.1 to ~2.0. However, the Elliott et al. (2 002) study differed from the current study in 2 ways: 1) the Elliott et al. (2002) study utilized much larger soil columns, where of a pore volume was 500 mL, and 4 monthl y leachings were necessary to reach 1 pore volume of drainage; and 2) Bahiagrass was grown in the El liott et al. (2002) soil columns, reducing the quantity of P available for le aching. Data published separately (O’Connor et al., 2004) showed that Bahiagrass took up 29-57% of applied P at the 56 kg P ha-1 application rate. In the dynamic laboratory incubation, ~4 pore vol umes of drainage were collected versus 1 pore volume of leachate collected in the Elliott et al. (2002) study. The small columns in the current study included no plants and were flushed with more pore volumes of water than the large glasshouse columns, which would encourage P release a nd movement downward (a nd out) of the small

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41 columns. Given the differences in experimental design between the current study and Elliott et al. (2002) study, raising the critical value from 1.1 to ~2 is proba bly not justified. While there is no clear mathematical relationship between cumula tive P release and PSI, it is evident that P release increases when PSI > 2.0. P release appears to be maximized (~80% of applied P) at PSI values > 2.0 The second major objective of dynamic laborator y study was to examine the kinetics of P release. Figures 3-4a and b show cumulative P released as a per centage of P applied per leaching event for the 56 and 224 kg P ha-1 rates, respectively. While the ul timate quantity of P released is important, the rate at which P is released is al so important. When large amounts of P are released from a material quickly, more P is in the soil so lution at any given time and is subject to leaching in periodic rain events, increasing the risk of ground and surface water impairment. Slow rates of P release provide plants more time to take up bi osolids-P, decreasing the amount of P subject to loss from the soil profile. Materials with high PWEP values (OCUD E cake, Lakeland NS, GRU, OCUD S) released large quantities of P quickly (within the first 3 leachings). At the 224 kg P ha-1 application rate (Figure 3-4b), the thermally dried materials (Milorg anite, GreenEdge, and Tallahassee) and the conventionally produced Brow ard cake released < 7% of applied P during the first leaching event and the remaining materials released >15% of applie d P. The quantity of P released from Milorganite and GreenEdge wa s ~55% less than P released by the highly-P soluble materials during the first leaching event. Phosphorus release from the cake and slurry materials began to decrease (slow) in leaching 4, but P release from Milorganite and GreenEdge continued to increase through leaching 5. As disc ussed above, high rates of P release from BPR and BPR-like materials increase the quantity of P in the soil solution at a ny given point in time.

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42 The increase in soil solution P suggests that BPR and BPR-like biosolids could be excellent fertilizers, but also makes BPR and BPR-like re siduals more likely to negatively affect the environment, when soil solution P is washed through the soil profile into ground and surface waters. We can roughly convert total PVs leached to re sidence time in a field setting. One PV of leachate represents ~5.64 cm drainage. Cumula tive leaching (~480 mL) represented 22.6 cm of drainage. Yearly rainfall in s outh Florida averages ~140 cm yr-1 (Obeysekera et al., 2004) and evapotranspiration is ~70% of rainfall (Nachab e et al., 2005). Subtrac ting evapotranspiration from rainfall (140 cm yr-1 – 100 cm yr-1) yields 40 cm yr-1 drainage. Assuming 40 cm drainage yr-1, we can calculate the number of PVs leached per year (40 cm yr-1/5.64 cm PV-1 = 7.09 PV yr1). Thus, the 4 PVs leached in this study equate to ~7 months in the field. This study represents an extreme case of biosolids la nd application where the soil used had minimal P sorbing capacity and no plants were grown to take up applied P. This experiment was key to understanding biosolids P leaching characteristics in a representative “worst-case” scenario. Glasshouse Study A glasshouse study was run concurrently w ith the laboratory leaching study. Seven biosolids were used and TSP was included as a re ference. Biosolids were mixed with 13 cm (4 kg) samples of Immokalee soil and placed on top of 30 cm of base sand. Two biosolids evaluated had low PWEP (<1.1%) values: Mi lorganite, and GreenEdge, 1 bi osolids had a moderate PWEP (Disney, 8.4%), and 4 biosolids had high PWEP ( 15%) values: Lakeland NS, OCUD S, GRU, Disney, and Boca Raton. Bahiagrass was grown a nd harvested monthly for 4 months. After each harvest, columns were leached to attain ~500 mL (1/2 pore volume ) drainage. Statistical analysis (ANOVA) showed significant treatment (biosolids), rate (P-rate), and rate X treatment effects on

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43 yield, P uptake, and P leaching (SAS Institute, 1999; Tables A-1, 2, and 3, respectively). Thus, results are discussed within each P applicati on rate and not across P application rates. Yields We provided excessive N and ot her macronutrients (S, K, Mg) to isolate P as the only nutrient variable. The lowest ra te of P application (56 kg P ha-1) provides more than adequate P for Bahiagrass. As a result, yields (Appendix Tabl e A-4) were expected to be equal across all materials and application rates. Equal yields are cr itical since harvest yields are used to calculate P uptake. At the 56 kg P ha-1 application rate, there were no si gnificant differences in cumulative yield between biosolids source tr eatments, and all treatment yiel ds were significantly greater than the control (Figure 3-5a). At the 112 kg P ha-1 application rate, all treatment yields were greater than the control, but th e cumulative yield for OCUD S bi osolids was greater than yields for TSP, Disney, and GreenEdge (Figure 3-5b). At the 224 kg P ha-1 application rate (Figure 35c), all the yields for all materials except for Lakeland NS and Disney were different from the control. The cumulative yield for the Lakeland NS material was smaller than yields for all other materials with the exception of the Disn ey compost. Yields at the 224 kg P ha-1 application rate for Bahiagrass grown in soil amended with Lake land NS were highly variable, and Bahiagrass growth was inexplicably reduced in 2 of the 4 soil columns. At the high P rate, the cumulative yield of the OCUD S biosolids wa s not different from the yields of the other materials (Figure 35c). Because ANOVA showed rate and treatmen t interactions affecting yield, we cannot statistically compare yields for treatments acro ss rates. Figure 3-6 shows that most cumulative yields approached the average yields across trea tments (except controls) (~28 mg; horizontal line on Figure 3-6).

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44 To validate that Bahiagrass N uptake was su fficient, we analyzed tissue from all four harvests at the highest rate of P application (Figure 3-7). We analyzed only tissue from the 224 kg P ha-1 rate because most of the N at this rate was assumed to come from N mineralization from the biosolids. If we misjudged the N minera lization rate to be 40% we would anticipate N deficiencies to be more apparent at the 224 kg P ha-1 rate. Recall that N was equalized across P application rates and treatments us ing ammonium nitrate. More a mmonium nitrate was needed at the 56 and 112 kg P ha-1 rates than at the 224 kg P ha-1 rate. The ammonium nitrate would be immediately available to the Bahiagrass, thus we would not expect N deficiencies due to slower (or smaller) than expected N mineralization from the biosolids. Tissue N concentration was used to calculate yield-weighted N concentrations for each treatme nt over the entire growing season using eqution 3-1. where trt = treatment H1 = harvest H2 = harvest 2 trt yieldH1 x NH1 + trt yieldH2 x NH2 + trt yieldH2 x NH2 trt yieldH2 x NH2 (3-1) cumulative trt yield Measured N concentrations were sufficient for grazing beef cattle (minimum 1.12 g N g1; NRC, 1996). Based on the N content per harvest (Figure 3-7), it appears we underestimated the quantity of N that would mineralize from the bios olids initially (first harvest), and overestimated N mineralization throughout the rest of the growing season. Figure 3-8 shows that yieldweighted N concentrations for all bioso lids treatments were above the minimum N concentrations required for beef cattle. The yi eld-weighted tissue N concentrations were sufficient for us to believe N was not affecting yiel ds. Micronutrients were also considered as the source of yield variation. Micronutrients were not supplied during the gr owing season, however

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45 research has shown micronutrient deficiencies in Bahiagrass are rare and do not affect yields (Chambliss and Adjei, 2006). P Uptake and Relative Phytoavailability The 224 kg P ha-1 rate of P application resulted in the greatest cumulative P uptake (Figures 3-9a – c; Appendix Table A-2). P upt ake ranged from 23-52 % of P applied at the low application rate (Figure 3-9a). In a simila r study by O’Connor et al. (2004), P uptake ranged from 29-57% of applied P at the same lo w P application rate. At the 224 kg P ha-1 rate, P uptake in the current study ranged from 7-28% (Figure 3-9c), whereas O’Connor et al. (2004) reported P uptake ranging from 11-29% of applied P at the 224 kg P ha-1 rate. Recall that yields for Bahiagrass grown in two repli cates of soil amended with the Lakeland NS biosolids were reduced at the highest rate of P application; ther efore, average P uptake at this rate was lowered. Cumulative yield-weighted tissue P concentrations ranged from 0.5 g kg-1 to 4.5 g kg-1 (Table 37). Bahiagrass grown in soil with no added P (control) accumulated the least P, and soil amended with TSP at 224 kg P ha-1 resulted in the highest yield-we ighted P concentration. Adjei and Rechcigl (2002) suggested that a sufficient tissue P concentra tion for Bahiagrass is 2.0 g kg-1. However, the critical concentra tion (P concentration necessary for survival) for Bahiagrass is likely lower, and may even be closer to 1.0 g kg-1 (personal communicatio n, Dr. Jerry Sartain, 2007). Milorganite applied at the 56 and 112 kg P ha-1 resulted in tissue P c oncentrations slightly below the hypothesized cr itical value of 1.0 g kg-1. However, cumulative yields of Milorganite and GreenEdge treatments were not different from yields in the fertilizer-P (TSP) treatment (Figures 3-5a-c). Thus, the low tissue P concentr ations in Milorganite and GreenEdge treatments did not limit above ground growth. Bahiagrass gr own in control columns (no added P) yielded less than all other trea tments. Over the course of the 4-month growing season, no above ground P

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46 deficiencies were noted for any treatment. Plant r oots were not examined for P-deficiency as the glasshouse study is ongoing. Relative phytoavailability (RPP) was estimated using a slope-ratio approach. Cumulative P uptake was plotted as a function of P app lied for each biosolids (Figure 3-10). Linear regressions were fit to the data for each P source with a common intercept of 8.48 mg (mean cumulative P uptake for the control columns). To calculate RPP, the slope of the regression line for each material was divided by the slope of th e regression line for TSP (Table 3-7). O’Connor et al. (2004) used the same approach to esti mate RPP for 12 biosolids on the Immokalee soil. Table 3-7 also lists RPP values for biosolids pr oduced or marketed in Florida determined by O’Connor et al. (2004). We atte mpted to fit both linear and 2nd degree polynomials to the data from the current study. The polynomials resulted in slightly greater r2 values, but greater coefficients of variability (CV) (Table 3-8). Comparison of polynomials by comparing slopes is also difficult, leading us to choose linear regres sions to determine RPP. While a linear regression through only the 56 and 112 kg P ha-1 rates had slightly higher r2 and lower CV values than linear regressions thr ough all 3 rates, r2 and CV values for regressions including all 3 rates were acceptable and significant at p 0.05 (Table 3-8). Recall the pur pose of including 3 rates of P application was to better define the RPP curve; therefore, we opted to include all rates for regression fit. O’Connor et al. (2004) proposed 3 groupings of relative phytoavailab ility: high (>75% of TSP), moderate (25-75% of TSP), and low (<25% of TSP). With the exceptions of Disney, all of the BPR and BPR-like materials fit into the high RPP category. The Disney biosolids is a composted mixture of BPR biosolids and yard wa ste, with PWEP (8.4%) and PSI (0.43) values less than the PWEP and PSI of the other BPR bi osolids included in th e glasshouse study. The

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47 PSI value for the Disney biosolid s indicates a greater quantity of Fe and Al than the BPR or BPR-like biosolids. Stratful et al. (1999) reported that BPR biosolids contained more phytoavailable P compared to conventionally produced residuals. The OCUD S material was 110% as phytoavailable as TSP. Interestingly, the OCUD S material is not a BPR material, but has a hi gh PWEP (21%), exceeding to the average PWEP value (14%), for BPR materials (Brandt et al ., 2004). To calculate th e regression slope for Lakeland NS biosolids, 2 P uptake replic ates were excluded at the 224 kg P ha-1 rate. Recall that Bahiagrass yields were inexplicably reduced in 2 replicates of the Lakeland NS amended soil at the high P rate, reducing P uptake. Excluding data points reduces pow er of statistical comparison; however when cumulative yields from all 4 replicates were used for regression, the linear correlation was very poor (r2 = 0.09). Thus, the regression coefficient and r2 values for Lakeland NS listed in Table 3-7 reflect only 2 replications. The linear regression model describe d the data for Milorganite poorly (r2 = 0.51). We, therefore, estimated RPP values for Milorganite vi a point estimates (Table 3-9) calculated using equation 3-2. Point Estimate RPP = (P uptake source P uptake control ) / P applied source (3-2) (P uptakeTSPP uptakecontrol) / P appliedTSP At the 56, 112, and 224 kg P ha-1 rates, P in Milorganite was 38%, 31%, and 23% as phytoavailable as TSP, respectively. Thus, on averag e, Milorganite is ~31% as phytoavailable as TSP, placing it in the lower end of the modera te category of RPP values proposed by O’Connor et al., (2004). Milorganite would be assumed a priori to be in the low category of RPP values, based on PWEP (0.58%) and PSI ( 0.55) values, however the data support a moderate RPP for Milorganite. We also fit the P uptake data for Milorganite to a pl ateau model (Equation 3-2, Figure 3-10).

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48 where a = concentration of P in control (no added P) b = P concentration plateau incr ement above the background (mg) c = rate constant for change in uptake for a gi ven change in the cumula tive amount of P applied P applied = rate of P application Uptake (mg) = a + b(1-e-c*Papplied) (3-2; Barbarick et al., 1995) The good fit of the data to the plateau mode l confirms the unique P characteristics of Milorganite. We can calculate a similar RPP fo r Milorganite by dividing the mean cumulative P uptake for Milorganite (30.9 mg) by the mean cumulative P uptake for TSP (106 mg) at the 224 kg P ha-1 application rate: 30.9 mg/ 106 mg *100 = 29% RPP. Even at the high P loads (224 kg P ha-1) associated with N-based application rates, Milorganite is only ~29% as phytoavailable as TSP (consistent with point estimate). The regression equation for the Lakeland NS uptake data resulted in a weak r2 value (0.54), so we confirmed the RPP calculated via th e slope-ratio approach using point estimates (Table 3-9). Averaging the point estimates for 56, 112, and 224 kg P ha-1 resulted in a RPP of 90% for the Lakeland NS biosolids (consis tent with slope-ratio approach). We attempted to correlate RPP with bios olids-PWEP, but the correlation did not adequately explain the relationship between RPP and biosolids-PWEP (r = 0.64). However, when RPP is plotted as a function of biosolid s-PWEP, (Figure 3-12) a logarithmic relationship exists (r2 = 0.79). The logarithmic correlation is no t strong enough to pred ict RPP using PWEP. However, it appears that biosolids-PWEP 14% segregates biosolids with greater RPP values from biosolids with lesser RPP values. Recall th e same trend was noted with the P release data from the dynamic laboratory incubati on; biosolids with PWEP values 14% could be assumed to result in a larger negative environmental impa ct than biosolids with PWEP values < 14%. In the glasshouse study, biosolids with PWEP valu es < 14% had RPP values below 60% (moderate

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49 RPP category), compared to bi osolids with PWEP values 14%, which had RPP values 90% (high RPP category). The glasshouse study conducted here, and earlier work by O’Connor et al. (2004), demonstrates the wide range of RPP values possible for various biosolids. Knowledge of biosolids-RPP is key to adjusti ng application rates, should P-ba sed limitations on biosolids land application be imposed. Results of the glasshous e study indicate that no change in biosolids application rate is needed (or justified) for BP R and BPR-like biosolids with RPP values in the high RPP category. However, application ra tes for Disney and GreenEdge could be approximately doubled that necessary to meet crop P needs. Based on the plateau model, Milorganite could be applied at rates 224 kg P ha-1, and will only be about 1/3 as available as TSP. The low RPP of Milorganite does not ne cessarily imply that Milorganite is a poor Pfertilizer; Bahiagrass grown in Milorganite -amended soil showed no signs of above ground P deficiency during the course of the experiment and Bahiagrass yields were equivalent to TSP treatment yields for each application rate. P Leaching A similar glasshouse study by Elliott et al (2002) used a base sand with minimal Psorbing capacity. The base sand used in this st udy had moderate P-sorb ing capacity (RPA = 8.6%). Elliott et al. (2002) showed that a Florida sand with even moderate P-sorbing capacity (RPA=15.3%) can limit P leaching. Minimal P leachi ng occurred in the current glasshouse. Only TSP and BPR materials applied at the highest ra te resulted in signifi cant P leaching (Appendix Table A-3). The base sand is lik ely retarding the advance of P through the soil column. This study is on going, and it is possible that P reta ined in the column th rough the first growing

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50 season will eventually leach during subsequent croppings. Given the deep rooting of Bahiagrass, the P sorbed to the base sand is also accessible for plant uptake.

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51 Table 3-1. Materials received for labor atory characterization Material Class Stabilization BPR (Y/N)Final Treatment WWTP Milorganite AA Aerobic N Thermally dried Milwaukee, WI Broward B Anaerobic N Thickene d, dewatered North District Jacksonville (JEA) Cake AA Anaerobi c N Thickened, dewatered Buckman GreenEdge AA Anaerobic N Thermally dried Buckman Lakeland Glendale AA Aerobic N Thickened, dewatered, BiosetTM system Glendale Lakeland North Side AA Aerobic, ATAD systemN Thic kened, dewatered North side Clay Fleming B Aerobic N Thicke ned, bio-N removal Fleming Island Clay Miller B Anaerobic/Lime Stab.aN Thickened, dewatered Miller Street OCUD S Cake B Anaerobic N Thickened, dewa tered, bio-N removal South OCUD E Cake NAb Un-stabilized Y Thickened, dewatered Eastern OCUD E Dry NA Un-stabilized Y Thermally dried Eastern Tampa AA Anaerobic N Thermally dried Howard F. Curren West Palm Beach Central AA Aerobic N Composted material East Central Region Disney Compost AA Composted Y Composted material Reedy Creek Pinellas Cake B Aerobic N Thic kened, dewatered South Cross Bayou Pinellas Dry AA Aerobic N Ther mally dried South Cross Bayou Tallahassee Smith AA Anaerobic/aerobic N Thickened, dewatered Thomas P. Smith Orlando City B Lime Stabilized N Thickened, dewatered Iron Bridge Boca Raton B Anaerobic Y Thickened, dewatered Glades Road Gainesville Regional Utilities (GRU) B Aerobic N Thickened Kanapaha Ocala AA Anaerobic N Thermally dried City of Ocala #3 alime stabilized. bNA = not applicable. Bolded mate rials used in glasshouse study.

