Quantitative approach for Assessment of Phosphorus Loss Risk from Alaquod and Paleudult Soil profiles

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Quantitative approach for Assessment of Phosphorus Loss Risk from Alaquod and Paleudult Soil profiles
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english
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Chakraborty,Debolina
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Doctorate ( Ph.D.)
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University of Florida
Degree Disciplines:
Soil and Water Science
Committee Chair:
Nair, Vimala D
Committee Members:
Harris, Willie G
Rhue, Roy D
Comerford, Nicholas B
Cropper, Wendell P

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al -- change -- equilibrium -- langmuir -- plant -- soil
Soil and Water Science -- Dissertations, Academic -- UF
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Soil and Water Science thesis, Ph.D.
bibliography   ( marcgt )
theses   ( marcgt )
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Abstract:
Phosphorus (P) transported from agricultural fields can be a major contributor to eutrophication of aquatic systems. Sandy soils have higher risk of P loss because of limited P retention capacity. Vertical movement of P through the soil profile results in its contact with Bh horizons of Alaquods and Bt horizons of Paleudults which may act as P sinks. The purpose of this study was to evaluate a new tool, the ?safe? soil P storage capacity (SPSC), based on a threshold P saturation ratio (PSR) value, to quantitatively assess P release potential from fertilizer-impacted Alaquod- and Paleudult- soil profiles which are of extensive occurrence in the SE United States coastal plain. Soil samples from Alaquod and Paleudult sites located within Florida were sampled by horizon. The SPSC calculated from P, Fe and Al using oxalate extractant was related to water-soluble P and equilibrium P concentrations (EPC0) obtained from traditional Langmuir isotherms. Plant P availability was determined using iron-oxide impregnated filter paper (FeO-P). A different threshold PSR was obtained for Bh and Bt horizons compared to that of sandy surface horizons of Florida, reflecting the differences in soil components between these horizons. Greater desorption potential of Bh in comparison to Bt likely relates to weaker bonding of P with organically-complexed Al. Environmental risk of P loss from Bt samples, may also be predicted from SPSC. The result indicates that although Bt soils have high P retentive capacity due to crystalline Fe oxides along with phyllosilicates, noncrystalline metal oxides extracted by oxalate are the components that bind P most tenaciously and that control sorption below PSR threshold. Plant P availability from fertilizer-impacted Alaquod and Paleudult subsurface horizons as inferred from FeO-P suggests deep-rooted plants can remove P from subsurface horizons in phytoremediation. Water soluble P, EPC0 and FeO-P are minimum when SPSC is positive and begin to increase when SPSC becomes zero. Results of this research support the validity of SPSC for quantitatively predicting the amount of P that can be safely added to a soil before a given horizon will likely constitute a P loss risk.
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In the series University of Florida Digital Collections.
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by Debolina Chakraborty.
Thesis:
Thesis (Ph.D.)--University of Florida, 2011.
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Adviser: Nair, Vimala D.
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RESTRICTED TO UF STUDENTS, STAFF, FACULTY, AND ON-CAMPUS USE UNTIL 2012-02-29

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1 QUANTITATIVE A PPROACH FOR ASSESSMENT OF PHOSPHORUS LOSS RISK FROM ALAQUOD AND PALEUDUL T SOIL PROFILES By DEBOLINA CHAKRABORT Y A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILL MENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2011

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2 2011 Debolina Chakraborty

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3 T o my parents

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4 ACKNOWLEDGMENTS I would like to thank my Almighty and His blessings throughout my degree program. First and foremost I am heartily thankful to my advisor, Dr. Vimala D. Nair for her scientific imagination, intellect, supervision and an excellent person for having faith in my abilities and guiding me throughout the PhD program. Her mentorship support o utside the academia also helped me propel efficiently. I would like to express my sincere thanks to Wi llie G. Harris for teaching me M ineralogy and being enthusiastic about my work. I am thankful for his valuable advice and answering my doubts whenever I n eeded him. I would also like to thank my committee members: Dr Dean Rhue, Dr. Nick Comerford and Dr. Wendell Cropper for their academic guidance. I would also like to make a special reference to Dawn Lucas, for technical support on my experiments. Last but not the least, it is a pleasure to thank my close friends (Rishi Prasad and Pinaki Deb) and lab group members (Myrlene Chrysostome, Solomon Haile and Manohardeep Josan) for sharing and supporting me during this period. Above all, I owe my deepest gratitud e to my parents Mr. Arun Chakraborty and Ms. Sipra Chakraborty behind all my inspirations.