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52 Table 3-2. Selected chemical and physical properties of biosolids P Source C N N C to N ratioSolids LOIb pH EC Fe Al Ca Average Producera g kg-1 % uS cm-1 g kg-1 Milorganiteg 360 60 60 6.0 95 72 6.3 2900 41 2.7 15 Milorganite Greens Grade 370 62 60 5.9 95 74 6.0 3630 39 3.0 19 Broward County 390 53 69 7.3 13 74 7.9 3570 16 6.6 39 Jacksonville (JEA) Cake 390 57 60 6.8 20 76 8.2 3170 11 7.1 24 GreenEdgeg 350 50 52 7.0 93 71 6.9 2600 15 8.4 25 Lakeland Glendale 170 30c 24 5.7 35c 17 12c 6200 2.2c 3.16c 310c Lakeland North Sideg 380 59 70 6.4 3 75 8.5 6550 4.5 11 22 Baltimore 300 43 52 7.1 87 61 5.9 2300 60 24 15 Clay Fleming 340 55 44 6.2 2 69 7.8 245 51 9.0 13 Clay Miller 350 54 NPd 6.3 19 64 9.3 932 6.6 6.8 119 Orange County Southg 380 60 71 6.3 11 76 7.8 2750 5.4 5.6 24 Orange County East Cake 430 70 82 6.2 16 84 5.9 2700 2.2 7.7 17 Orange County East Dry 430 70 NP 6.2 95 84 5.9 1069 1.9 7.5 17 Tampa 410 56 52 7.4 96 76 7.1 743 8.8 8.8 42 West Palm Beach Compost 420 16 NP 26 64 56 6.5 2200 NDe ND ND Disney Compostg 410 28 22 15 66 77 5.7 5190 37 10 16 Pinellas Cake 310 43 54 7.3 24 68 7.5 1173 27 15 27 Pinellas Dry 320 48 62 6.8 92 69 6.9 1157 28 19 35 Tallahassee Smith 430 65 41 6.6 98 20 5.9 1673 8 13 26 Orlando City 280 42 51 6.6 20 49 13 7730 2.6 3.5 159 Boca Ratong 370 62 50 6.0 13 76 7.5 3390 12 6.4 25 GRUg 400 64 62 6.2 5 80 6.4 1108 7.7 5.5 14 Ocala ND ND NP ND 93 ND 5.9 1833 11 9.8 20 TSPfg ND ND ND ND 92 21 5.9 ND 16 10 140 aProducer supplied data. bLOI = loss on ignition. cData from Brandt and Elliott, 2005. dNP = data not provided. eND = not determined. fTSP data from O’Conn or et al. (2004). gMaterials used in glasshouse study.

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53 Table 3-3. Selected phosphorus properties of materials P Source Total P Fe-Strip Oxalate Extractable DeterminedProducera P WEP PWEP P Al Fe PSI g kg-1 % g kg-1 Milorganiteg 21 23 0.08 0.12 0.58 16 1.2 25 0.55 Milorganite Greens Grade 20 23 ND 0.19 0.85 15 1.4 24 0.53 Broward County 20 19 0.08b 1.3b 6.7 18 6.0 5.0 2.0 Jacksonville 15 20 0.05 0.31 2.0 13 10 5.0 1.2 GreenEdgeg 17 19 0.12 0.19 1.1 13 5 13 1.0 Lakeland Glendale 11b NDc ND 0.08† 0.92† 1.9 0.4 0.4 NAd Lakeland NSg 29 29 0.35 14 47 22 3.2 8.3 2.0 Baltimore 23 27 ND 0.04 0.15 21 12 52 0.5 Clay Fleming 31 18 ND 0.47 1.4 32 8.1 52 0.83 Clay Miller 16 ND ND 0.04 0.23 4.2 1.4 1.8 1.6 Orange County Southg 23 30 0.14 4.8 21 23 5.0 4.4 2.9 Orange County East Cake 20 23 0.34 8.0 41 17 1.3 3.1 4.1 Orange County East Dry 23 23 1.4 2.7 11 22 4.5 1.1 3.8 Tampa 21 25 0.29 0.07 0.29 17 5.6 6.0 1.8 West Palm Beach Compost 7.9 ND ND 0.71 8.1 9.1 1.8 6.5 1.6 Disney Compostg 11 27 0.95 0.02 0.22 11 7 20.0 0.43 Pinellas Cake 31 41 ND 0.27 0.78 30 11 12 1.6 Pinellas Dry 33 41 0.11 0.16 0.44 27 14 32 0.79 Tallahassee Smith 21 31 ND 1.4 6.1 19 6.5 5.2 1.8 Orlando City 17 20 0.003 0.04 0.23 13 1.7 2.4 NA Boca Ratong 26 39 0.02 3.9 15 33 14 7.3 2.1 GRUg 31 48 1.7 7.9 26 21 6.4 3.7 2.1 Ocala 21 28 0.74 0.63 3 20 11 5.6 1.5 TSPg 190 210 ND 170 85 186 11 6.8 NA aProducer supplied data. bData from Brandt and Elliott, 2005. cND = not determined. dNA = not applicable. gMaterials used in glasshouse study.

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54 Table 3-4. Comparison of biosolids-TP concentrations determined by 3 digestion methods P Source EPA3050A Anderson Perchloric Producera g kg-1 Milorganite ND 21 24 23 Broward 23 20 26 19 JEA Cake 18 15 20 20 GreenEdge ND 17 ND 19 Lakeland NS 37 29 38 29 OCUD S 26 21 32 30 OCUD E Cake 24 20 29 23 Disney ND 11 ND 27 Orlando 18 17 19 18 Boca Raton 34 26 39 39 GRU ND 31 ND 48 Standard Reference 22 (91%) 21 (88%) 23 (96%) 24 aProducer-supplied data. bND: not determined.

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55 Table 3-5. Dynamic laboratory incubation: cumulative net SRP released and SRP released as a percentage of applied P. Means 1 standard error, n = 3. Cumulative P P Source Rate Cumulative P released released kg P ha-1 % of applied P Control 0 0.67 0.062 NA TSP 56 8.33 0.318 80.9 3.08 TSP 224 30.5 1.11 74.0 2.69 Milorganite 56 3.96 1.11 38.5 10.8 Milorganite 224 7.84 1.54 19.0 3.73 GreenEdge 56 4.12 0.442 40.0 4.29 GreenEdge 224 11.3 0.842 27.4 2.04 Disney 56 5.66 0.252 42.0 1.34 Disney 224 21.6 2.42 39.9 1.80 GRU 56 6.90 0.239 67.0 2.32 GRU 224 28.2 1.08 68.5 2.63 Boca Raton 56 9.03 0.505 87.7 4.90 Boca Raton 224 32.7 0.756 79.3 1.84 Lakeland NS 56 9.27 0.228 90.0 2.21 Lakeland NS 224 25.7 0.770 62.4 1.87 OCUD E Cake 56 9.56 0.347 92.8 2.15 OCUD E Cake 224 32.9 0.275 79.9 1.14 OCUD E Dry 56 7.16 0.221 69.5 2.05 OCUD E Dry 224 25.7 0.469 62.4 1.05 OCUD S 56 10.0 0.212 97.3 3.37 OCUD S 224 33.0 0.434 80.0 0.667 Broward 56 6.33 0.753 61.4 7.31 Broward 224 13.0 0.856 31.5 2.08 Tallahassee 56 5.43 0.138 52.8 1.34 Tallahassee 224 16.6 0.742 40.3 1.80

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56 0 10 20 30 40 50 60 70 80 90 100M i l org ani t e GreenE d ge Di s ney T a l l ahas s e e B ro ward GRU OCUD E Dry T S P B o ca R at o n L a k el a n d NS OCUD E Ca k e OCUD SP SourceCumulative P Released (% of Applied P)aa ab abc abcd bcdcd de ef ef ef f 0 10 20 30 40 50 60 70 80 90 100M i l org ani t e GreenE d ge B ro ward Di s ney T a l l ahas s e e OCUD E Dry L a k el a n d NS GRU T S P B o ca R at o n OCUD E Ca k e OCUD SP SourceCumulative P Released (% of Applied P)a ab b b b c c cd de e e e Figure 3-1. Cumulative SRP released (% of applie d P) as a function of P source. Means capped with the same letter are no t different (Tukey’s Test, p 0.05). A) P-rate: 56 kg P ha-1. B) P-Rate: 224 kg P ha-1. A B

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57 y = 10.4 Ln(x) + 45.4 r2 = 0.646 CV = 18.7%0 10 20 30 40 50 60 70 80 90 100 0102030405060708090Biosolids-PWEP (%)P Leached (% of applied) y = 11.1 Ln(x) + 30.7 r2 = 0.692 CV = 21.5%0 10 20 30 40 50 60 70 80 90 1000102030405060708090Biosolids-PWEP (%)P Leached (% of applied) Figure 3-2. Dynamic laboratory incubation: cumulative P released (% of applied P) as a function of biosolids-PWEP. Error bars represent 1 standard error. Vertical line at biosolidsPWEP = 14% indicates when increased nega tive environmental impact may occur. A) P-Rate: 56 kg P ha-1. B) P-Rate: 224 kg P ha-1 A B

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58 0 10 20 30 40 50 60 70 80 90 100 0.00.51.01.52.02.53.03.54.04.5PSICumulative P Released (% of applied) 0 10 20 30 40 50 60 70 80 90 100 0.00.51.01.52.02.53.03.54.04.5PSICumulative P Released (% of applied) Figure 3-3. Dynamic laboratory inc ubation: cumulative P released as a function of PSI. Dashed vertical line at 1.1 PSI represents change point proposed by Elliott et al. (2002). Solid vertical line at 2.0 PSI represen ts increased critical PSI va lue suggested by data in the current study. A) P-Rate: 56 kg P ha-1. B) P-Rate: 224 kg P ha-1. A B

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59 0 10 20 30 40 50 60 70 80 90 100 12345678 Leaching EventCumulative P Released (% of Applied P) OCUD S OCUD E Cake Lakeland Northside Boca Raton TSP OCUD E Dry GRU Broward Tallahassee Disney GreenEdge Milorganite Figure 3-4. Dynamic laboratory incubation: cumulative P released (% of applied P) per leaching event. A) P-Rate: 56 kg P ha-1. B) PRate: 224 kg P ha-1. A

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60 0 10 20 30 40 50 60 70 80 90 100 12345678Leaching EventCumulative P Released (% of Applied P) OCUD S OCUD E Cake Lakeland Northside Boca Raton TSP OCUD E Dry GRU Disney Tallahassee Broward GreenEdge Milorganite Figure 3-4. Continued B

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61 0 5 10 15 20 25 30 35 40C o n tro l Di s ney M i l org ani t e T S P GRU B o ca R at o n GreenE d ge L a k el a n d NS OCUD SP SourceCumulative yield (g)a b b b bb bb b 0 5 10 15 20 25 30 35 40C o n tro l T S P Di s ney GreenE d ge M i l org ani t e B o ca R at o n GRU L a k el a n d NS OCUD SP SourceCumulative Yield (g)a bb b bc bc bcbc c Figure 3-5. Cumulative Bahiagrass yields after 4 harvests. P-rate: 112 kg P ha-1. Means capped with the same letter are not different (Tukey Test, p 0.05). A) P-Rate: 56 kg P ha-1. B) P-Rate: 112 kg P ha-1. C) P-Rate: 224 kg P ha-1. A B

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62 0 5 10 15 20 25 30 35 40Control Lak el and NS D i sn ey T SP M i l o rgan i te GreenEdge Boca Ra t o n GRU OCU D SP SourceCumulative Yield (g)a ab b b b bb baFigure 3-5. Continued 0 5 10 15 20 25 30 3556112224P Applied (kg ha-1)Dry Matter Yield (g) TSP Milorganite Disney GRU Boca Raton Lakeland NS OCUD S Figure 3-6. Cumulative Bahiagrass yiel ds after 4 harvests for all P application rates. Horizontal line at ~28 g dry matter yield represents average dry matter yield across rates and treatments. Error bars represent 1 standard error. C

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63 0 5 10 15 20 25 30 35T S P M i l org ani t e GreenE d ge Di s ney GRU B o ca R at o n L a k el a n d NS OCUD SP SourceN Content per Harvest g N kg-1 Harvest 1 Harvest 2 Harvest 3 Harvest 4 Figure 3-7. Bahiagrass N tissue concentra tion per harvest. P-rate: 224 kg P ha-1. Error bars represent 1 standard error. 0 2 4 6 8 10 12 14 16 18OCUD SGreenedgeGRUMilorganiteLakelandTSPBoca RatonDisneyP SourceYield-weighted N Concentration (g kg-1) Figure 3-8. Bahiagrass yield-wei ghted N concentrati on after 4 harvests. P-rate: 224 kg P ha-1. Error bars represent 1 standard error.

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64 0 10 20 30 40 50 60 MilorganiteDisneyGreenEdgeBoca RatonGRUTSPOCUD SLakeland NSP SourceP Uptake (% of P Applied)a a a bbc bc bcc 0 10 20 30 40 50 60 MilorganiteGreenEdgeDisneyGRUBoca RatonTSPLakeland NS OCUD SP SourceP Uptake (% of P Applied)a aa b bb b b 0 10 20 30 40 50 60 MilorganiteDisneyGreenEdgeLakeland NSBoca RatonGRUTSPOCUD SP SourceP Uptake (% of P Applied)a a a a b b bb Figure 3-9. Cumulative Bahiagrass P uptake after 4 harvests. P -rate = 112 kg P ha-1. Means capped with the same letter are not different (Tukey Test, p 0.05). A) P-Rate: 56 kg P ha-1. B) P-Rate: 112 kg P ha-1. C) P-Rate: 224 kg P ha-1. A B C

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65 Table 3-6. Cumulative Bahiagrass yield-weight ed tissue P concentrations after four harvests. Yield-Weighted Tissue P concentration P Source Rate g kg-1 Control 0 0.531 0.06 TSP 56 1.86 0.09 TSP 112 2.71 0.21 TSP 224 4.20 0.40 Milorganite 56 0.91 0.06 Milorganite 112 0.97 0.10 Milorganite 224 1.18 0.08 GreenEdge 56 1.07 0.17 GreenEdge 112 1.39 0.7 GreenEdge 224 1.90 0.03 Disney 56 1.43 0.11 Disney 112 1.90 0.05 Disney 224 2.50 0.10 GRU 56 1.65 0.13 GRU 112 2.25 0.09 GRU 224 3.22 0.26 Boca Raton 56 1.59 0.16 Boca Raton 112 2.35 0.24 Boca Raton 224 3.16 0.49 Lakeland NS 56 1.81 0.11 Lakeland NS 112 2.45 0.04 Lakeland NS 224 3.50 0.21 OCUD S 56 1.71 0.09 OCUD S 112 2.41 0.14 OCUD S 224 3.42 0.16

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66 0 20 40 60 80 100 120 050100150200250P Applied (kg P ha-1)Cumulative P Uptake TSP GRU Lakeland NS OCUD S Boca Raton Milorganite GreenEdge DisneyFigure 3-10. Cumulative Bahiagrass P uptake as a function of P applied Table 3-7. R phosphorus phytoavailability of biosolids to TSP P Source r2 Linear Regression Coefficient RPP (%) Category Reference Study TSP 0.89 0.472 100 high Current OCUD S 0.90 0.519 110 high Current GRU 0.91 0.439 93 high Current Lakeland NS 0.54 0.435 92 high Current Boca Raton 0.86 0.429 91 high Current GreenEdge 0.88 0.222 47 moderate Current Disney 0.70 0.220 47 moderate Current Regression equation: y = ___x + 8.48 Current Milorganite 31* moderate Current TSP 0.400 100 O'Connor et al. (2004) Largo Cake 0.297 74 moderate O'Connor et al. (2004) Largo Pellets 0.193 48 moderate O'Connor et al. (2004) Baltimore Cake 0.136 34 moderate O'Connor et al. (2004) Tarpon Springs Cake 0.124 31 moderate O'Connor et al. (2004) Regression equation: y = ___x + 20.544; R2 = 0.91 O'Connor et al. (2004)aDetermined via point estimates.

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67 Table 3-8. Various RPP estimate model fit statistics 2 Rates Linear 2 Rates Polynomial (2) All Rates Linear All Rates Polynomial (2) P Source r2 CV r2 CV r2 CV r2 CV TSP 0.94 14.0 0.98 22.1 0.89 19.3 0.96 29.4 GRU 0.96 12.1 0.98 19.2 0.91 17.5 0.98 23.0 Lakeland NS 0.90 18.8 0.95 37.2 0.54 38.3 0.97 78.8 OCUD S 0.97 10.2 1.0 12.4 0.90 18.8 0.98 22.7 Boca Raton 0.96 12.4 0.96 27.2 0.86 22.1 0.95 33.0 Milorganite 0.80 19.2 0.93 32.4 0.51 27.6 0.88 35.3 Disney 0.93 14.4 0.95 17.8 0.7 26.7 0.97 23.7 GreenEdge 0.87 17.1 0.97 20.4 0.88 17.5 0.97 12.6

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68 Table 3-9. Point estimates of RPP for Milorganite and Lakeland NS biosolids P Source Rate RPP % Average TSP 56 100 100 TSP 112 100 TSP 224 100 Milorganite 56 38 31 Milorganite 112 31 Milorganite 224 23 Lakeland NS 56 108 90 Lakeland NS 112 106 Lakeland NS 224 55 0 5 10 15 20 25 30 35 40 050100150200250300P Rate (kg P ha-1)P Uptake (mg)0 5 10 15 20 25 30 35 40Uptake = 8.55 + 22.2(1-e-0.0203*P applied) Figure 3-11. Plateau model: P uptake of M ilorganite as a function of P applied

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69 y = 14.6 Ln(x) + 42.5 r2 = 0.7930 20 40 60 80 100 120 0102030405060708090 Biosolids-PWEPRPP (%) Figure 3-12. Relative phosphorus phytoavailabil ity (RPP) as a function of biosolids-PWEP. Vertical line at 14% PWEP indi cates when increased negative e nvironmental impact may occur.

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70 CHAPTER 4 CONCLUSIONS Dynamic Laboratory Incubation The objectives of the dynamic laboratory incuba tion were to quantify soluble P release, study kinetics of P release, and evaluate the le aching hazard of various biosolids sources. The experiment was designed to mimic an extreme situ ation of biosolids land application; the soil used had minimal P-sorbing capacity and no plants were grown to utilize supplied P. We accept our second hypothesis that P le aching would be significantly greater from BPR and BPR-like products than conventionally treated materials. P release from BPR and BPR-like biosolids was equal to TSP, thus we reject our third hypothesis that P lability from all biosolids would be less than TSP. This experiment is key to understand ing the environmental ha zard specific residuals may pose. Biosolids-PWEP is an excellent indication of how a biosolids will impact the environment when land applied to sandy, low P-so rbing soils. Biosolids with high PWEP values, including BPR and BPR-like materials yielded the greatest cumulative P leached. Biosolids with PWEP values 14% should be assumed to have a larger potential negative e nvironmental impact than biosolids with PWEP values <14%. PSI can al so be used to gauge the environmental impact of biosolids land applied to sandy soils with minimal P-sorbing capacity. Given the observed trends in PWEP and PSI values based on bios olids treatment process, (i.e. PWEP and PSI increase for BPR and BPR-like biosolids) e nvironmental hazard can be roughly gauged by a biosolids treatment process. While exceptions ex ist, much research has shown that BPR and BPR-like materials have a greater risk of P loss compared to conventionally produced and pelletized biosolids. In this study, the differences in cumulative P mass leached between the dried and BPR or BPR-like materials appear to re flect both physical and chemical controls on P

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71 solubility. The pellets of thermally dried material s did not completely dissolve over the course of the experiment, leading to smaller quantities of P released. Relatively high concentrations of Fe and Al in the Milorganite material also apparently decreased P release. Thermally dried and conventionally produced re siduals have a slower rate of P release than BPR and BPR-like products. Knowledge of the kinetics of P rel ease is important to understanding the effects a residual will have on th e environment. A slower rate of P release is desirable, because opportunity for plant uptake is in creased and there is less P in the soil solution at any given moment. The less P in the soil solu tion at any given time means less P is available for leaching through and out of the soil profil e, risking impairment of water bodies. The dynamic laboratory incubation demonstrates that biosolids land application should not be regulated by assuming all biosolids have e qual amounts of labile P. Measurements such as PWEP and PSI, should be considered in regu lating biosolids land application. Assuming all biosolids to have equal amounts of labile P, and requiring P-ba sed application rates without considering a residual’s individual environmenta l hazard would unfairly bu rden municipalities facing disposal problems or unfairly adva ntage WWTP producing BPR products. Blanket regulation of biosolids land appli cation is also unwise given the benefits biosolids can have to soil and crops when land applied. Biosolids land application can decreas e chemical fertilizer inputs. Chemical fertilizers designed to be water-s oluble and provide instan t plant nutrition are a greater environmental hazard than conventionally produced or thermally dried residuals. While BPR and BPR-like biosolids treatment processes ar e environmentally beneficial to reduce P in wastewater effluent, these mate rials likely pose a greater envir onmental hazard due to more P and greater P lability when land applied.

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72 Glasshouse Study If biosolids are to be applie d to agricultural land under P-based restrictions, the quantity of P that will be available to the crop beco mes critical. If a residual has low phytoavailability, and is applied at a P-based rate, the crop will be N and P deficient, requiring additional mineral fertilizer input. For BPR or BRP-like material s, P-based application to crops would provide sufficient P, but require supplemental N fertilizer to meet crop needs. Three BPR or BPR-like materials, and 1 conventionally pr oduced biosolids (OCUD S) exam ined herein, fit into the high category (>75% of TSP) proposed by O’Connor et al. (2004). One BPR (Dis ney) and 2 thermally dried materials (Milorganite and GreenEdge) were in the moderate RPP category (25-75% of TSP). Milorganite fits into the moderate ca tegory proposed by O’Connor et al. (2004), despite expectation that it would be a low RPP material. Based on determ ined RPP values for BPR and BPR-like biosolids, we accept our first hypothesi s that RPP would be greater from BPR and BPR-like biosolids than conventional biosolid s [with the exception of the conventionally digested OCUD S biosolids (RPP = 110% of TSP)]. Materials in the high category for RPP also had the greater cumulative P leached in the la boratory incubation. Materi als with high watersoluble P have more P available for plant up take. Materials with high RPP make excellent fertilizers, but can also pose a greater environmental risk for P loss. The 1995 U.S. EPA design manual (USEPA, 1995) suggests the average “relative effectiveness” for biosolids-P to be 50% of mi neral fertilizer. While the relative effectiveness factor admits not all P in bios olids is phytoavailable, this st udy, as well as a similar study by O’Connor et al. (2004), shows the wide range in the relative phytoavailability of biosolids. Again, P phytoavailability and leaching hazard are linked to biosolids treatment processes. The Milorganite biosolids, which is relatively hi gh in Fe and Al, showed the lowest relative phytoavailability (31%). The moderate RPP of the Di sney compost is likely due to fact that the

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73 material is a mixture of composted yard wa ste and biosolids, lo wering the quantity of soluble/available P. Materials with the greate st PWEP values showed the greatest relative phytoavailability. If and when biosolids P-base d regulation of biosolid s land application is imposed, it would be wise to consider individua l residual’s P characteristics (PWEP and PSI). Given the range of biosolids P characteristics, regu lating all biosolids as if residuals were all the same could unnecessarily limit beneficial biosolid s land application. Most states use a P-index approach to predicting P loss from a material, and most states do not differentiate biosolids by treatment process or characteristics such as PWEP. Currently, Florida uses the same source coefficient for all biosolids (0.015). Elliott et al. (2006) suggested calculating PSC values by multiplying by the WEP (PSC = 0.102 x WEP0.99), based on runoff P studies. Research not detailed in this thesis used 4 biosolids (Milorganite, OCUD S, Lakeland NS, and Disney) and TSP in rainfall simulations a nd measured TP, TDP, a nd biologically (algae) available P (BAP) in runoff and leachate from Immokalee soil. Flow-weighted TP, TDP, and BAP were all highly correlated to biosolids-PW EP values. With the exception of Lakeland NS, BAP losses from all biosolids and TSP was pre dominantly via leaching. The low solids content (3%), of the Lakeland NS biosolids, however, resu lted in extensive soil surface coverage with a layer of fine material that wa s particularly susceptible to ra in drop impact and runoff loss. Cumulative BAP in runoff and leachate for all bi osolids treatements was significantly less than from TSP treatments. Thus, in the short term, bi osolids-P (even with very high PWEP values) is much less of an environmental threat than ferti lizer-P. The results of the rainfall simulation confirm that leaching is the predominant P loss mechanism in typical Florida sands.

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74 Land-Applying BPR or BPR-Like Residuals Municipalities using BPR biosolids treatment processes have several options to reduce the impact the residuals will have on the envi ronment; however, each option has advantages and disadvantages. If supported by the P-Index, biosolid s can be land applied at P-based rates, which will reduce the labile P in the soil solution at any given time, decreasing the chance of negative environmental impact. P-based application rate s of BPR and BPR-like biosolids will provide sufficient crop P, but will require additional mi neral fertilizer input of N. While applying residuals at a P-based rate is environmentally sound, more land area is required for disposal and disposal costs will increase. Farmers will also face increased costs from purchasing additional N fertilizer, which may discourage them from utilizi ng biosolids as fertilizer. Soil incorporation can also reduce P loss, especially in soils with sufficient P sorbing capacity. Biosolids can also be co-applied with WTRs O’Connor and Elliott (2000) suggested that co-applying biosolids with water treatment residuals (WTR) increases soil P retention capacity and reduce P mobility. Agyin-Biriko rang et al. (2007) demonstrated that P sorbed to WTRs is retained long-term. The dynamic laboratory incubation experiment de monstrated the benefits of high Fe and Al concentrations in limiting P loss, and WWTPs could add Fe a nd Al salts to BPR and BPR-like products to reduce environmental risk, however th is would significantly increase biosolids mass, leading to transportation and disposal problems. The simplest approach is to apply biosolids to soils with sufficient P-sorption capacity (easily determined). Elliott et al. (2002) demons trated that even soils with moderate P-sorbing capacity could prevent significant P loss. Applying biosolids to land with sufficient P-sorbing capacity may require transporting biosolids longer distances, increasing transportation costs.

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75 Lastly, thermally drying biosolids can reduce labile P and significantly reduce biosolids mass, decreasing the negative environmental imp act. The trend for thermal drying to reduce P lability was not noted when the OCUD E cake material was dried, however the OCUD E cake material is un-digested, and therefore may not be land applied, which may produce unique P characteristics.

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76 APPENDIX GLASSHOUSE ANOVA AND CUMULATIVE DATA Table A-1. Cumulative Bahiagra ss P uptake after 4 harvests. Sum of Source DF Squares Mean Square F Value Pr > F Model 27 30.6 1.13 52.5 <.0001 Error 72 1.56 0.022 Corrected Total 99 32.2 R-Square Coeff Var Root MSE loguptake Mean 0.952 3.75 0.147 3.92 Source DF Type I SS Mean Square F Value Pr > F Treatment (source) 7 24.3 3.04 141 <.0001 Block 3 0.024 0.008 0.37 0.772 P-Rate 2 4.81 2.40 111 <.0001 Treatment*Rate 14 1.45 0.104 4.81 <.0001 Source DF Type III SS Mean Square F Value Pr > F Treatment (source) 7 10.8 1.55 71.3 <.0001 Block 3 0.024 0.008 0.37 0.772 PRate 2 4.81 2.40 111 <.0001 Treatment*Rate 14 1.45 0.104 4.81 <.0001

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77 Table A-2. ANOVA for cumulative Bahi agrass yield after 4 harvests. Sum of Source DF Squares Mean Square F Value Pr > F Model 27 3887782 143991 9.77 <.0001 Error 72 1061590 14744 Corrected Total 99 4949373 R-Square Coeff Var Root MSE sqyield Mean 0.786 15.8 121 771 Source DF Type I SS Mean Square F Value Pr > F Treatment (source) 7 2658619 3323274 22.5 <.0001 Block 3 49493 16497 1.12 0.3472 P-Rate 2 1 246 62078 4.21 0.0187 Treatment*Rate 14 1055512 75393 5.11 <.0001 Source DF Type III SS Mean Square F Value Pr > F Treatment (source) 7 1554892 222127 15.1 <.0001 Block 3 494934 16497 1.12 0.3472 P-Rate 2 124156 62078 4.21 0.0187 Treatment*Rate 14 1055512 75393 5.11 <.0001

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78 Table A-3. ANOVA for cumulative P l eached in glasshouse experiment. Sum of Source DF Squares Mean Square F Value Pr > F Model 27 87.8 3.25 45.5 <.0001 Error 72 5.14 0.071 Corrected Total 99 92.9 R-Square Coeff Var Root MSE lgleached Mean 0.945 49.2 0.267 0.543 Source DF Type I SS Mean Square F Value Pr > F Treatment 7 22.6 2.82 39.5 <.0001 Block 3 0.600 0.199 2.80 0.046 Rate 2 36.9 18.5 258 <.0001 Treatment*Rate 14 27.7 1.98 27.7 <.0001 Source DF Type III SS Mean Square F Value Pr > F Treatment 7 21.5 3.08 43.0 <.0001 Block 3 0.599 0.199 2.80 0.05 Rate 2 36.9 18.46 258 <.0001 Treatment*Rate 14 27.7 1.98 27.7 <.0001

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79 Table A-4. Glasshouse study: cu mulative Bahiagrass yields after 4 harvests. Means 1 standard error, n = 4. Rate Cumulative Yield Material kg P ha-1 g Control 0 15.9 1.3 TSP 56 26.6 1.0 TSP 112 26.2 0.49 TSP 224 25.1 0.84 Milorganite 56 26.6 1.1 Milorganite 112 28.4 0.70 Milorganite 224 26.3 2.0 GreenEdge 56 28.6 1.0 GreenEdge 112 26.7 0.23 GreenEdge 224 28.5 0.63 Disney 56 25.7 0.85 Disney 112 26.4 0.88 Disney 224 23.4 0.62 GRU 56 27.6 0.55 GRU 112 29.9 1.0 GRU 224 30.8 1.0 Boca Raton 56 28.1 0.79 Boca Raton 112 29.6 0.21 Boca Raton 224 30.1 0.48 Lakeland NS 56 29.5 1.3 Lakeland NS 112 30.6 0.63 Lakeland NS 224 16.8 4.0 OCUD S 56 30.9 1.2 OCUD S 112 33.1 1.1 OCUD S 224 33.5 1.6

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80 Table A-5. Glasshouse study: cumulative P uptake fo r Bahiagrass after 4 harvests. Means 1 standard error, n = 4. Cumulative P Uptake Material Rate mg Control 0 8.48 1.0 TSP 56 49.4 1.1 TSP 112 71.0 3.6 TSP 224 105 6.6 Milorganite 56 24.0 1.1 Milorganite 112 27.6 1.8 Milorganite 224 30.9 2.0 GreenEdge 56 30.5 1.5 GreenEdge 112 37.1 0.72 GreenEdge 224 54.0 88 Disney 56 36.8 2.3 Disney 112 50.1 1.2 Disney 224 58.5 1.7 GRU 56 45.4 2.0 GRU 112 67.1 2.5 GRU 224 99.0 4.7 Boca Raton 56 44.6 2.9 Boca Raton 112 69.8 3.4 Boca Raton 224 94.9 7.0 Lakeland NS 56 53.2 1.7 Lakeland NS 112 75.1 6.4 Lakeland NS 224 58.3 14 OCUD S 56 52.8 1.3 OCUD S 112 79.5 1.6 OCUD S 224 115 6.0

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81 Table A-6. Glasshouse experiment: cumulative P leached after 4 leachings. Means 1 standard error, n = 4. Cumulative Cumulative Material Rate P Leached P Leached kg P ha-1 mg % of P Applied Control 0 0.044 0.006 NA TSP 56 0.000 0.005 0.042 0.005 TSP 112 0.895 0.373 0.46 0.181 TSP 224 33.6 4.88 8.17 1.18 Milorganite 56 0.011 0.11 0.053 0.011 Milorganite 112 0.008 0.006 0.025 0.003 Milorganite 224 0.008 0.008 0.012 0.002 GreenEdge 56 0.005 0.006 0.046 0.005 GreenEdge 112 0.028 0.011 0.034 0.005 GreenEdge 224 0.042 0.009 0.021 0.002 Disney 56 0.002 0.006 0.004 0.002 Disney 112 0.002 0.002 0.001 0.000 Disney 224 0.008 0.015 0.001 0.002 GRU 56 0.028 0.009 0.069 0.009 GRU 112 0.423 0.106 0.226 0.051 GRU 224 13.6 3.73 3.30 0.906 Boca Raton 56 0.009 0.004 0.051 0.004 Boca Raton 112 0.261 0.199 0.147 0.096 Boca Raton 224 5.10 1.24 1.25 0.301 Lakeland NS 56 0.030 0.005 0.070 0.005 Lakeland NS 112 0.480 0.118 0.254 0.057 Lakeland NS 224 6.33 2.13 1.55 0.518 OCUD S 56 0.035 0.012 0.076 0.011 OCUD S 112 0.554 0.246 0.290 0.119 OCUD S 224 5.20 0.538 1.27 0.131

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82 LIST OF REFERENCES Agyin-Birikorang, S., G.A. O'Connor, L.W. J acobs, K.C. Makris, and S.R. Brinton. 2007. Longterm phosphorus immobilization by a drinking wa ter treatment residual. J. Environ. Qual. 36:316-323. Andersen, J.M. 1976. An ignition method for de termination of total phosphorus in lake sediments. Water Research 10: 329-331. Association of Official Anal ytical Chemists. 1990. Official methods of analysis of the Association of Official Analytical Chemists. 15th ed. Arlington, VA. Brandt, R.C. and H.A. Elliott 2005. Agricultural recycling of BiosetTM. Consulting report prepared for Biosolids Distribution Services, Inc. Brandt, R.C., H.A. Elliott, and G.A. O’Connor. 2004. Water-extractable phosphorus in biosolids: implications for land-based recyclin g. Water Environ. Research, 76:121-129. Butkes, M.A., D. Grasso, C.P. Schuthess, a nd H. Wijnja. 1998. Surface Complexation Modeling of Phosphate Adsorption by Water Treatment Residual. J. Environ. Qual. 27:1055-1065. Carpenter, S.R., N.F. Caraco, D.L., R.W. Ho warth, A.N. Sharpley, and V.H. Smith. 1998. Nonpoint pollution of surface water with phosphor us and nitrogen. Ecol. Applic., 8:559-568. Chambliss, C.G. and M.B. Adjei. Bahiagrass 2006. Bahiagrass. UF/I FAS Publication SS-AGR36. Univ. of FL, Gainesville. Chambliss, C., P. Miller, and E. Lo rd. 2001. Florida Cow-Calf Management, 2nd Ed.Forages. UF/IFAS Publication AN118. Univ. FL, Gainesville. Chardon, W.J., R.G. Menon, and S.H. Chien. 1996. Ironoxide impregnated filter paper (Pi test): I. A review of its development and methodol ogical research. Nutr. Cycling Agroecosyst. 46:41–51 Corey, R.B. 1992. Phosphorus regulations: Impact of sludge regulati ons. Crop Soils. 20:5-10. Elliott, H.A. and G.A. O’Connor. 2007. Phosphorus management for sustainable biosolids recycling in the United States. Soil Biol and Biochem. Dec. 26, 2006 [in press]. Elliott, H.A., R.C. Brandt, P.J.A. Kleinman, A.N. Sharpley, and D.B. Beegle. 2006. Estimating source coefficients for p hosphorus site indices. J. Environ. Qual. 35:2195-2201. Elliott, H.A., R.C. Brandt, and G.A. O’C onnor. 2005. Runoff phosphorus losses from surfaceapplied biosolids. J. Environ. Qual. 34: 1632-1639. Elliott, H.A., G.A. O’Connor, and S. Brinton. 2002. Phosphorus leaching of biosolids-amended sandy soils. J. Environ. Qual. 31:681-689.

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83 [FDEP] Florida Department of Environmental Protection. 2005. Summary of Class AA residuals. www.dep.state.fl.us/water/wastewater/dom/ docs/2004AA.pdf. Florida Department of Environmental Protection. Tallaha ssee, Florida. March 2007. Harris, W.G., R.D. Rhue, G. Kidder, R.B. Brow n, and R. Little. 1996. Phosphorus retention as related to morphology and sandy coastal plain soil materials. Florida Coop. Ext. Serv. Circ. 817. Univ. of Florida, Gainesville He, Z.L., A.K. Alva, and Y.C. Li. 1999. Sorptio n-desorption and solution concentration of phosphorus in fertilized sandy soil. J. Environ. Qual. 28: 1804-1810. Kidder, G., E.A. Hanlon, C.G. Chambliss. UF/I FAS Standardized Fertilizer Recommendations for Agronomic Crops. Univ. FL., Coop. Ext. Serv., IFAS, SL-129. 1998. Loeppert, R.H., W.P. Inskeep. 1997. Iron (Chapter 23) In: Sparks et al. (e ds). Methods of Soil Analysis. Part 3: Chemical Me thods. SSSA, Madison, WI. P. 649-650. Maguire, R.O., J.T. Sims, S.K. Dentel, F.J. Coale, and J.T. Mah. 2001. Relationship between biosolids treatment process and soil phosphor us availability. J. Environ. Qual. 30:10231033. Murphey, J. and J.P. Riley. 1962. Phosphorus analysis procedure. Methods of soil analysis. Part 2. A.L. Page (Ed.) 413-426. ASA and SSSA. Madison, WI. Nachabe, M., N. Shah, M. Ross, and J. Vomacka. 2005. Evapotranspiration of two vegetation covers in a shallow water table environment. Soil Sci. Soc. Am. J. 69:492-499. NRC. 1996. Nutrients requirements of beef cattle, 6th Ed; National Academy Press: Washington, DC. Obeysekera, J., J. Browder, L. Hornung, and M.A. Harwell. 2004. The natural south Florida system I: Climate, geology, and hydrology. Urban Ecosystems. 3:223-244. O’Connor, G.A. and D. Sarkar. 1999. Fate of land applied residuals-bound phosphorus. DEP WM 661. Florida Environ. Protection Agency, Tallahassee. O’Connor, G.A., S. Brinton, and M.L. Silvei ra. 2005. Evaluation and selection of soil amendments for field testing to reduce P losse s. Soil Crop Sci. Soc. Florida Proc. 64:2234. O’Connor, G.A. and H.A. Elliott. 2000. Co-app lication of biosolids and water treatment residuals. Final Report. Florida Department of Environ. Protection, Tallahassee, Florida. O’Connor, G.A., D. Sarkar, S.R. Brinton, H.A. E lliott, and F.G. Martin. 2004. Phytoavailability of biosolids phosphorus. J. Environ. Qual. 33:703-712.

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85 BIOGRAPHICAL SKETCH Sarah Chinault was born in Lakeland, Florida, on November 24, 1981 to Edward and Linda Chinault. Sarah has an older brother (Chr is, 28) and a younger sist er (Amanda, 23). Sarah obtained her B.S. degree from the University of Florida in 2004, majoring in environmental science. Sarah’s career goals include working for an environm ental advocacy or animal rights group. Always an animal lover, Sarah has 5 sma ll dogs that she considers children: Mocha (10), Mini-Me (7), Maynard (4), Hank (11), and Bauer (1). Mitch (11) recently passed from cancer and will be missed.


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Permanent Link: http://ufdc.ufl.edu/UFE0019385/00001

Material Information

Title: Agronomic and environmental characterization of phosphorus in biosolids produced and/or marketed in Florida
Physical Description: Mixed Material
Language: English
Creator: Chinault, Sarah L. ( Dissertant )
O'Connor, George A. ( Thesis advisor )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007
Copyright Date: 2007

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: UFE0019385:00001

Permanent Link: http://ufdc.ufl.edu/UFE0019385/00001

Material Information

Title: Agronomic and environmental characterization of phosphorus in biosolids produced and/or marketed in Florida
Physical Description: Mixed Material
Language: English
Creator: Chinault, Sarah L. ( Dissertant )
O'Connor, George A. ( Thesis advisor )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2007
Copyright Date: 2007

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: UFE0019385:00001


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AGRONOMIC AND ENVIRONMENTAL CHARACTERIZATION OF PHOSPHORUS IN
BIOSOLIDS PRODUCED AND/OR MARKETED IN FLORIDA





















By

SARAH L. CHINAULT


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

UNIVERSITY OF FLORIDA

2007
































O 2007 Sarah L. Chinault



































To Mom, Dad, Amanda, Chris, and Richelle.