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5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 7 LIST OF FIGURES ................................ ................................ ................................ .......... 8 ABSTRACT ................................ ................................ ................................ ................... 10 CHAPTER 1 INTRODUCTION ................................ ................................ ................................ .... 12 2 REVIEW OF LITERATURE ................................ ................................ .................... 17 Excess Application of P ................................ ................................ .......................... 17 Surface and Subsurface Loss of P ................................ ................................ ......... 17 Soil P Distribution ................................ ................................ ................................ ... 18 Extractants Used for P Measurement ................................ ................................ ..... 19 Adsorption of P ................................ ................................ ................................ ....... 21 Desorption of P ................................ ................................ ................................ ....... 25 Determination of Environmental P Risk ................................ ................................ .. 26 3 SOIL PHOSPHORU S STORAGE CAPACITY IN MANURE IMPACTED ALAQUODS: IMPLICATIONS FOR WATER TABLE MANAGEMENT ................... 29 Materials and Methods ................................ ................................ ............................ 30 Soil Sampling ................................ ................................ ................................ ... 30 Chemical Analyses ................................ ................................ ........................... 31 Calculations ................................ ................................ ................................ ...... 32 Statistical Analyses ................................ ................................ .......................... 33 Results and Discussion ................................ ................................ ........................... 34 Soil Characterization ................................ ................................ ........................ 34 Phosphorus Saturation Ratio Change Points and SPSC for Soil Horizons ...... 35 .......................... 37 Summary ................................ ................................ ................................ ................ 38 4 COMPOSITIONAL DIFFERENCES BETWEEN ALAQUODS AND PALEUDULTS AFFECTING PHOSPHORUS SORPTION DESORPTION BEHAVIOR ................................ ................................ ................................ ............. 51 Materials and Methods ................................ ................................ ............................ 52 Chemical Analyses ................................ ................................ ........................... 52 Mineralogical Analysis ................................ ................................ ...................... 53 Phosphorus Sorption ................................ ................................ ........................ 53

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6 Phosphorus Desorption ................................ ................................ .................... 54 Calculations ................................ ................................ ................................ ...... 54 Statistical Analyses ................................ ................................ .......................... 55 Results and Discussion ................................ ................................ ........................... 55 Soil Characterization ................................ ................................ ........................ 55 Phosphorus Sorption and Desorption ................................ ............................... 56 Correlation of Phosphorus Sorption Parameters with Soil Properties .............. 58 Environmental Implications ................................ ................................ ............... 60 Summary ................................ ................................ ................................ ................ 61 5 A COMPARISON OF P DYNAMICS BETWEEN ALAQUODS AND PALEUDULTS: IMPLICATIONS FOR ENVIRONMENTAL RISKS AND PHYTOREMEDIATION. ................................ ................................ .......................... 76 Materials and Methods ................................ ................................ ............................ 77 Soil Sampling ................................ ................................ ................................ ... 77 Soil Characterization ................................ ................................ ........................ 77 Determination of Observed and Predicted SPSC ................................ ............. 78 Calculations ................................ ................................ ................................ ...... 79 Statistical Analyses ................................ ................................ .......................... 80 Results and Discussion ................................ ................................ ........................... 80 Soil Characterization ................................ ................................ ........................ 80 Environmental Risk of P Release ................................ ................................ ..... 81 Effectiveness of SPSC in Loamy to Clayey Soil Horizons ................................ 83 Implications of Phytoremediation of Subsurface P ................................ ........... 84 Summary ................................ ................................ ................................ ................ 85 6 CONCLUSIONS ................................ ................................ ................................ ..... 96 LIST OF REFERENCES ................................ ................................ ............................. 101 BIOGRAPHIC AL SKETCH ................................ ................................ .......................... 112