ACKNOWLEDGMENTS

I would first like to thank Dr. O'Connor, my supervisory committee chair. While there

were times of great frustration (for both of us!) I am much better prepared for a professional

career thanks to his teachings. Thanks also go to Drs. Sartain and Elliott for serving on my

committee. I must thank Scott Brinton. Without his help, this proj ect would have been beyond

my capability. Scott has the ability to handle endless interruptions and stupid questions without

ever losing patience, for which I am grateful. Scott tended to daily greenhouse responsibilities,

and provided maj or help during harvests and teachings. Thanks go to Sampson Agyin-

Birikorang, who helped with the statistical manipulations of data. Sampson also has endless

patience and always made time to assist, even when his own duties were great. When I was

swamped with laboratory analyses, Matt Miller was a great help with dishes and other "lab

monkey" duties, which helped me maintain my sanity. Thanks go to Maria Silveria, who helped

me learn laboratory procedures when I started my working on my degree. Thanks go to the

College of Agriculture and Life Science (CALS) for providing a matching assistantship to pay

for my tuition. Additional stipend and research support was provided by the Florida Water

Environment Association (FWEA)-Utilities Council and Milorganite, Inc. Lastly, thanks go to

my family and friends, who supported me emotionally and financially (Dad!) through all my

years at UF.












TABLE OF CONTENTS


page


ACKNOWLEDGEMENTS ........._... ...........4........... .....


LIST OF TABLES ............... ............7... ......... ....


LIST OF FIGURES ............... ...........8.............. ....


AB STRAC T ......__.............. ............12.. ....


CHAPTER


1 INTRODUCTION ............... ...........14...................


Hypotheses and Research Obj ectives ............... ............................17
Study Approach ............... ...........18...................

2 MATERIALS AND METHODS ............... ...........19..................


M ateri als ........... .. ... ........ ............. ..........1
Year 1 Glasshouse and Static Incubation Studies ............... ....................19
Laboratory Characterization ............... ............20.. ...............
Dynamic Laboratory Incubation ............... ..............................23
Glasshouse Study ............... ............26.. ...............
Statistical Analysis ............... ...........29...................


3 RESULTS AND DISCUSSION ............... ...........31..................


Laboratory Characterization ............... ...........31...................
Dynamic Laboratory Incubation ............... ...............................35
Glasshouse Study ............... ............42.. ...............
Y ields.............. .... ............. ...........4
Phosphorus Uptake and Relative Phytoavailability ............... ...............45
Phosphorus Leaching ............... ...........49...................

4 CONCLUSIONS ............... ............70.. ...............


Dynamic Laboratory Incubation ............... ..............................70
Glasshouse Study ................... .. ........... ............72 .......
Land Applying BPR or BPR-like Residuals ............... .......... ............74


APPENDIX GLAS HOUSE ANOVA AND CUMULATIVE DATA. ................. ............76











LIST OF REFERENCES ...........__ ...........82.......... .....


BIOGRAPHICAL SKETCH ............... ............85.. ...............

































































6










LIST OF TABLES


Table page

2-1 Selected properties oflImmokalee fine sand ............... ......... .............30

3-1 Materials received for laboratory characterization ............... ............ ......51

3-2 Selected general chemical properties of materials ............... ........... ........52

3-3 Selected phosphorus properties of materials ............... .......... ............53

3-4 Comparison of TP concentrations determined by 3 digestion methods ................... ...54

3-5 Dynamic laboratory incubation: cumulative SRP released and SRP released
(% of applied P). ........._ .. ...........55......__. ....

3-6 Cumulative Bahiagrass tissue P concentrations after 4 harvests........... ..._.........65

3-7 Relative phosphorus phytoavailability of biosolids to TSP. ............... ..............66

3-8 Various RPP estimate model fit statistics ....._____ ......___ ............_67

3-9 Point estimates of RPP for Milorganite and Lakeland NS
biosolids ............... ............69.. ...............

A-1 Cumulative Bahiagrass P uptake after 4 harvests ANOVA. ............... ...............76

A-2 Cumulative Bahiagrass yield after 4 harvests ANOVA. ............... ............... 77

A-3 Cumulative P leached in glasshouse experiment ANOVA ............... .............78

A-4 Cumulative Bahiagrass yields after 4 harvests ............... ............... ...._79

A-5 Cumulative P uptake for Bahiagrass after 4 harvests ........._._. .........___.....80

A-6 Cumulative P leached after 4 leachings ............... ..........................81










LIST OF FIGURES


Figure page

3-la P rate: 56 kg P ha- Cumulative SRP released (% of applied P) as a function of
P source. ........._.._ ............56....___ .....

3-1b P rate: 224 kg P ha- Cumulative SRP released (% of applied P) as a function of
P source. ........._.._ ...........56...___ .....

3-2a P rate: 56 kg P ha- Dynamic laboratory incubation: cumulative P released (% of applied
P) as a function of biosolids-PWEP. ............... ............ ......... .....57

3 -2b P rate: 224 kg P ha- Dynamic laboratory incubation: cumulative P released (% of
applied P) as a function of biosolids-PWEP ............... ......... .............57

3-3a P rate: 56 kg P ha- Dynamic laboratory incubation: cumulative P released as a function
of bi osoli ds-P SI ............ ............58...__ __ ....

3-3b P rate: 224 kg P ha- Dynamic laboratory incubation: cumulative P released as a function
of bi osoli ds-P SI ............ ...........58....__ ....

3-4a P rate: 56 kg P ha- Dynamic laboratory incubation: cumulative P released (% of applied
P) per released event. ............... ...........59..................

3 -4b P-Rate: 224 kg P ha- Dynamic laboratory incubation: cumulative P released (% of
applied P) per released event. ............... ......... ......... .........6

3-5a P rate: 56 kg P ha- Cumulative Bahiagrass yields after 4 harvests .............. .... .......61

3-5b P-rate: 112 kg P ha- Cumulative Bahiagrass yields after 4 harvests ........... ....... .....61

3-5c P rate: 224 kg P ha- Cumulative Bahiagrass yields after 4 harvests ............. ...... ......62

3-6 Cumulative Bahiagrass yield-weighted tissue P concentrations after 4 harvests ...........62

3-7 P rate: 224 kg P ha- Bahiagrass N tissue concentrations in each harvest. .................. 63

3-8 P rate: 224 kg P ha- Bahiagrass yield-weighted N concentrations after 4 harvests.......63

3-9a P rate: 56 kg P ha- Cumulative Bahiagrass P uptake after 4 harvests. ................... ....64

3-9b P-rate: 112 kg P ha- Cumulative Bahiagrass P uptake after 4 harvests ................... ....64

3-9c P-rate: 224 kg P ha- Cumulative Bahiagrass P uptake after 4 harvests. ................... ..64

3-1 0 Cumulative Bahiagrass P uptake as a function of P applied ............... ..............66











3-11 Plateau model: P uptake from Milorganite treatments as a function of P applied........... 68

3-12 Relative phosphorus phytoavailability (RPP) as a function of biosolids-PWEP. ...........69









LIST OF ABBREVIATIONS


Al aluminum

AN ammonium nitrate

ANOVA analysis of variance

BAP biologically available phosphorus

BPR biological phosphorus removal

C carbon

Ca calcium

DDI distilled, de-ionized water

EC electrical conductivity

FDEP Florida Department of Environmental Protection

Fe iron

ICP inductively coupled plasma spectrophotometry

K potassium

LOI loss on ignition

Mg magnesium

N nitrogen

P phosphorus

PSC phosphorus source coefficient

PSI phosphorus saturation index

PV pore volume

PWEP percent water-extractable phosphorus

RPA relative phosphorus adsorption









RPP relative phosphorus phytoavailability

SRP soluble reactive phosphorus

S sulfur

TC total carbon

TN total nitrogen

TP total phosphorus

TRT treatment

TSP triple super phosphate

UJF University of Florida

USEPA United States Environmental Protection Agency

WEP water-extractable phosphorus

WTR water treatment residual

WWTP wastewater treatment plant









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

AGRONOMIC AND ENVIRONMENTAL CHARACTERIZATION OF PHOSPHORUS IN
BIOSOLIDS PRODUCED AND/OR MARKETED IN FLORIDA

By

Sarah L. Chinault

May 2007

Chair: George O'Connor
Major Department: Soil and Water Science

Land application of biosolids can result in an accumulation of soil phosphorus (P). While

excess soil P is typically not harmful to crops, P can migrate offsite and can lead to surface and

groundwater impairment. Increased concern over accelerated eutrophication of water bodies has

led to heightened scrutiny and regulation of biosolids land application. Regulation could include

limiting application rates to match crop P requirements (P-based rates). If P-based regulations are

imposed, it will be critical to understand biosolids P phytoavailability and the potential for

surface and groundwater impairment from biosolids P. We conducted laboratory and glasshouse

studies to provide understanding. A laboratory incubation was conducted using small soil

columns to assess P release potential: 11 biosolids and triple super phosphate (TSP) were

individually mixed with 400 g of a typical low-P sorbing Florida soil (Immokalee fine sand) at

two rates: 56 and 224 kg P ha- .

Columns were leached bi-weekly for 14 weeks to attain 60 mL of drainage in each

leaching. Soluble reactive P (SRP) was determined and summed over the 8 teachings.

Cumulative P release (as a percentage of P applied) was greatest from biological P removal

(BPR) and BPR-like biosolids. Phosphorus release from Milorganite, a thermally dried biosolids

high in Fe and Al oxides (44 g kg- ), released ~39% of applied P at the 56 kg P ha-l rate,









indicating that P release was limited by association of P with Fe and Al and by heat drying. In

contrast to the moderate P release from Milorganite, P release from the Lakeland NS biosolids, a

BPR-like product with low percent solids (3%), and low Fe and Al content (~12 g kg- ), was

~90% of P applied at 56 kg P ha- .

A glasshouse study utilizing large soil columns was conducted: 7 biosolids and TSP were

individually mixed with 4 kg samples of Immokalee soil and Bahiagrass (Paspalum notatum

Flugge) was grown. Bahiagrass was harvested monthly for 4 months and tissue total P (TP) was

measured. Four of the biosolids chosen for the glasshouse study had high PWEP values (>15%),

and their P was expected be highly plant available. Indeed, the OCUD S, Lakeland NS, GRU,

and Boca Raton biosolids fit into the "high" category of relative P phytoavailability (RPP; >75%

of TSP). Two biosolids with low P-solubility (PWEP I 1.1%) fit into the moderate RPP category

(25-75% of TSP): Milorganite, and GreenEdge. One biosolids (Disney) with a moderate PWEP

(8.4%) also fit into the moderate RPP category. Results of the glasshouse study indicate that no

change in biosolids application rate is needed (or justified) for BPR and BPR-like biosolids with

RPP values in the high RPP category. However, application rates for Disney and GreenEdge

could be approximately doubled to meet crop P needs. Phosphorus in Milorganite is only ~1/3 as

phytoavailable as P in TSP, indicating that Milorganite may be applied at P rates as great as 224

kg P ha-l (based strictly on phytoavailability). Given the wide range of RPP values and leaching

risks of various biosolids, land application of biosolids should not be regulated en masse. PWEP,

and PSI are easily determined and excellent gauges of both biosolids agronomic value and P

leaching hazard. PWEP is a better indication of how a biosolids might affect the environment

than biosolids-TP or soil test P.









CHAPTER 1
INTTRODUCTION

Throughout history, human and animal wastes have been recycled to agricultural land to

supply nutrients for crops. However, the development of centralized wastewater treatment

systems, and an ever-increasing human population has created biosolids disposal challenges. The

U.S. produced an estimated 6.5 X 106 Mg of biosolids in 2000 and approximately 50-60% of

biosolids were disposed of via land-based recycling (USEPA, 1999). Biosolids production is

expected to increase to 7.5 X 106 Mg yrl by 2010. The state of Florida produces about 2.7 X 105

dry Mg of biosolids per year; 66% of the biosolids are land applied, 17% are land filled, and 17%

are marketed and distributed to the public (FDEP, 2005). In addition to biosolids produced

within the state of Florida, 9. 1 X 104 Mg of class AA pelletized biosolids are imported each year.

Given the large quantities of biosolids produced, land-based recycling of biosolids becomes a

critical disposal route for municipalities. Biosolids land application can also be an

environmentally sound and beneficial practice.

Biosolids are a source of essential plant elements such as N, P, sulfur, and micronutrients.

Thus, land-based recycling of biosolids to agricultural land can supply farmers with an economic

alternative to chemical fertilizers. Biosolids are also high in organic matter, which can be

important in Florida, where soils are typically sandy and low in organic matter. While the land

application of biosolids is beneficial, long-term biosolids application can result in accumulation

of soil P (O'Connor et al., 2005). When biosolids are applied at an N-based rate to meet crop N

requirements, P is typically oversupplied due to differences in biosolids N:P than crop needs.

The excessive P accumulation it is not harmful to crops (Person et al., 1994), but leads to

accumulation of P in amended soils and potential environmental problems. Migration of P off-

site to ground and surface waters is a cause for concern as P is generally the limiting nutrient in









fresh water ecosystems for accelerated eutrophication (Carpenter et al., 1998). P can migrate off-

site either in dissolved form, as biosolids particles, or attached to soil particles (Elliott et al.,

2005). Most soils in the U.S. have sufficient P-sorbing capacity (due to Fe and Al oxides) to

prevent P leaching. Elliott et al. (2002) showed that even sandy Florida soils with moderate P-

sorbing capacity can prevent P leaching. In soils with adequate P-sorbing capacity, P loss occurs

mostly through erosion and runoff, and erosion control measures can help control P loss in these

soils. Atlantic Coastal Plain soils (including most Florida soils), however, are naturally low in Fe

and Al oxides. In such soils, P leaching and loss of P dissolved in subsurface flow become the

dominant P loss mechanism (He et al., 1999).

Excess P in water bodies can lead to accelerated eutrophication. Increased concern over

water quality has led to amplified scrutiny of biosolids land application programs and

recommendations that biosolids application be limited to meet crop P needs (P-based). Limiting

biosolids land application to P-based rates would significantly reduce biosolids application rates.

When application rates are decreased, more land area is required for disposal, increasing disposal

costs. Lower biosolids application rates also mean additional N fertilizer is required, increasing

costs to farmers, and making land-based recycling of biosolids for agronomic benefits less

attractive.

Recent research suggests that limiting biosolids application to P-based rates is probably

unnecessary for conventionally produced biosolids (Brandt et al., 2004). Biosolids-P is not

necessarily as labile as P in mineral fertilizers or manures, and liability can be greatly influenced

by the wastewater treatment process (Maguire et al., 2001). Treatment processes such as thermal

drying can significantly reduce P liability of biosolids compared to conventionally produced cake

(Smith et al., 2002). A possible exception may be biological P removal (BPR) biosolids, in









which the wastewater treatment process is engineered to promote luxury uptake of P by bacteria.

While the BPR process reduces P concentrations in wastewater effluent, the resulting biosolids

have a higher concentration of P than conventionally produced residuals, and labile P in BPR

biosolids may be higher than for conventional or heat-dried biosolids (Elliott et al., 2002; Brandt

et al., 2004; O'Connor et al., 2004).

Total P (TP) concentration of the biosolids is generally a poor indicator of P liability and

phytoavailability. Only a small fraction of P from most conventionally produced biosolids is

soluble, making most biosolids less likely to negatively impact the environment compared to

soluble P sources (mineral fertilizer, manures). The water-extractable P (WEP) content of

biosolids has been highly correlated to P liability (Brandt et al., 2004). For typical biosolids,

percent water-extractable P (PWEP = WEP/TP*100) is < 5% (Brandt et al., 2004), and

phytoavailability (plant-available) P is only 40-50% of TSP (USEPA, 1995). Biosolids produced

using iron (Fe) and aluminum (Al) salts may have even lower P liability and PWEP values

(<0.5%) (Corey, 1992; Brandt et al., 2004). BPR biosolids may have much greater soluble P

concentrations than conventionally produced biosolids, and greater PWEP (~ 14%) (Brandt et

al., 2004).

The phosphorus saturation index (PSI) has also been correlated to environmental P

leaching risk (Elliott et al., 2002). PSI is calculated as the molar ratio of oxalate-extractable P to

Fe and Al ([Pox]/[Alox + Feox]). When biosolids have PSI values less than 1.1, little P leaching is

expected to occur, even in sandy, low P-sorbing soils (Elliott et al., 2002). Both PWEP and PSI

can serve as a priori estimates of biosolids-P liability. Both measures can better estimate how P

in biosolids will affect the environment when land applied than biosolids-TP or soil test P

measures (Maguire et al., 2001; Elliott et al., 2002; Brandt et al., 2004; O'Connor et al., 2004).










Given the nutrient concerns that accompany biosolids land application, each state's

Natural Resources Conservation Service (NRCS) is required by the Unified Strategy for Animal

Feeding Operations (USDA/USEPA, 1999) to develop P management strategies. Under code

590, states have three options to manage P: agronomic soil test P recommendations,

environmental soil P thresholds, or a P site index to evaluate vulnerability to potential P loss

(Elliott and O'Connor, 2007). Most states have chosen a P-index approach as both P source and

transport factors are taken into account. The P-index acknowledges that for negative

environmental impacts to occur, both a soluble P source and a transport mechanism are required

(Sharpley et al., 2003). The state of Florida is in the midst of developing a P-index to manage P

nutrient concerns.

Hypotheses and Research Objectives

A good understanding of biosolids P phytoavailability relative to fertilizer-P is critical to

making adjustments to biosolids application rates should P-based application restrictions be

imposed. All biosolids do not have the same potential to negatively affect the environment,

hence, it is important to know which biosolids-P chemical characteristics can be used to judge a

priori the environmental impact a biosolids will have once land applied.

* Hypothesis 1: Relative P phytoavailability is greater for BPR biosolids than conventionally
produced biosolids.

* Hypothesis 2: P leaching is significantly greater from (sandy, low P-sorbing) soil amended
with BPR residuals than the same soil amended with conventionally treated biosolids.

* Hypothesis 3: P liability of all biosolids is less than fertilizer-P (TSP).

* Objective 1: Characterize the agronomic value of various biosolids important in Florida so
adjustments can be made to biosolids application rates if biosolids P-based regulations are
imposed.










* Objective 2: Develop sufficient data to demonstrate that most biosolids pose less of an
environmental hazard (with the possible exception of BPR biosolids) than readily soluble P
sources.

* Objective 3: Expand the database of knowledge to include a wider variety of biosolids
production schemes, specifically materials produced or marketed in Florida. Research was
focused on materials not previously studied in detail, specifically BPR materials.

Study Approach

A full laboratory characterization was conducted on 21 biosolids produced or marketed in

Florida to identify materials warranting further study in glasshouse and laboratory experiments.

Seven residuals were chosen for a glasshouse study to judge agronomic P availability and

environmental liability. Eleven biosolids were chosen for a dynamic laboratory incubation, the

purpose of which was to quantify water soluble P, examine the kinetics of P release, and

determine the leaching hazard of various biosolids materials.









CHAPTER 2
MATERIALS AND METHODS

Materials

Wastewater treatment plants (WWTPs) throughout Florida were invited to participate in

the research effort by completing a survey (developed by Robert Morrell of PBS&J consulting)

of plant operations and materials characteristics. Completed surveys were submitted by 24

WWTPs, representing 22 residuals products, and results were forwarded to UF personnel. Based

on survey results, 20 Florida products were requested from WWTPs for analysis. A few samples

of biosolids produced in other states, but marketed in Florida, were also requested. Milorganite, a

commercially available biosolids product from Wisconsin, was chosen to be included in this

study. In total, 21 materials were subjected to laboratory characterization.

Year 1 Glasshouse and Static Incubation Studies

In 2005, glasshouse and static laboratory incubation studies were conducted with 9

biosolids: Milorganite, GreenEdge, Jacksonville Cake, Tampa, Disney Compost, Pinellas Cake,

Boca Raton, and Orange County Utilities Division (OCUD) east dry and cake materials. The

residuals were individually amended to a typical Florida Spodosol (Immokalee fine sand) at 2 P-

application rates: 56 and 224 kg P hal to represent P-based and N-based biosolids application

rates, respectively. Most of the soil was used in the glasshouse study, but some was used in a

static laboratory incubation. The glasshouse study was intended to provide measures of P

leaching risk and relative P phytoavailability to pasture grass of various biosolids. Amended soils

used in the static laboratory incubation were sampled at various times for WEP and TP

determination, and the data were intended to yield information about the kinetics of biosolids-P

release. Both the glasshouse study and the static laboratory incubation experiments were

terminated in December 2005 because of apparent un-equal P loadings in treatments. We have









no explanation for the unequal P loads, but without equal P loadings, conclusions on relative P

phytoavailability and P leaching were not possible. Similar studies were begun anew in 2006.

Laboratory Characterization

Biosolids percent solids was determined by drying (105o C) "as is" materials to constant

weight. Biosolids pH and electrical conductivity (EC) were determined using a 1:10 ratio of

biosolids (dry weight equivalent) to distilled, de-ionized water (DDI), and equilibrated by static

incubation at room temperature for 2 hours. After the 2 hr equilibration, the biosolids-DDI water

mixture was stirred and allowed to settle, and pH and EC were determined on the solution. Total

carbon/ total nitrogen (TC/TN) was determined on dried, ball-milled biosolids by combustion at

10100 C using a Carlo Erba (Milan, Italy) NA-1500 CNS analyzer.

Loss on ignition (LOI), a measure of biosolids organic matter content, was determined by

measuring 0.2 g of oven-dried and ball-milled biosolids into pre-weighed 50 mL beakers. The

materials were ashed at 2500C for 30 minutes, followed by ashing at 5500C for an additional 4

hours. The samples were allowed to cool, and the beakers were weighed again. Mass lost during

the ash process is a measure of organic matter (Sparks, 1996).

To analyze for total phosphorus (TP), samples of biosolids were first oven-dried and

ground in a ball mill to a fine powder. The biosolids (0.2 g) samples were then ashed (2500C for

30 minutes and 5500C for 4 hours) in a muffle furnace to destroy organic matter. The ashed

samples were digested with ~2 mL of DDI water and 20 mL of 6 M HC1. The beakers were

placed on a hotplate at 110o C until the HCI evaporated, and the residual was dry. The hotplate

temperature was then increased to the hottest setting (~3000C) for 1 hour. The beakers were

allowed to cool, and ~2 mL of DDI and 2.25 mL of 6 M HCI was added to the residual material

and the beakers were placed on a hot plate (highest setting) until small bubbles started to form

(solution began to boil). The solution was removed from the hotplate and allowed to cool. The









solution was transferred quantitatively to a funnel containing a Whatman #42 fi1ter, and allowed

to drain into 50 mL volumetric flasks. The fi1ter paper was rinsed 3 times with DDI and allowed

to drain completely between each rinse (Andersen, 1976). The solutions were brought to volume

and analyzed for P using the molybdenum blue method (Murphey and Riley, 1962). Digests from

the Andersen (1976) method were also analyzed for total Fe, Al, and Ca via inductively coupled

plasma spectroscopy (ICP).

We also determined biosolids-TP using EPA method 3050A (USEPA, 1995) to verify TP

values determined by the Andersen (1976) method were accurate. Method EPA3050A required 2

g (dry weight equivalent) of biosolids. Samples were pre-digested with 10 mL of 1:1 HNO3,

covered with reflux caps, and heated at 110oC for 10-15 minutes. After the pre-digestion, an

additional 5 mL of HNO3 WAS added and the samples were refluxed for 30O minutes. This second

step was repeated until brown fumes were no longer visible. The reflux caps were removed and

the digestion solution was allowed to evaporate (2-3 h) to a volume of 5 mL. The flasks were

removed from the hotplate and allowed to cool. Then, 30 mL of 30% hydrogen peroxide and 2

mL of DDI was added and new reflux caps were place on top of the flasks. The samples were

returned to the hotplate set at 110oC until effervescence subsided. Additional 1 mL aliquots of

30% hydrogen peroxide were added (not exceeding 10 mL) until effervescence ceased. After the

peroxide reaction, 5 mL of concentrated HNO3 WAS added and the samples were refluxed for 30

minutes. The samples were then cooled, and filtered through a Whatman #41 fi1ter into 50 mL

volumetric flasks. The fi1ters were rinsed 3 times with DDI and allowed to drain completely

between each rinse. Filtered digests were brought to volume and analyzed for P via ICP.

Biosolids-TP was also determined by an outside laboratory via perchloric acid digestion

(Association of Official Analytical Chemists, 1990; The Fertilizer Institute, 1982) to further









confirm TP values. One gram of dried and powdered biosolids were boiled with 30 mL of

concentrated HNO3 for ~20 minutes. The samples were cooled and 20 mL of perchloric acid was

added until the solutions were colorless and started to fume. Once samples were colorless, and

white fumes were noted, the digestion was continued for an additional 20 minutes. Following the

second 20-minute digestion, 30 mL of DDI was added and the samples were boiled for 5

minutes. Samples were then cooled and filtered through an Ahlstrom Grade 54, 12.5 cm filter

paper into a 100 mL volumetric flask. Samples were brought to volume and analyzed for P via

ICP.

Water-extractable P (WEP) was determined using a 1:200 biosolids (dry weight

equivalent) to DDI water (Sharpley and Moyer, 2000). The residuals/water mixture was shaken

on an orbital shaker at 200 strokes per minute for 1 hour. A sub-sample of the mixture was

centrifuged for 10 minutes at 4000 rpm, and the supernatant was vacuum-filtered through a 0.45

Cpm- Eilter. The solution was analyzed for P using the molybdenum blue method (Murphey and

Riley, 1962). Percent WEP (PWEP) was calculated by dividing WEP by TP and multiplying by

100 (PWEP = WEP/TP*100). Brandt et al. (2004) concluded that PWEP was a good measure of

the environmentally relevant portion of total P in biosolids and manures.

Oxalate-extractable P, Fe, and Al was determined by shaking 0.5 (dry weight equivalent)

of biosolids with 30 mL of 0. 175 M ammonium oxalate and 0. 1 M oxalic acid for 4 hours on an

orbital shaker at 200 strokes per minute (Loeppert and Inskeep, 1997). The samples were shaken

in a sealed box to avoid exposure to light. After shaking, the samples were centrifuged for 10

minutes at 4000 rpm, and vacuum filtered through a Whatman #42 fi1ter. The supernatant was

analyzed for P, Fe, and Al via ICP. Moles of oxalate-extractable P, Fe, and Al were used to









calculate PSI, an indication of labile P in residuals [PSI = moles P/ (moles Fe + mole Al)] (Elliott

et al., 2002).

Fe-oxide extractable P (Fe-strip P) in biosolids was determined using Fe-oxide

impregnated strips (Chardon, 1996). Strips were prepared by soaking Whatman #42 filter paper

in 0.65 M FeCl3-6H20 + 0.6 M HCI solution overnight. The strips were removed and allowed to

air dry. The strips were immersed for 30 seconds in 2.7 M NH40H, then rinsed twice in DDI

water, left to sit in clean DDI water for 1 hour, and then air dried before use. Fe-strip P was

determined by shaking the prepared strips with 1 g (dry weight equivalent) of biosolids and 60

mL of 0.01 M CaCl2 in a 120 mL bottle for 16 hours on an orbital shaker at 125

oscillations/minute. The original method was changed from 40 mL CaCl2 to 60 mL CaCl2 to

ensure the biosolids were completely covered with solution. During the CaCl2 WASh, P is

removed from the biosolids and is retained on the Fe-strip. After shaking, the strips were

removed from the glass bottles and rinsed thoroughly with DDI to remove biosolids particles.

The rinsed strips were placed in 125 mL Erlenmeyer flasks and shaken with 40 mL of 0. 1 M

H2SO4 On an orbital shaker for 1 hour at 125 oscillations/minute. The 0.1 M H2SO4 extracts P

from the Fe-strip, and the solutions were then analyzed for P using the molybdenum blue method

(Murphey and Riley, 1962). Fe-strip P is measure of biologically available P in soil (Sharpley,

1993a and b).

Dynamic Laboratory Incubation

Eleven biosolids and TSP were chosen for a dynamic laboratory incubation. Biosolids

were mixed at 2 rates, equivalent to 56 and 224 kg P ha l, with 400 g samples of Immokalee A

horizon soil (Immokalee fine sand, sandy, siliceous, hyperthermic Arenic Alaquods; Table 2-1)

and enough water (40 mL) to reach field capacity. The biosolids-amended soil was incubated for

2 weeks in zip-lock plastic bags. The bags of soil were mixed and opened daily during the initial









incubation to avoid anaerobic conditions. As in the glasshouse study (below), ammonium nitrate

was added to the soil to supply additional N. Originally, we intended to equalize varying N levels

among the materials at both P rates to 300 kg N ha-l plant available N (PAN). We initially

applied 75 kg N hal to the biosolids-amended soil at the start of the 2-week equilibration, with

the intention of split applying the remaining N after leachings. However, the columns of soil

were near field capacity for the duration of the experiment, and applying AN in solution would

have induced unintentional leaching; applying AN in crystalline form would not allow for N

distribution throughout the soil column. Thus, the remaining 225 kg N ha-l was not applied.

Incubation columns were constructed of 17 cm x 5 cm sections of polyvinyl chloride

(PVC) tubing with screening in the bottom to prevent soil loss. At the end of the initial 2-week

bag incubation, 400 g biosolids-amended soils were packed into the incubation columns to a

depth of 13 cm and a bulk density of 1.51 g cm-3. A total of 75 columns was used (12 materials x

2 rates x 3 reps + 3 controls = 75). The columns were positioned vertically in wooden racks for

leaching events.

Preliminary experiments were conducted to determine a representative column pore

volume (PV). Two methods were used to determine PV, gradual wetting and flood wetting. Four

incubation columns were filled with 400 g of dry soil and weighed. Tap water was gradually

added to two of the columns until 1 or 2 drops of water exited the bottom (gradual wetting). The

retained water volume (~118 mL) was assumed to be 1 PV. The other two columns were flooded

with 250 mL of tap water and allowed to drain overnight. When drainage was complete, the

columns were re-weighed and the difference in weight (~120 g) was assumed to be 1 PV. One

PV was taken to be 120 mL.









Every 2 weeks, sufficient tap water (adjusted to pH 5.0) was added to the columns to

result in 60 mL (1/2 PV) of drainage. We adjusted the pH of the water to 5.0 to simulate the pH

of rainfall in south Florida. Laboratory tap water was analyzed for soluble reactive (inorganic) P

(below detection limit; 0.001 ppm). For the first 2 leachings, P analysis of the leachates included

total phosphorus (TP), total dissolved phosphorus (TDP) and soluble reactive phosphorus (SRP);

pH and EC was also determined. Total P in the leachate was determined by digesting 5 mL of

unfiltered leachate with 0.3 5 g of potassium persulfate and 1 mL of 5.5 M H2SO4 On a digestion

block at 1250 C until only 5 mL of solution remained (USEPA, 1993). The temperature was then

increased to 150o C until 0.5 mL of solution remained. Reflux caps were placed on top, and the

temperature was further increased to 3800 C and digestion continued until the solution was clear.

TDP was determined in the same way, however the leachates were vacuum filtered through a

0.45 Cpm- filter to remove particulates before digestion. The digested leachate was analyzed for P

via the molybdenum blue method (Murphey and Riley, 1962). SRP was determined by vacuum

filtering leachate through a 0.45 Cpm- filter. The filtered leachate (undigested) was analyzed for P

using the molybdenum blue method. Organic P was determined by subtracting SRP from TDP.

Results from the first 2 leachings, revealed that the SRP represented the maj ority (>80%) of the

total P leached from the amended soils, and that organic P was minimal (<10% of TP). Thus in

subsequent leaching events, TP and TDP were measured only for select (highly colored or

cloudy) samples: Lakeland NS, OCUD S, OCUD E cake and OCUD E dry. TDP and TP values

were determined on these samples to ensure organic P and particulate P was minimal. Leachate

pH and EC was measured directly on unfiltered/undigested leachate.









Glasshouse Study

Seven biosolids and TSP were chosen for the glasshouse experiment for a total of 8

materials. Two biosolids were selected to represent (expected) low-P availability biosolids:

Milorganite, and GreenEdge (PWEP I 1.1%). Four biosolids were selected as high P-availability

biosolids (Boca Raton, GRU, Lakeland NS, and OCUD S), which are BPR or BPR-like residuals

(PWEP > 15%). One biosolids selected (Disney) had a moderate PWEP (8.4%) and biosolids-P

was expected to be moderately plant available. Biosolids were also selected based on PSI and

PWEP values. BPR and BPR-like biosolids typically have PSI and PWEP values greater than

traditionally produced residuals. We chose biosolids with high PSI and PWEP values to expand

the existing relative P phytoavailability database. Much work has been done on the

phytoavailability and liability of conventionally produced biosolids, including some Florida

materials, and some BPR materials (O'Connor et al., 2004; Elliott et al., 2002), but the database

is limited. Materials were mixed with 4 kg of A horizon Immokalee soil (Table 2-1) at 3 rates:

56, 112, and 224 kg P ha- The 56 and 224 kg P ha-l rates represent P-based and N-based

application rates, respectively. The 112 kg P ha-l rate was added to better define the relative P

phytoavailability response curve of the materials. Immokalee fine sand was chosen to represent a

typical, P-deficient, low-P sorbing Florida soil. A P-deficient and low P-sorbing soil is necessary

to represent a "worst-case" scenario of biosolids land application, and to maximize plant

response to P additions. The Immokalee soil does not retain P and can allow P movement to

ground and surface waters.

The biosolids-amended soils were equilibrated (at field capacity) in zip-lock plastic bags

for 2 weeks in the laboratory prior to use in the glasshouse. Ammonium nitrate (AN) was added

to the amended soils to equalize varying amounts of N supplied by the biosolids. N was applied

at an equivalent rate of 300 kg ha-l plant available nitrogen (PAN). The GreenEdge material









supplied the most PAN (240 kg ha l) at the high P rate. We opted to supply an additional 60 kg

hal of N to ensure N limitations would not affect P release or uptake. This rate is excessive for

Bahiagrass (179 kg N ha-l recommended; Kidder et al., 1998), but could not be avoided due to

the N:P ratio of the materials and the high targeted P rate of 224 kg ha- N mineralization was

assumed to be 40% of the total N in all of the biosolids, based on previous experience (O'Connor

and Sarkar, 1999). The total supplemental AN needed was split-applied, with '/ applied prior to

incubation, and the remaining split applications added throughout the growing season (following

the first 3 leaching events). AN is fully soluble in water and therefore is immediately available

for plant uptake. Thus, AN was split-applied to ensure sufficient N was available for uptake

throughout the growing season. A blend of potassium-magnesium sulfate ("sul-po-mag"; 22% S,

18% K, 11% Mg) was added (0.91 g, equivalent to ~444 kg ha l) to supply adequate and uniform

S, K, and Mg.

Containers for the glasshouse study were constructed of 15 cm diameter X 45 cm long

sections of polyvinyl chloride (PVC) tubing. A screen was fitted to the bottom to prevent soil

loss. A PVC cap fitted with plastic tubing was attached to the bottom of the column to allow

leachate collection. A total of 100 columns was used (8 materials X 4 replicates X 3 rates + 4

controls = 100). The columns were arranged in a randomized complete block design in wooden

racks holding 6 columns each. The experiment was blocked to minimize glasshouse positioning

effects. The columns were rotated one position within each block weekly to further minimize

glasshouse effects on grass growth. O'Connor et al. (2004) used the same container and

experimental design to quantify P uptake and leaching for 12 biosolids products in the same soil.

Thirty cm of sand (~8.5 kg) was packed into the columns as a support layer (TP = 12 g

kg- WEP = 0.12 mg kg- pH = 5.1, RPA = 8.6%). The sand was included to provide additional









rooting depth for the grass. The sand was flooded and allowed to freely drain to wet the layer to

field capacity and to remove soluble constituents. Following the 2-week laboratory incubation, 4

kg of biosolids-amended soil was placed on top of the sand layer in each column, and 5 g of

Bahiagrass seed was planted. Five grams of Bahiagrass seed per pot is a seeding rate equivalent

to~-28.6 Mg ha- the recommended seeding rate is ~10.9 Mg ha-l (Chambliss et al., 2001). We

increased the seeding rate to ensure sufficient and rapid soil surface coverage. The seeds were

covered with a layer of sand (~0.5 cm) and misted every 3-4 hours until germination. The grass

was allowed to grow for approximately 7 weeks before the first harvest. Subsequent harvests

occurred at approximately 4-week intervals.

The Bahiagrass was harvested to a height of 3.8 cm using scissors. The wet clippings

were placed in pre-weighed paper bags and dried at 680 C to constant weight to represent grass

yields. The dried tissue was ground to pass a #20 sieve with a Wiley mill, digested (Andersen,

1976) and analyzed for P via the molybdenum blue method (Murphey and Riley, 1962).

Phosphorus uptake was calculated as yield times tissue P concentration. Individual

harvest P uptake masses were summed to give cumulative P uptake mass. Tissue N content of

plants from the 224 kg P ha-l rate for all treatments was also measured for all 4 harvests. Tissue

N was determined by grinding the tissue to a fine powder, and analyzing for N by combustion at

10100 C using a Carlo Erba (Milan, Italy) NA-1500 CNS analyzer.

Following each harvest, sufficient tap water (adjusted to pH 5.0) was applied to each

column to yield ~500 mL (~0.25 pore volume) of leachate. Soluble reactive (inorganic) P (SRP)

of glasshouse tap water was measured (below detection limit; 0.001 ppm) via the molybdenum

blue method (Murphey and Riley, 1962). Leachate was analyzed for SRP using the molybdenum

blue method. Leachate volume times leachate P concentration yielded mass of P leached.









Leachates from the Lakeland NS material (high P rate) were highly colored. TP was determined

on the leachates to ensure organic P loss from the material was not significant.

Statistical Analysis

Cumulative P leached from the laboratory incubation was subj ected to a time-series

analysis (SAS Institute, 1989). Data were tested for normality using PROC UNIVARIATE. To

normalize yield and P uptake data, logarithmic transformations were needed. P leaching data

were normalized with a square transformation. Transformed cumulative yield, P uptake, and P

leached from the glasshouse study were statistically analyzed using PROC GLM. Means

separation of treatment differences was by Tukey test (p < 0.05) on transformed data. Relative

phytoavailability was calculated by fitting a linear regression to P uptake as a function of P

applied data using a slope- ratio approach. All P sources were regressed through a common

intercept of 8.48 mg, the average value of P uptake for the control, resulting in a response

proportional to the rate of P application.









Table 2-1. Selected properties of Immokalee fine sand.
Parameter, units Value
Sand, % 95a
pH 4.8
Organic matter, g kg-l 7.0 a
Oxalate-extractable P, mg kg-l 13.1 a
Oxalate-extractable Fe, mg kgl 85.6 a
Oxalate-extractable Al, mg kgl 40.1 a
PSI" 0.14 a
RPAd, % 2.0
Total P, mg kg-l 15.5
Mehlich 1-extractable P, mg kgl 1.47
KCL-extractable P, mg kgl 1.9 a
NaOH-extractable P, mg kg-l 3.3 a
HCl-extractable P, mg kg-l 0.9 a
Sequenced sum, mg kg-l 6.1 a
aData from O'Connor et al. (2004). cPhosphorus Saturation Index. dRelative phosphorus
adsorption [fraction of 400 mg P kg-l soil load sorbed (Harris et al., 1996)].









CHAPTER 3
RESULTS AND DISCUSSION

Laboratory Characterization

The laboratory characterization was key to determining which materials warranted further

study in the dynamic laboratory incubation and glasshouse studies. Twenty-one biosolids were

received and analyzed (Table 3-1). As detailed below, both basic chemical properties and P

characteristics were important for material selection. Recall that a goal of both the glasshouse

and dynamic laboratory incubation experiments was to include materials not previously studied,

specifically BPR and BPR-like products.

Total nitrogen (TN) concentrations ranged from 16 to 70 g kgl (1.6 to 7%). Biosolids

C:N ratios were generally low (6-15), with the exception of the West Palm Beach Compost

material (C:N of 26) (Table 3-2). The TN and C:N ratios are typical of U. S. produced biosolids

(USEPA, 1995). C:N ratios are important for predicting N mineralization from biosolids. In

general, when the C:N ratio of an organic material is less than 20: 1, N will be released into the

soil. If the C:N ratio exceeds 30: 1, N can be immobilized by soil microbes, and unavailable for

plant uptake. Thus, we selected materials with C:N ratios below 20: 1. The Disney material was

chosen as the representative compost residual to avoid possible complications with N

immobilization from high C:N ratio of the West Palm Beach biosolids.

Biosolids pH varied with source and product form (Table 3-2). Cakes were circum-

neutral to alkaline, and thermally dried products were slightly acidic. Lime stabilized products

had the highest pH values, as lime stabilization increases the pH of the final product (pH > 12).

We excluded materials with pH values > 9 from the glasshouse study as Bahiagrass prefers an

acidic environment (pH~-5.0; Chambliss and Adjei, 2006). O'Connor et al. (2004) reported









severely limited growth of Bahiagrass when biosolids with high pH (>12) values were applied to

the Immokalee soil at N-based rates.

TP concentrations of biosolids (Table 3-3) ranged from 7.9 to 33 g kg-l (0.79 to 3.3%),

typical of TP concentrations of biosolids produced conventionally nationwide (~20 to 40 g kg- ),

and > 40 g kg-l for BPR materials (USEPA, 1995). The difference in TP values results from the

differences in wastewater characteristics and treatment practices (Brandt et al., 2004). TP

concentrations were not used to include/exclude materials, but TP concentration was an

important measurement, as the laboratory determined TP values were used to calculate the mass

of biosolids needed to attain selected P application rates.

TP values for the materials were determined using 3 methods: Andersen (Andersen,

1976), EPA 3050A (USEPA, 1995) and perchloric acid (Association of Official Analytical

Chemists, 1990; The Fertilizer Institute, 1982) (Table 3-4). The Andersen and EPA 3050A

analyses were performed at UF. The perchloric acid analysis was conducted at an independent

laboratory for additional TP verification. The ability to recover P from the biosolids differs

among the techniques, which is reflected in the variability of the reported TP concentrations. UF

researchers were not provided information on how the individual WWTPs analyzed materials for

TP, which could explain the variability between determined and producer-supplied P values. A

standard reference biosolids material (National Institute of Standards and Technology, Standard

2781: Domestic Sludge) was used to gauge the ability of digestion methods to recover P. All

three methods had excellent P recovery percentages (88-96%).

Researchers chose to use the TP values determined by the Andersen (1976) method for

this study, primarily because of its ease of use. The EPA 3050A method is tedious and time

consuming, making the method impractical for the large number of samples involved in this









study. The perchloric acid analysis requires special facilities to handle the explosive nature of

perchloric acid, which were not available in the UF laboratory. In contrast, the Andersen (1976)

and EPA 3050A methods use hydrochloric and nitric acid, respectively, which are much safer to

handle. In a preliminary experiment, the Andersen-TP concentrations were used to calculate the

quantity of biosolids necessary to reach a target P rate of 224 kg P ha- A small quantity (200g)

of Immokalee soil was amended with the calculated masses of biosolids. When the biosolids-

amended soils were analyzed for TP using the Andersen (1976) method, the target P rate was

reached, indicating that the TP values obtained from the Andersen (1976) method were adequate

measures of the total P in the biosolids.

Total Fe, Al, and Ca concentrations were measured on the Andersen-TP extracts via ICP

(Table 3-2). Total metal concentrations were representative of biosolids produced nationally and

reflected the individual biosolids treatment processes. Total Fe ranged from 2.2 to 60 g kg-l (0.2

to 6%), Al ranged from 1.7 to 24 g kg-l (0.17 to 2.4%) and Ca ranged from 13 to 310 g kg-l (1.3

to 31%). The Lakeland Glendale material is lime stabilized, which is reflected in the high total

Ca (310 g kg- ). The greater a residual's Fe and Al content, the better the material is able to

retain P, leading to lower phytoavailability and lower leaching risks (Elliott et al., 2002). As

discussed below, Milorganite (41 g kg-l Fe, 2.7 g kg-l Al) has relatively high amounts of Fe and

Al, and resulted in decreased P release and P phytoavailability.

Water-extractable P (WEP) ranged from 0.04 to 14 g kg-l (Table 3-3). Brandt et al.

(2004) demonstrated that WEP is a good measure of the environmentally relevant portion of P in

biosolids. WEP is used to calculate percent water-extractable P (PWEP = WEP/ TP*100). Most

of the non-BPR materials analyzed had PWEP values < 5%, which is typical of non-BPR

biosolids produced in the U.S. (Brandt et al., 2004). BPR materials, (Boca Raton, OCUD E cake









and dry) had PWEP values > 11%. Brandt et al. (2004) determined the average PWEP for

various BPR biosolids sampled nationwide to be > 14%. PWEP was high for both Lakeland NS

(47%) and GRU (26%). These materials are not produced via BPR processes, but personal

communication with plant operators suggests that P removal is likely occurring in both systems.

We have categorized these materials as "BPR-like".

Both the Lakeland NS and GRU materials are low percent solids (3 and 5%, respectively,

Table 3-2), and we decided to analyze the liquid and solid phases of both materials to determine

the concentration of TP. Phosphorus in the liquid phase would be expected to be highly labile,

and we suspected that the high PWEP values were due in part to high concentrations of P in the

liquid phase. To determine the TP concentrations in the separated liquid and solid phases of each

residual, we centrifuged sub-samples at 12,000 rpm for 15 minutes to separate the liquid phase

from the solid phase. The separated phases were then analyzed for TP, the solid phase via the

Andersen (1976) method, and the liquid phase via persulfate digestion (USEPA, 1993). Analysis

showed that 50% and 20% of TP was in the liquid phase for the Lakeland NS and GRU

materials, respectively. The smaller concentration of P in the liquid phase for GRU than

Lakeland NS is reflected in the smaller PWEP value for GRU (26%) versus Lakeland NS (47%).

Disney is a BPR biosolids, however the PWEP (8.4%) is below average for a BPR

residual. The Disney material is a composted mixture of biosolids, food, and yard waste. Brandt

et al. (2004) reported that composting an anaerobically digested cake decreased WEP by 10-fold.

The yard waste itself could decrease PWEP; the Disney compost was sieved to pass through a 2

mm sieve prior to analysis, however small pieces of wood were obvious. The yard waste

composted with the Disney biosolids decreases the mass of biosolids per kg of land applied

finished product (composted biosolids + yard waste, even after sieving), thus reducing labile P.









Oxalate-extractable Fe, Al, and P concentrations (Table 3-3) were used to calculate PSI

values for the materials. PSI can be used a priori to gauge the liability of P in many biosolids in

sandy soils (Elliott et al., 2002). PSI relates the moles of oxalate-extractable P to the moles of

extractable Fe and Al (PSI = moles P / [moles Fe + moles Al]). Biosolids with high

concentrations of Fe and Al tend to have less labile P. PSI has no meaning for biosolids whose P

chemistry is controlled by Ca (lime stabilized materials). Elliott et al. (2002) suggested a critical

PSI value of 1.1 for non-lime stabilized materials. That is, if the PSI of a material exceeds the

critical value, appreciable P leaching may occur from amended, sandy soils with limited P

retention capacity. Biosolids with PSI values I 1.1 resulted in minimal P leaching in the Elliott et

al. (2002) study. Most of the samples analyzed in the current study were BPR or BPR-like

materials, and the PSI values exceed the critical value proposed by Elliott et al. (2002). We

would expect significant leaching when these materials were land applied to Immokalee soil that

retains P poorly.

Dynamic Laboratory Incubation

Eleven biosolids and TSP were individually mixed with 13 cm (400 g) samples of

Immokalee soil for the dynamic incubation study. Soil columns were leached a total of 8 times

(~4 total PV) over 5.5 months. The first 7 leachings were conducted bi-weekly to attain ~60 mL

(1/2 PV) of drainage each time. Significant P release (leaching) ceased after 5 leachings (2.5

months). A time-series analysis (SAS Institute, 1989) showed no difference in cumulative P

released for leachings 5-7. We waited 2 additional months to conduct the final leaching to allow

for P dissolution and distribution through the individual columns of soil and to confirm P release

from all materials was maximized. Indeed, P loss from all materials during leaching 8 was

minimal (< Img). Data from the final leaching was added to the time-series analysis and, again,

showed no change in cumulative P released between leachings 5-8. Three months passed









between leachings 5 and 8. Because cumulative P release did not change over the 3-month time

frame, we assumed that P release from the materials had ceased, and the experiment was

terminated. SRP in leachate was taken to represent total P released, as SRP constituted the

maj ority (>85% of TP) of P lost to leaching. To calculate P released as a percentage of applied P,

the mean mass of P released from the control treatment was subtracted from the mass of P

released for all other treatments, and the difference divided by the appropriate mass of P

originally applied.

One obj ective of the study was to quantify water soluble P (mass of P released) from

various biosolids representing a range of chemical characteristics. Biosolids with lower

quantities of water soluble P are less likely to negatively affect the environment. The quantity of

water soluble P is governed by several factors, including biosolids treatment processes

[especially heat drying (Smith et al., 2002; Maguire et al., 2001)], and biosolids chemical

composition (especially the quantity of Fe and Al oxides in the material). Residuals high in Fe

and Al oxides retain P, and result in less P leaching (Brandt et al., 2004). Thus, we expected

significantly more P release from BPR biosolids low in Fe and Al oxides than thermally dried

residuals high in Fe and Al.

ANOVA showed significant source (P-source), rate (P-rate) and source by rate

interactions. As a result, comparisons of cumulative P released and cumulative P leached as a

percent of applied P are discussed within each P application rate and not across P application

rates. Cumulative P release was greatest from BPR and BPR-like materials (Lakeland NS, GRU,

Boca Raton, and OCUD E dry and cake) (Table 3-5). Figures 3-la and b show cumulative P

release (percentage of applied P) in bar graph form for the 56 and 224 kg P hal rates,

respectively. P release from Lakeland NS, GRU, Boca Raton, and OCUD E cake biosolids was









equal to TSP at both the 56 and 224 kg P ha-l application rates (Figures 3-la and b). The OCUD

E dry material was produced by thermally drying the OCUD E cake material. The OCUD E cake

is undigested biosolids and is not lawfully land applied, but was included for scientific interest.

Heat drying the OCUD E cake created a class AA material that may be land applied. Heat drying

typically decreases labile P (Smith et al., 2002), and P release was less for the OCUD E dry

biosolids than for the OCUD E cake biosolids. However, P release from the OCUD E dry

biosolids at the 56 kg P ha-l application rate was equal to that from TSP, indicating the OCUD E

dry biosolids still had high quantities of labile P.

P release from the Disney biosolids was less than TSP and most BPR and BPR-like

biosolids at both the 56 and 224 kg P ha-l rates. At the 56 kg P ha-l rate, P release from Disney

was equal to GRU. As previously mentioned, Disney is a composted mix of biosolids, yard, and

food waste, which results in a PWEP (8.4%) less than the other BPR and BPR-like biosolids (>

15%) in this study. The PSI (0.45) of Disney reflects relatively large quantities of Fe and Al,

which likely reduced P release.

At 56 kg P ha- P release from Milorganite and GreenEdge was significantly lower than

from TSP. Both Milorganite and GreenEdge are thermally dried. Thermal drying typically

lowers quantities of labile P. Milorganite also has relatively high total Fe + Al concentrations (44

g kg- ) compared to typical biosolids total Fe + Al concentrations (20 g kg- ), which we expected

to further reduce P liability. P release from Milorganite and GreenEdge was not significantly

different, suggesting that P release from Milorganite and GreenEdge could be controlled by

physical properties (pellet dissolution). When the laboratory incubation was dismantled, pellets

of Milorganite and GreenEdge were still apparent, suggesting that even though the columns were

near field capacity for the duration of the experiment, the length of time was not sufficient for









complete pellet dissolution. Milorganite Greens Grade, which is the same product as

Milorganite, but passed through a smaller sieve, has a slightly greater PWEP value (0.85%) than

Milorganite (0.58%). We delayed the final leaching for 2 months following leaching 7 to allow

dissolved P to diffuse through soil pores (a time limited reaction), and the columns of soil were

maintained near field capacity during the 2-month break. Despite the elapsed time and sufficient

moisture, P release from all materials was < 1 mg in leaching 8. Time series analysis also

indicated that P release was minimal over the last 3-month period (leachings 5-8), suggesting

that P release from the P sources was maximized.

We expected GreenEdge to release a greater quantity of P than Milorganite based on the

biosolids PSI values, total Fe and Al concentrations, and PWEP values. GreenEdge has greater

PSI (1.0) and PWEP (1.1%) values than Milorganite, (PWEP: 0.58%, PSI: 0.55) and Milorganite

has greater Fe and Al (44 g kg- ) concentrations than GreenEdge (Fe + Al = 23 g kg- ). Based on

the P chemistry, we expected a greater quantity of P release from GreenEdge, however the data

did not support our a priori assumption. We hypothesized that calcium was influencing P

liability, however the Ca concentration of GreenEdge is not great enough to suggest that Ca is

controlling P solubility. We then ground a sample of GreenEdge with a mortar and pestle and

determined PWEP on the finely ground biosolids. The PWEP of GreenEdge did not increase

after grinding, (1.3%, compared to 1.1% on un-ground biosolids) indicating that pellet size was

not influencing P solubility. We currently have no explanation for the equal quantities ofP

released from GreenEdge and Milorganite. Butkes et al. (1998) studied P retention of water

treatment residuals (WTRs) and suggested that cationic polymers added during the water

treatment processes can retain P. During the dewatering of GreenEdge, a polymer (Ciba Zetag









8849FS) is added, and it is possible that the dewatering polymer has the capacity to sorb P, thus

reducing P liability.

Cumulative mass of P released from the OCUD S material was equal to TSP at the 56 kg

P ha-l application rate and greater than TSP at the 224 kg P ha-l rate (Figures 3-la and b). The

OCUD S material is a conventionally produced biosolids; however, the PWEP (21%) and the

PSI (2.9) values of the OCUD S material are high, and consistent with the high quantity of P

leached. Given the treatment process of the OCUD S biosolids anaerobicallyy digested) we

would not expect PWEP and PSI values to be so high. However the total Fe + Al concentrations

of the OCUD S material are low (11Ig kg- ), resulting in the high PSI value and quantities of P

released equal to TSP.

As previously mentioned, biosolids-TP is not a good indication of P liability. However,

PWEP can be used to gauge the environmental impact a residual will have once land-applied. A

logarithmic relationship exists between cumulative P released (% of applied P) and biosolids-

PWEP at both rates (Figures 3-2a and b). The correlation was similar for the 56 kg P ha-l rate (r2

= 0.65) and the 224 kg P ha-l application rate (r2 = 0.69). The correlation between cumulative P

released (% of applied P) and biosolids-PWEP was not strong enough to indicate that PWEP can

be used to predict the amount of P release that will occur when a biosolids is land applied.

However, Brandt et al. (2004) demonstrated that PWEP is a superior measure of the

environmentally relevant portion of P in biosolids and manures than biosolids-TP or soil test P.

Biosolids-PWEP can be used a priori to gauge the potential of a residual to negatively affect the

environment. PWEP is a measure of the water-soluble P in biosolids, thus materials with PWEP

values > 14% (vertical line in Figures 3-2a and b) should be assumed to have a larger negative

environmental impact than biosolids with PWEP values < 14%. Recall that Brandt et al. (2004)









reported an average PWEP value for BPR biosolids sampled nationwide to be > 14%. Given the

ease with which WEP/PWEP can be determined, PWEP can be used as a quick and efficient

gauge of a residual's potential to negatively impact the environment once land applied. Elliott et

al. (2006) used source WEP to improve P source coefficient assignments (PSC = 0. 102 x

WEP0.99) for state P-indices, and runoff dissolved P was well correlated (r2 = 0.80) with source-

WEP.

Figures 3-3a and b show P released (% of applied P) as a function of PSI for the 56 and

224 kg P ha-l rates, respectively. Elliott et al. (2002) demonstrated that for biosolids with PSI

values < 1.1, no appreciable leaching occurred from another sample of the Immokalee soil

amended with biosolids. Several materials used in this study had PSI values above the suggested

critical point of 1.1, which would portend significant P losses measured from the BPR and BPR-

like materials. Data from the current study indicate that a critical PSI value of ~2.0 better

separates biosolids where leaching was greatest, suggesting that the critical PSI value be raised

from 1.1 to ~2.0. However, the Elliott et al. (2002) study differed from the current study in 2

ways: 1) the Elliott et al. (2002) study utilized much larger soil columns, where '/ of a pore

volume was 500 mL, and 4 monthly leachings were necessary to reach 1 pore volume of

drainage; and 2) Bahiagrass was grown in the Elliott et al. (2002) soil columns, reducing the

quantity of P available for leaching. Data published separately (O'Connor et al., 2004) showed

that Bahiagrass took up 29-57% of applied P at the 56 kg P ha-l application rate. In the dynamic

laboratory incubation, ~4 pore volumes of drainage were collected versus 1 pore volume of

leachate collected in the Elliott et al. (2002) study. The small columns in the current study

included no plants and were flushed with more pore volumes of water than the large glasshouse

columns, which would encourage P release and movement downward (and out) of the small









columns. Given the differences in experimental design between the current study and Elliott et

al. (2002) study, raising the critical value from 1.1 to ~2 is probably not justified. While there is

no clear mathematical relationship between cumulative P release and PSI, it is evident that P

release increases when PSI > 2.0. P release appears to be maximized (~80% of applied P) at PSI

values > 2.0

The second maj or obj ective of dynamic laboratory study was to examine the kinetics of P

release. Figures 3-4a and b show cumulative P released as a percentage of P applied per leaching

event for the 56 and 224 kg P ha-l rates, respectively. While the ultimate quantity of P released is

important, the rate at which P is released is also important. When large amounts of P are released

from a material quickly, more P is in the soil solution at any given time and is subj ect to leaching

in periodic rain events, increasing the risk of ground and surface water impairment. Slow rates of

P release provide plants more time to take up biosolids-P, decreasing the amount of P subject to

loss from the soil profile.

Materials with high PWEP values (OCUD E cake, Lakeland NS, GRU, OCUD S)

released large quantities ofP quickly (within the first 3 leachings). At the 224 kg P ha-l

application rate (Figure 3-4b), the thermally dried materials (Milorganite, GreenEdge, and

Tallahassee) and the conventionally produced Broward cake released < 7% of applied P during

the first leaching event and the remaining materials released >15% of applied P. The quantity of

P released from Milorganite and GreenEdge was ~55% less than P released by the highly-P

soluble materials during the first leaching event. Phosphorus release from the cake and slurry

materials began to decrease (slow) in leaching 4, but P release from Milorganite and GreenEdge

continued to increase through leaching 5. As discussed above, high rates of P release from BPR

and BPR-like materials increase the quantity of P in the soil solution at any given point in time.









The increase in soil solution P suggests that BPR and BPR-like biosolids could be excellent

fertilizers, but also makes BPR and BPR-like residuals more likely to negatively affect the

environment, when soil solution P is washed through the soil profie into ground and surface

waters .

We can roughly convert total PVs leached to residence time in a Hield setting. One PV of

leachate represents ~5.64 cm drainage. Cumulative leaching (~480 mL) represented 22.6 cm of

drainage. Yearly rainfall in south Florida averages ~140 cm yrl (Obeysekera et al., 2004) and

evapotranspiration is ~70% of rainfall (Nachabe et al., 2005). Subtracting evapotranspiration

from rainfall (140 cm yr- 100 cm yr- ) yields 40 cm yr- drainage. Assuming 40 cm drainage

yr- we can calculate the number of PVs leached per year (40 cm yr- /5.64 cm PV-1 = 7.09 PV yr

1). Thus, the 4 PVs leached in this study equate to ~7 months in the Hield. This study represents

an extreme case of biosolids land application where the soil used had minimal P sorbing capacity

and no plants were grown to take up applied P. This experiment was key to understanding

biosolids P leaching characteristics in a representative "worst-case" scenario.

Glasshouse Study

A glasshouse study was run concurrently with the laboratory leaching study. Seven

biosolids were used and TSP was included as a reference. Biosolids were mixed with 13 cm (4

kg) samples of Immokalee soil and placed on top of 30 cm of base sand. Two biosolids evaluated

had low PWEP (<1.1%) values: Milorganite, and GreenEdge, 1 biosolids had a moderate PWEP

(Disney, 8.4%), and 4 biosolids had high PWEP (215%) values: Lakeland NS, OCUD S, GRU,

Disney, and Boca Raton. Bahiagrass was grown and harvested monthly for 4 months. After each

harvest, columns were leached to attain ~500 mL (1/2 pore volume) drainage. Statistical analysis

(ANOVA) showed significant treatment (biosolids), rate (P-rate), and rate X treatment effects on









yield, P uptake, and P leaching (SAS Institute, 1999; Tables A-1, 2, and 3, respectively). Thus,

results are discussed within each P application rate and not across P application rates.


Yields

We provided excessive N and other macronutrients (S, K, Mg) to isolate P as the only

nutrient variable. The lowest rate of P application (56 kg P ha- ) provides more than adequate P

for Bahiagrass. As a result, yields (Appendix Table A-4) were expected to be equal across all

materials and application rates. Equal yields are critical since harvest yields are used to calculate

P uptake. At the 56 kg P ha-l application rate, there were no significant differences in cumulative

yield between biosolids source treatments, and all treatment yields were significantly greater

than the control (Figure 3-5a). At the 112 kg P ha-l application rate, all treatment yields were

greater than the control, but the cumulative yield for OCUD S biosolids was greater than yields

for TSP, Disney, and GreenEdge (Figure 3-5b). At the 224 kg P ha-l application rate (Figure 3-

Sc), all the yields for all materials except for Lakeland NS and Disney were different from the

control. The cumulative yield for the Lakeland NS material was smaller than yields for all other

materials with the exception of the Disney compost. Yields at the 224 kg P ha-l application rate

for Bahiagrass grown in soil amended with Lakeland NS were highly variable, and Bahiagrass

growth was inexplicably reduced in 2 of the 4 soil columns. At the high P rate, the cumulative

yield of the OCUD S biosolids was not different from the yields of the other materials (Figure 3-

Sc). Because ANOVA showed rate and treatment interactions affecting yield, we cannot

statistically compare yields for treatments across rates. Figure 3-6 shows that most cumulative

yields approached the average yields across treatments (except controls) (~28 mg; horizontal line

on Figure 3-6).









To validate that Bahiagrass N uptake was sufficient, we analyzed tissue from all four

harvests at the highest rate of P application (Figure 3-7). We analyzed only tissue from the 224

kg P ha-l rate because most of the N at this rate was assumed to come from N mineralization

from the biosolids. If we misjudged the N mineralization rate to be 40%, we would anticipate N

deficiencies to be more apparent at the 224 kg P ha-l rate. Recall that N was equalized across P

application rates and treatments using ammonium nitrate. More ammonium nitrate was needed at

the 56 and 112 kg P ha-l rates than at the 224 kg P ha-l rate. The ammonium nitrate would be

immediately available to the Bahiagrass, thus we would not expect N deficiencies due to slower

(or smaller) than expected N mineralization from the biosolids. Tissue N concentration was used

to calculate yield-weighted N concentrations for each treatment over the entire growing season

using eqution 3-1.

where
trt = treatment
H1 = harvest
H12 = harvest 2

trt yieldH1 x NH1 + trt yieldH2 x NH2 + trt yieldH2 x NH2 trt yieldH2 x NH2 (3-1)
cumulative trt yield

Measured N concentrations were sufficient for grazing beef cattle (minimum 1.12 g N g-

1; NRC, 1996). Based on the N content per harvest (Figure 3-7), it appears we underestimated the

quantity of N that would mineralize from the biosolids initially (first harvest), and overestimated

N mineralization throughout the rest of the growing season. Figure 3-8 shows that yield-

weighted N concentrations for all biosolids treatments were above the minimum N

concentrations required for beef cattle. The yield-weighted tissue N concentrations were

sufficient for us to believe N was not affecting yields. Micronutrients were also considered as the

source of yield variation. Micronutrients were not supplied during the growing season, however









research has shown micronutrient deficiencies in Bahiagrass are rare and do not affect yields

(Chambliss and Adjei, 2006).

P Uptake and Relative Phytoavailability

The 224 kg P ha-l rate of P application resulted in the greatest cumulative P uptake

(Figures 3-9a c; Appendix Table A-2). P uptake ranged from 23-52 % of P applied at the low

application rate (Figure 3-9a). In a similar study by O'Connor et al. (2004), P uptake ranged

from 29-57% of applied P at the same low P application rate. At the 224 kg P ha-l rate, P uptake

in the current study ranged from 7-28% (Figure 3-9c), whereas O'Connor et al. (2004) reported P

uptake ranging from 1 1-29% of applied P at the 224 kg P ha-l rate. Recall that yields for

Bahiagrass grown in two replicates of soil amended with the Lakeland NS biosolids were

reduced at the highest rate of P application; therefore, average P uptake at this rate was lowered.

Cumulative yield-weighted tissue P concentrations ranged from 0.5 g kg-l to 4.5 g kg-l (Table 3-

7). Bahiagrass grown in soil with no added P (control) accumulated the least P, and soil amended

with TSP at 224 kg P ha-l resulted in the highest yield-weighted P concentration. Adj ei and

Rechcigl (2002) suggested that a sufficient tissue P concentration for Bahiagrass is 2.0 g kg-l

However, the critical concentration (P concentration necessary for survival) for Bahiagrass is

likely lower, and may even be closer to 1.0 g kgl (personal communication, Dr. Jerry Sartain,

2007). Milorganite applied at the 56 and 112 kg P ha-l resulted in tissue P concentrations slightly

below the hypothesized critical value of 1.0 g kg l. However, cumulative yields of Milorganite

and GreenEdge treatments were not different from yields in the fertilizer-P (TSP) treatment

(Figures 3-5a-c). Thus, the low tissue P concentrations in Milorganite and GreenEdge treatments

did not limit above ground growth. Bahiagrass grown in control columns (no added P) yielded

less than all other treatments. Over the course of the 4-month growing season, no above ground P









deficiencies were noted for any treatment. Plant roots were not examined for P-defieiency as the

glasshouse study is ongoing.

Relative phytoavailability (RPP) was estimated using a slope-ratio approach. Cumulative

P uptake was plotted as a function of P applied for each biosolids (Figure 3-10). Linear

regressions were fit to the data for each P source with a common intercept of 8.48 mg (mean

cumulative P uptake for the control columns). To calculate RPP, the slope of the regression line

for each material was divided by the slope of the regression line for TSP (Table 3-7). O'Connor

et al. (2004) used the same approach to estimate RPP for 12 biosolids on the Immokalee soil.

Table 3-7 also lists RPP values for biosolids produced or marketed in Florida determined by

O'Connor et al. (2004). We attempted to fit both linear and 2nd degree polynomials to the data

from the current study. The polynomials resulted in slightly greater r2 ValUeS, but greater

coefficients of variability (CV) (Table 3-8). Comparison of polynomials by comparing slopes is

also difficult, leading us to choose linear regressions to determine RPP. While a linear regression

through only the 56 and 112 kg P hal rates had slightly higher r2 and lower CV values than

linear regressions through all 3 rates, r2 and CV values for regressions including all 3 rates were

acceptable and significant at p < 0.05 (Table 3-8). Recall the purpose of including 3 rates of P

application was to better define the RPP curve; therefore, we opted to include all rates for

regression fit.

O'Connor et al. (2004) proposed 3 groupings of relative phytoavailability: high (>75% of

TSP), moderate (25-75% of TSP), and low (<25% of TSP). With the exceptions of Disney, all of

the BPR and BPR-like materials fit into the high RPP category. The Disney biosolids is a

composted mixture of BPR biosolids and yard waste, with PWEP (8.4%) and PSI (0.43) values

less than the PWEP and PSI of the other BPR biosolids included in the glasshouse study. The









PSI value for the Disney biosolids indicates a greater quantity of Fe and Al than the BPR or

BPR-like biosolids. Stratful et al. (1999) reported that BPR biosolids contained more

phytoavailable P compared to conventionally produced residuals.

The OCUD S material was 110% as phytoavailable as TSP. Interestingly, the OCUD S

material is not a BPR material, but has a high PWEP (21%), exceeding to the average PWEP

value (14%), for BPR materials (Brandt et al., 2004). To calculate the regression slope for

Lakeland NS biosolids, 2 P uptake replicates were excluded at the 224 kg P ha-l rate. Recall that

Bahiagrass yields were inexplicably reduced in 2 replicates of the Lakeland NS amended soil at

the high P rate, reducing P uptake. Excluding data points reduces power of statistical

comparison; however when cumulative yields from all 4 replicates were used for regression, the

linear correlation was very poor (r2 = 0.09). Thus, the regression coefficient and r2 ValUeS foT

Lakeland NS listed in Table 3-7 reflect only 2 replications.

The linear regression model described the data for Milorganite poorly (r2 = 0.51). We,

therefore, estimated RPP values for Milorganite via point estimates (Table 3-9) calculated using

equation 3-2.

Point Estimate RPP = (P uptakesou~rc P uptakecontroi) / P appliedsource (3 -2)
(P uptakeTrSP- P uptakecontrol) / P appliedTrSP

At the 56, 112, and 224 kg P ha-l rates, P in Milorganite was 38%, 31%, and 23% as

phytoavailable as TSP, respectively. Thus, on average, Milorganite is ~31% as phytoavailable as

TSP, placing it in the lower end of the moderate category of RPP values proposed by O'Connor

et al., (2004). Milorganite would be assumed a priori to be in the low category of RPP values,

based on PWEP (0.58%) and PSI (0.55) values, however the data support a moderate RPP for

Milorganite. We also fit the P uptake data for Milorganite to a plateau model (Equation 3-2,

Figure 3-10).









where
a = concentration of P in control (no added P)
b = P concentration plateau increment above the background (mg)
c = rate constant for change in uptake for a given change in the cumulative amount of P applied
P applied = rate of P application

Uptake (mg) = a + b(1-e-c*Papplied) (3-2; Barbarick et al., 1995)

The good fit of the data to the plateau model confirms the unique P characteristics of

Milorganite. We can calculate a similar RPP for Milorganite by dividing the mean cumulative P

uptake for Milorganite (30.9 mg) by the mean cumulative P uptake for TSP (106 mg) at the 224

kg P ha-l application rate: 30.9 mg/ 106 mg *100 = 29% RPP. Even at the high P loads (224 kg P

ha- ) associated with N-based application rates, Milorganite is only ~29% as phytoavailable as

TSP (consistent with point estimate).

The regression equation for the Lakeland NS uptake data resulted in a weak r2 ValUe

(0.54), so we confirmed the RPP calculated via the slope-ratio approach using point estimates

(Table 3-9). Averaging the point estimates for 56, 112, and 224 kg P ha-l resulted in a RPP of

90% for the Lakeland NS biosolids (consistent with slope-ratio approach).

We attempted to correlate RPP with biosolids-PWEP, but the correlation did not

adequately explain the relationship between RPP and biosolids-PWEP (r = 0.64). However,

when RPP is plotted as a function of biosolids-PWEP, (Figure 3-12) a logarithmic relationship

exists (r2 = 0.79). The logarithmic correlation is not strong enough to predict RPP using PWEP.

However, it appears that biosolids-PWEP > 14% segregates biosolids with greater RPP values

from biosolids with lesser RPP values. Recall the same trend was noted with the P release data

from the dynamic laboratory incubation; biosolids with PWEP values > 14% could be assumed

to result in a larger negative environmental impact than biosolids with PWEP values < 14%. In

the glasshouse study, biosolids with PWEP values < 14% had RPP values below 60% (moderate









RPP category), compared to biosolids with PWEP values > 14%, which had RPP values > 90%

(high RPP category).

The glasshouse study conducted here, and earlier work by O'Connor et al. (2004),

demonstrates the wide range of RPP values possible for various biosolids. Knowledge of

biosolids-RPP is key to adjusting application rates, should P-based limitations on biosolids land

application be imposed. Results of the glasshouse study indicate that no change in biosolids

application rate is needed (or justified) for BPR and BPR-like biosolids with RPP values in the

high RPP category. However, application rates for Disney and GreenEdge could be

approximately doubled that necessary to meet crop P needs. Based on the plateau model,

Milorganite could be applied at rates > 224 kg P ha l, and will only be about 1/3 as available as

TSP. The low RPP of Milorganite does not necessarily imply that Milorganite is a poor P-

fertilizer; Bahiagrass grown in Milorganite-amended soil showed no signs of above ground P

deficiency during the course of the experiment and Bahiagrass yields were equivalent to TSP

treatment yields for each application rate.

P Leaching

A similar glasshouse study by Elliott et al. (2002) used a base sand with minimal P-

sorbing capacity. The base sand used in this study had moderate P-sorbing capacity (RPA =

8.6%). Elliott et al. (2002) showed that a Florida sand with even moderate P-sorbing capacity

(RPA=15.3%) can limit P leaching. Minimal P leaching occurred in the current glasshouse. Only

TSP and BPR materials applied at the highest rate resulted in significant P leaching (Appendix

Table A-3). The base sand is likely retarding the advance of P through the soil column. This

study is on going, and it is possible that P retained in the column through the first growing









season will eventually leach during subsequent croppings. Given the deep rooting of Bahiagrass,

the P sorbed to the base sand is also accessible for plant uptake.








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Table 3-4. Comparison of biosolids-TP concentrations determined


by 3 digestion methods
EPA3050A Anderson
g kgl


P Source


Perchloric Producera


Milorganite
Broward
JEA Cake
GreenEdge
Lakeland NS
OCUD S
OCUD E Cake
Disney
Drl ando
Boca Raton
GRU
Standard Reference


ND
23
18
ND
37
26
24
ND
18
34
ND
22 (91%)


21
20
15
17
29
21
20
11
17
26
31
21 (88%)


24
26
20
ND
38
32
29
ND
19
39
ND
23 (96%)


aProducer-supplied data. bND: not determined.










Table 3-5. Dynamic laboratory incubation: cumulative net
SRP released and SRP released as a percentage
of applied P. Means & 1 standard error, n = 3.


Cumulative P
released
% of applied

NA
80.9 & 3.08
74.0 & 2.69
38.5 A 10.8
19.0 & 3.73
40.0 & 4.29
27.4 & 2.04
42.0 & 1.34
39.9 & 1.80
67.0 & 2.32
68.5 & 2.63
87.7 & 4.90
79.3 A 1.84
90.0 & 2.21
62.4 & 1.87
92.8 & 2.15
79.9 & 1.14
69.5 & 2.05
62.4 & 1.05
97.3 & 3.37
80.0 + 0.667
61.4 & 7.31
31.5 & 2.08
52.8 & 1.34
40.3 A 1.80


Cumulative P
released



0.67 & 0.062
8.33 & 0.318
30.5 A 1.11
3.96 & 1.11
7.84 & 1.54
4.12 & 0.442
11.3 & 0.842
5.66 & 0.252
21.6 & 2.42
6.90 + 0.239
28.2 & 1.08
9.03 & 0.505
32.7 & 0.756
9.27 & 0.228
25.7 & 0.770
9.56 & 0.347
32.9 & 0.275
7.16 & 0.221
25.7 & 0.469
10.0 + 0.212
33.0 + 0.434
6.33 & 0.753
13.0 + 0.856
5.43 & 0.138
16.6 & 0.742


P Source



Control
TSP
TSP
Milorganite
Milorganite
GreenEdge
GreenEdge
Disney
Disney
GRU
GRU
Boca Raton
Boca Raton
Lakeland NS
Lakeland NS
OCUD E Cake
OCUD E Cake
OCUD E Dry
OCUD E Dry
OCUD S
OCUD S
Broward
Broward
Tallahassee
Tallahassee


Rate


kg P ha '
0
56
224
56
224
56
224
56
224
56
224
56
224
56
224
56
224
56
224
56
224
56
224
56
224










S100
-J
90

a70
60
50
40
S30
S20

10


"
d'' .i": "
u
si"qB r' rArg, oC~
8` sOG~~
o\'
oC` oC`

P Source


e


de


P Source

Figure 3-1. Cumulative SRP released (% of applied P) as a function of P source. Means capped
with the same letter are not different (Tukey's Test, p<0.05). A) P-rate: 56 kg P ha-1.
B) P-Rate: 224 kg P ha-1.


iiab


S90

70 -0
a 60
,50 -
S 40
30 -1 P
. 20

10






















y = 10.4 Ln(x) + 45.4
S= 0.646
CV = 18.7%


0 10 20 30 40 50 60 70 80 90
Biosolids-PWEP (%)


y = 11.1 Ln(x) + 30.7
S= 0.692
CV = 21.5%


0 10 20 30 40 50
Biosolids-PWEP (%/)


60 70 80 90


Figure 3-2. Dynamic laboratory incubation: cumulative P released (% of applied P) as a function
of biosolids-PWEP. Error bars represent 1 standard error. Vertical line at biosolids-
PWEP 14% indicates when increased negative environmental impact may occur.
A) P-Rate: 56 kg P ha- B) P-Rate: 224 kg P ha-l


Ef
f

E





1.0 1.5 2.0 2.5 3.0
PSI


*


0.5 1.0 1.5 2.0 2.5 3.0 3.5


4.0 4.5


Figure 3-3. Dynamic laboratory incubation: cumulative P released as a function of PSI. Dashed
vertical line at 1.1 PSI represents change point proposed by Elliott et al. (2002). Solid
vertical line at 2.0 PSI represents increased critical PSI value suggested by data in the
current study. A) P-Rate: 56 kg P ha- B) P-Rate: 224 kg P ha- .













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5-
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Figure 3-5. Cumulative Bahiagrass yields after 4 harvests. P-rate: 112 kg P ha l. Means capped
with the same letter are not different (Tukey Test, p<0.05). A) P-Rate: 56 kg P ha-l
B) P-Rate: 112 kg P ha- C) P-Rate: 224 kg P ha-l


















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P Source


Figure 3-5. Continued


-r~ 01Vilorganite
30 T ... T "-
A Disney
25 AGRU
~a II II 1 I I II II-I-F[ IO Boca Raton
O ~Lakeland NS
S20-
2 OCUD S
15-




5-


56 112 224

P Applied (kg ha l)


Figure 3-6. Cumulative Bahiagrass yields after 4 harvests for all P application rates. Horizontal
line at ~28 g dry matter yield represents average dry matter yield across rates and
treatments. Error bars represent 1 standard error.












35
-
r 30

25

20 ,

S15

10 ,


O Harvest 1
El Harvest 2
5 Harvest 3
5 Harvest 4


T,


a
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Figure 3-7. Bahiagrass N tissue concentration per harvest. P-rate: 224 kg P ha l. Error bars
represent 1 standard error.




18 .


' 16

14

S12

g 10
-






2 2
-


OCUD S Greenedge


GRU IVilorganite Lakeland


TSP Boca Raton Disney


P Source


Figure 3-8. Bahiagrass yield-weighted N concentration after 4 harvests. P-rate: 224 kg P ha .
Error bars represent 1 standard error.













. 50
S40
e 30
20
S10
0


-a


a


i


Milorganite Disney Green Edge Boca Raton


T SP OCUD S Lakeland NS


GRU


P Source


S50
S40
S30
S20
S10


1Vilorganite GreenEdge


Disney


GRU Boca Raton


TSP Lakeland
NS


OCUD S


P Source


S40
S30
S20


0


a


Milorganite Disney GreenEdge Lakeland NS Boca Raton
P Source


TSP OCUD S


112 kg P ha- Means
p<0.05). A) P-Rate: 56 kg P


Figure 3-9. Cumulative Bahiagrass P uptake after 4 harvests. P-rate =
capped with the same letter are not different (Tukey Test,
ha- B) P-Rate: 112 kg P ha- C) P-Rate: 224 kg P ha- .


a a










Table 3-6. Cumulative Bahiagrass yield-weighted tissue P concentrations after four
harvests.

Yield-Weighted
Tissue P
concentration


g kg'
0.531 & 0.06
1.86 & 0.09
2.71 & 0.21
4.20 + 0.40
0.91 & 0.06
0.97 & 0.10
1.18 & 0.08
1.07 & 0.17
1.39 & 0.7
1.90 + 0.03
1.43 & 0.11
1.90 + 0.05
2.50 + 0.10
1.65 & 0.13
2.25 & 0.09
3.22 & 0.26
1.59 & 0.16
2.35 & 0.24
3.16 & 0.49


2.45 & 0.04
3.50 + 0.21
1.71 & 0.09
2.41 & 0.14
3.42 & 0.16


P Source
Control
TSP
TSP
TSP
Milorganite
Milorganite
Milorganite
GreenEdge
GreenEdge
GreenEdge
Disney
Disney
Disney
GRU
GRU
GRU
Boca Raton
Boca Raton
Boca Raton
Lakeland NS
Lakeland NS
Lakeland NS
OCUD S
OCUD S
OCUD S


Rate
0
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224



































Table 3-7. R phosphorus phytoavailability of biosolids to TSP

Linear
Regression
P Source r2 COefflcient RPP (%) Category Reference Study
TSP 0.89 0.472 100 high Current
OCUD S 0.90 0.519 110 high Current
GRU 0.91 0.439 93 high Current
Lakeland NS 0.54 0.435 92 high Current
Boca Raton 0.86 0.429 91 high Current
GreenEdge 0.88 0.222 47 moderate Current
Disney 0.70 0.220 47 moderate Current
Regression equation: y = x + 8.48 Current


Milorganite 31* moderate Current


TSP 0.400 100 O'Connor et al. (2004)
Largo Cake 0.297 74 moderate O'Connor et al. (2004)
Largo Pellets 0.193 48 moderate O'Connor et al. (2004)
Baltimore Cake 0.136 34 moderate O'Connor et al. (2004)
Tarpon Springs Cake 0.124 31 moderate O'Connor et al. (2004)
Regression equation: y x + 20.544;
R2 0.91 O'Connor et al. (2004)

aDetermined via point estimates.


+ TSP
5 GRU
A Lakeland NS
X OCUD S
m Boca Raton
O Milorganite
+ GreenEdge
- Disney


"' P


x~ ,


,II
,I
,,


P Applied (kig P ha )

Figure 3-10. Cumulative Bahiagrass P uptake as a function of P applied



































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Table 3-9. Point estimates of RPP for Milorganite and Lakeland NS biosolids
P Source Rate RPP % Average
TSP 56 100 100
TSP 112 100
TSP 224 100
Milorganite 56 38 31
Milorganite 112 31
Milorganite 224 23
Lakeland NS 56 108 90
Lakeland NS 112 106
Lakeland NS 224 55


""""""""""" """-'' 30

--25

--20

--15

--10

Uptake = 8.55 + 22.2(1-e-0 0203*P apphied) -5


30

S25

S20

S15



10


50 100


150

P Rate (kg P ha l)


Figure 3-11i. Plateau model: P uptake of Milorganite as a function of P applied





















60-


40-

y = 14.6 Ln(x) + 42.5
20-2
r2 = 0.793



0 10 20 30 40 50 60 70 80 90

Biosolids-PWEP



Figure 3-12. Relative phosphorus phytoavailability (RPP) as a function of biosolids-PWEP.
Vertical line at 14% PWEP indicates when increased negative environmental impact may occur.









CHAPTER 4
CONCLUSIONS

Dynamic Laboratory Incubation

The obj ectives of the dynamic laboratory incubation were to quantify soluble P release,

study kinetics of P release, and evaluate the leaching hazard of various biosolids sources. The

experiment was designed to mimic an extreme situation of biosolids land application; the soil

used had minimal P-sorbing capacity and no plants were grown to utilize supplied P. We accept

our second hypothesis that P leaching would be significantly greater from BPR and BPR-like

products than conventionally treated materials. P release from BPR and BPR-like biosolids was

equal to TSP, thus we rej ect our third hypothesis that P liability from all biosolids would be less

than TSP. This experiment is key to understanding the environmental hazard specific residuals

may pose.

Biosolids-PWEP is an excellent indication of how a biosolids will impact the

environment when land applied to sandy, low P-sorbing soils. Biosolids with high PWEP values,

including BPR and BPR-like materials yielded the greatest cumulative P leached. Biosolids with

PWEP values > 14% should be assumed to have a larger potential negative environmental impact

than biosolids with PWEP values <14%. PSI can also be used to gauge the environmental impact

of biosolids land applied to sandy soils with minimal P-sorbing capacity. Given the observed

trends in PWEP and PSI values based on biosolids treatment process, (i.e. PWEP and PSI

increase for BPR and BPR-like biosolids) environmental hazard can be roughly gauged by a

biosolids treatment process. While exceptions exist, much research has shown that BPR and

BPR-like materials have a greater risk of P loss compared to conventionally produced and

pelletized biosolids. In this study, the differences in cumulative P mass leached between the

dried and BPR or BPR-like materials appear to reflect both physical and chemical controls on P









solubility. The pellets of thermally dried materials did not completely dissolve over the course of

the experiment, leading to smaller quantities of P released. Relatively high concentrations of Fe

and Al in the Milorganite material also apparently decreased P release.

Thermally dried and conventionally produced residuals have a slower rate of P release

than BPR and BPR-like products. Knowledge of the kinetics of P release is important to

understanding the effects a residual will have on the environment. A slower rate of P release is

desirable, because opportunity for plant uptake is increased and there is less P in the soil solution

at any given moment. The less P in the soil solution at any given time means less P is available

for leaching through and out of the soil profile, risking impairment of water bodies.

The dynamic laboratory incubation demonstrates that biosolids land application should

not be regulated by assuming all biosolids have equal amounts of labile P. Measurements such as

PWEP and PSI, should be considered in regulating biosolids land application. Assuming all

biosolids to have equal amounts of labile P, and requiring P-based application rates without

considering a residual's individual environmental hazard would unfairly burden municipalities

facing disposal problems or unfairly advantage WWTP producing BPR products. Blanket

regulation of biosolids land application is also unwise given the benefits biosolids can have to

soil and crops when land applied. Biosolids land application can decrease chemical fertilizer

inputs. Chemical fertilizers designed to be water-soluble and provide instant plant nutrition are a

greater environmental hazard than conventionally produced or thermally dried residuals. While

BPR and BPR-like biosolids treatment processes are environmentally beneficial to reduce P in

wastewater effluent, these materials likely pose a greater environmental hazard due to more P

and greater P liability when land applied.









Glasshouse Study

If biosolids are to be applied to agricultural land under P-based restrictions, the quantity

of P that will be available to the crop becomes critical. If a residual has low phytoavailability,

and is applied at a P-based rate, the crop will be N and P deficient, requiring additional mineral

fertilizer input. For BPR or BRP-like materials, P-based application to crops would provide

sufficient P, but require supplemental N fertilizer to meet crop needs. Three BPR or BPR-like

materials, and 1 conventionally produced biosolids (OCUD S) examined herein, fit into the high

category (>75% of TSP) proposed by O'Connor et al. (2004). One BPR (Disney) and 2 thermally

dried materials (Milorganite and GreenEdge) were in the moderate RPP category (25-75% of

TSP). Milorganite fits into the moderate category proposed by O'Connor et al. (2004), despite

expectation that it would be a low RPP material. Based on determined RPP values for BPR and

BPR-like biosolids, we accept our first hypothesis that RPP would be greater from BPR and

BPR-like biosolids than conventional biosolids [with the exception of the conventionally

digested OCUD S biosolids (RPP = 110% of TSP)]. Materials in the high category for RPP also

had the greater cumulative P leached in the laboratory incubation. Materials with high water-

soluble P have more P available for plant uptake. Materials with high RPP make excellent

fertilizers, but can also pose a greater environmental risk for P loss.

The 1995 U.S. EPA design manual (USEPA, 1995) suggests the average "relative

effectiveness" for biosolids-P to be 50% of mineral fertilizer. While the relative effectiveness

factor admits not all P in biosolids is phytoavailable, this study, as well as a similar study by

O'Connor et al. (2004), shows the wide range in the relative phytoavailability of biosolids.

Again, P phytoavailability and leaching hazard are linked to biosolids treatment processes. The

Milorganite biosolids, which is relatively high in Fe and Al, showed the lowest relative

phytoavailability (3 1%). The moderate RPP of the Disney compost is likely due to fact that the









material is a mixture of composted yard waste and biosolids, lowering the quantity of

soluble/available P. Materials with the greatest PWEP values showed the greatest relative

phytoavailability. If and when biosolids P-based regulation of biosolids land application is

imposed, it would be wise to consider individual residual's P characteristics (PWEP and PSI).

Given the range of biosolids P characteristics, regulating all biosolids as if residuals were all the

same could unnecessarily limit beneficial biosolids land application. Most states use a P-index

approach to predicting P loss from a material, and most states do not differentiate biosolids by

treatment process or characteristics such as PWEP. Currently, Florida uses the same source

coefficient for all biosolids (0.015). Elliott et al. (2006) suggested calculating PSC values by

multiplying by the WEP (PSC = 0. 102 x WEP0.99), based on runoff P studies.

Research not detailed in this thesis used 4 biosolids (Milorganite, OCUD S, Lakeland NS,

and Disney) and TSP in rainfall simulations and measured TP, TDP, and biologically (algae)

available P (BAP) in runoff and leachate from Immokalee soil. Flow-weighted TP, TDP, and

BAP were all highly correlated to biosolids-PWEP values. With the exception of Lakeland NS,

BAP losses from all biosolids and TSP was predominantly via leaching. The low solids content

(3%), of the Lakeland NS biosolids, however, resulted in extensive soil surface coverage with a

layer of fine material that was particularly susceptible to rain drop impact and runoff loss.

Cumulative BAP in runoff and leachate for all biosolids treatments was significantly less than

from TSP treatments. Thus, in the short term, biosolids-P (even with very high PWEP values) is

much less of an environmental threat than fertilizer-P. The results of the rainfall simulation

confirm that leaching is the predominant P loss mechanism in typical Florida sands.









Land-Applying BPR or BPR-Like Residuals

Municipalities using BPR biosolids treatment processes have several options to reduce

the impact the residuals will have on the environment; however, each option has advantages and

disadvantages. If supported by the P-Index, biosolids can be land applied at P-based rates, which

will reduce the labile P in the soil solution at any given time, decreasing the chance of negative

environmental impact. P-based application rates of BPR and BPR-like biosolids will provide

sufficient crop P, but will require additional mineral fertilizer input of N. While applying

residuals at a P-based rate is environmentally sound, more land area is required for disposal and

disposal costs will increase. Farmers will also face increased costs from purchasing additional N

fertilizer, which may discourage them from utilizing biosolids as fertilizer. Soil incorporation can

also reduce P loss, especially in soils with sufficient P sorbing capacity.

Biosolids can also be co-applied with WTRs. O'Connor and Elliott (2000) suggested that

co-applying biosolids with water treatment residuals (WTR) increases soil P retention capacity

and reduce P mobility. Agyin-Birikorang et al. (2007) demonstrated that P sorbed to WTRs is

retained long-term.

The dynamic laboratory incubation experiment demonstrated the benefits of high Fe and

Al concentrations in limiting P loss, and WWTPs could add Fe and Al salts to BPR and BPR-like

products to reduce environmental risk, however this would significantly increase biosolids mass,

leading to transportation and disposal problems.

The simplest approach is to apply biosolids to soils with sufficient P-sorption capacity

(easily determined). Elliott et al. (2002) demonstrated that even soils with moderate P-sorbing

capacity could prevent significant P loss. Applying biosolids to land with sufficient P-sorbing

capacity may require transporting biosolids longer distances, increasing transportation costs.










Lastly, thermally drying biosolids can reduce labile P and significantly reduce biosolids

mass, decreasing the negative environmental impact. The trend for thermal drying to reduce P

liability was not noted when the OCUD E cake material was dried, however the OCUD E cake

material is un-digested, and therefore may not be land applied, which may produce unique P

character stics.










APPENDIX
GLASSHOUSE ANOVA AND CUMULATIVE DATA


Table A-1. Cumulative Bahiagrass P uptake after 4 harvests.
Sum of
Source DF Squares Mean Square
Model 27 30.6 1.13
Error 72 1.56 0.022
Corrected Total 99 32.2
R-Square Coeff Var Root MSE
0.952 3.75 0.147
Source DF Type I SS Mean Square
Treatment (source) 7 24.3 3.04
Block 3 0.024 0.008
P-Rate 2 4.81 2.40
Treatment*Rate 14 1.45 0.104
Source DF Type III SS Mean Square
Treatment (source) 7 10.8 1.55
Block 3 0.024 0.008
P- Rate 2 4.81 2.40
Treatment*Rate 14 1.45 0.104


F Value
52.5


Pr > F
<.0001


loguptake Mean
3.92
F Value Pr >
141 <.00
0.37 0.77
111 <.00
4.81 <.00
F Value Pr >
71.3 <.00(
0.37 0.77:
111 <.00(
4.81 <.00(


F
01
r2
101
01
F
01
2
01
01










Table A-2. ANOVA for cumulative Bahiagrass vield after 4 harvests.


Sum of
DF Squares
27 3887782
72 1061590
99 4949373
'ar Root MSE
121
DF Type I SS
7 2658619
3 49493
2 1 246
14 1055512
DF Type III SS
7 1554892
3 494934
2 124156
14 1055512


Source
Model
Error
Corrected Total
R-Square Coeff V
0.786 15.8
Source
Treatment (source)
Block
P-Rate
Treatment*Rate
Source
Treatment (source)
Block
P-Rate
Treatment*Rate


Mean Square
143991
14744


sqyield Mean
771
Mean Square
3323274
16497
62078
75393
Mean Square
222127
16497
62078
75393


F Value Pr > F
9.77 <.0001






F Value Pr > F
22.5 <.0001
1.12 0.3472
4.21 0.0187
5.11 <.0001
F Value Pr > F
15.1 <.0001
1.12 0.3472
4.21 0.0187
5.11 <.0001










Table A-3. ANOVA for cumulative P leached in glasshouse experiment.


Sum of
Squares
87.8
5.14
92.9
Root MSE
0.267
Type I SS
22.6
0.600
36.9
27.7
Type III SS
21.5
0.599
36.9
27.7


Source DF
Model 27
Error 72
Corrected Total 99
R-Square Coeff Var
0.945 49.2
Source DF
Treatment 7
Block 3
Rate 2
Treatment*Rate 14
Source DF
Treatment 7
Block 3
Rate 2
Treatment*Rate 14


Mean Square F Value
3.25 45.5
0.071


Igleached Mean
0.543
Mean Square F Value
2.82 39.5
0.199 2.80
18.5 258
1.98 27.7
Mean Square F Value
3.08 43.0
0.199 2.80
18.46 258
1.98 27.7


Pr > F
<.0001






Pr > F
<.0001
0.046
<.0001
<.0001
Pr > F
<.0001
0.05
<.0001
<.0001










Table A-4. Glasshouse study: cumulative Bahiagrass yields after 4 harvests. Means & 1 standard
error, n = 4.


Rate

kg P ha '
0
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224


Cumulative Yield


15.9 & 1.3
26.6 & 1.0
26.2 & 0.49
25.1 & 0.84
26.6 & 1.1
28.4 & 0.70
26.3 & 2.0
28.6 & 1.0
26.7 & 0.23
28.5 & 0.63
25.7 & 0.85
26.4 & 0.88
23.4 & 0.62
27.6 & 0.55
29.9 & 1.0
30.8 & 1.0
28.1 & 0.79
29.6 & 0.21
30.1 & 0.48
29.5 A 1.3
30.6 & 0.63
16.8 & 4.0
30.9 & 1.2
33.1 +1.1
33.5 A 1.6


Material
Control
TSP
TSP
TSP
Milorganite
Milorganite
Milorganite
GreenEdge
GreenEdge
GreenEdge
Disney
Disney
Disney
GRU
GRU
GRU
Boca Raton
Boca Raton
Boca Raton
Lakeland NS
Lakeland NS
Lakeland NS
OCUD S
OCUD S
OCUD S










Table A-5. G
st~


Material
Control
TSP
TSP
TSP
Milorganite
Milorganite
Milorganite
GreenEdge
GreenEdge
GreenEdge
Disney
Disney
Disney
GRU
GRU
GRU
Boca Raton
Boca Raton
Boca Raton
Lakeland NS
Lakeland NS
Lakeland NS
OCUD S
OCUD S
OCUD S


lasshouse study: cumulative P uptake for Bahiagrass after 4 harvests. Means & 1
andard error, n = 4.


Cumulative P Uptake
mg
8.48 & 1.0
49.4 & 1.1
71.0 & 3.6
105 & 6.6
24.0 & 1.1
27.6 & 1.8
30.9 & 2.0
30.5 A 1.5
37.1 & 0.72
54.0 + 88
36.8 & 2.3
50. 1 1.2
58.5 A 1.7
45.4 & 2.0
67.1 & 2.5
99.0 & 4.7
44.6 & 2.9
69.8 & 3.4
94.9 & 7.0
53.2 & 1.7
75.1 & 6.4
58.3 A 14
52.8 & 1.3
79.5 A 1.6
115 & 6.0


Rate
0
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224










Table A-6. Glasshouse experiment: cumulative P leached after 4 leachings. Means & 1 standard
error, n = 4.


Cumulative
P Leached

mg
0.044 & 0.006
0.000 + 0.005
0.895 & 0.373
33.6 & 4.88


Cumulative
P Leached

% of P Applied
NA
0.042 & 0.005
0.46 & 0.181
8.17 &1.18
0.053 & 0.011
0.025 & 0.003
0.012 & 0.002
0.046 & 0.005
0.034 & 0.005
0.021 & 0.002
0.004 & 0.002
0.001 & 0.000
0.001 & 0.002
0.069 & 0.009
0.226 & 0.051
3.30 + 0.906
0.051 & 0.004
0.147 & 0.096
1.25 & 0.301
0.070 + 0.005
0.254 & 0.057
1.55 & 0.518
0.076 & 0.011
0.290 + 0. 119
1.27 & 0. 131


Material


Rate

kg P ha
0
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224
56
112
224


Control
TSP
TSP
TSP
Milorganite
Milorganite
Milorganite
GreenEdge
GreenEdge
GreenEdge
Disney
Disney
Disney
GRU
GRU
GRU
Boca Raton
Boca Raton
Boca Raton
Lakeland NS
Lakeland NS
Lakeland NS
OCUD S
OCUD S
OCUD S


0.011 &
0.008 &
0.008 &
0.005 &
0.028 &
0.042 &
0.002 &
0.002 &
0.008 &


0.11
0.006
0.008
0.006
0.011
0.009
0.006
0.002
0.015


0.028 & 0.009
0.423 & 0.106
13.6 & 3.73
0.009 & 0.004
0.261 & 0.199
5.10 &1.24
0.030 + 0.005
0.480 + 0. 118
6.33 & 2.13
0.035 & 0.012
0.554 & 0.246
5.20 + 0.538










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BIOGRAPHICAL SKETCH

Sarah Chinault was born in Lakeland, Florida, on November 24, 1981 to Edward and

Linda Chinault. Sarah has an older brother (Chris, 28) and a younger sister (Amanda, 23). Sarah

obtained her B.S. degree from the University of Florida in 2004, maj oring in environmental

science. Sarah's career goals include working for an environmental advocacy or animal rights

group. Always an animal lover, Sarah has 5 small dogs that she considers children: Mocha (10),

Mini-Me (7), Maynard (4), Hank (11), and Bauer (1). Mitch (11) recently passed from cancer

and will be missed.