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7 LIST OF TABLES Table page 3 1 Mean and SD by site (D = dairy; B = beef) and horizon for selected chemical properties of soils studied. ................................ ................................ .................. 39 3 2 Mean and SD by site (D = dairy; B = beef) and horizon for oxalate extractable P and metals, data used in PSR and SPSC calculations ................. 41 3 3 Estimated model parameters and statistics (with standard errors in parentheses). ................................ ................................ ................................ ...... 43 4 1 Mean and SD by site and horizon for chemical properties of soils studied. ........ 62 4 2 Mean and standard deviation (SD) by sites and horizons of P sorption capacity (P sorp ), determined using single point (1000 mg P kg 1 ) isotherm. ........ 63 4 3 Phosphorus sorption and desorption par ameters for Bh and Bt horizons. .......... 64 4 4 Correlation of sorption parameters with selected soil variable s for Bh samples studied (n=33) ................................ ................................ .................... 65 4 5 Correlation of sorption parameters with selected soil variable s for Bt samples studied (n=45) ................................ ................................ ................................ .. 66 5 1 Mean and SD by site and horizon for chemical p roperties of soil s studied. ........ 86 5 2 Mean and SD by site and horizon for oxalate extractable P and metals, data used in PSR and SPSC calculations and total P for the soils studied ................ 87

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8 LIST OF FIGURES Figure page 1 1 Alaquod soil profile ................................ ................................ ............................. 16 1 2 Paleudult soil profile ................................ ................................ ........................... 16 3 1 Location of the study sites. ................................ ................................ ................. 44 3 2 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in an oxalate extract ......... 45 3 3 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in Mehlich 1 extract .......... 46 3 4 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in Mehlich 3 extract. ......... 47 3 5 Relationship between soil phosphorus storage capacity (SPSC) and Capacity Factor for spodic horizons calculated using Mehlich 1 ................................ ....... 48 3 6 Relationship between soil phosphorus st orage capacity (SPSC) and Capacity Factor for spodic horizons calculated using Mehlich 3. ................................ ...... 48 3 7 Soil phosphorus storage capacity (SPSC) vs. water soluble P (WSP) of A and E horizons (using 0.10 as the change point P saturation ratio). ................... 49 3 8 Soil phosphorus storage capacity (SPSC) vs. water soluble P (WSP) of spodic horizons (using 0.05 as the change point P saturation ratio, Fig. 3.2). .... 49 3 9 Schematic diagram of a soil profile illustrating the movement of P to surface and subsurface water bodies and the effect of water table manipulations .......... 50 4 1 Location of the study sites. ................................ ................................ ................. 67 4 2 Comparison of A) oxalate extractable Al; B) CBD extractable Al; C) oxalate extractable Fe; D) CBD extractable Fe ................................ ............................... 68 4 3 Relationship between oxalate extractable Fe and Al, Ox Fe+Al and pyrophosphate extractable Fe and Al, Pyro Fe+Al for Bh and Bt horizons. ........ 70 4 4 Relationship b etween total carbon and oxalate extractable Al for A) E of Alaquods B) Bh of Alaquods C) E of Paleudults and D) Bt of Paleudults. .......... 71 4 5 X ray diffraction analysis of clay fractio n for the Alaquod profile. ........................ 73 4 6 X ray diffraction analysis of clay fraction for the Paleudult profile. ...................... 73

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9 4 7 Relationship between P sorbed (mg kg 1 ) versus P desorbed expressed as a fraction of sorbed P, DEF (%) for Bh and Bt horizons. ................................ ....... 74 4 8 Relationship between oxala te extractable Al, Ox Al (mmol kg 1 ) and P desorbed expre ssed as a fraction of sorbed P, DEF (%) for Bh horizons. .......... 74 4 9 Schematic diagram depicting seasonal scenarios of water and P movement trends in Alaquod (a and b) and Paleudult (c) soil profiles ................................ 75 5 1 Setup of Iron oxide impregnated filter paper. ................................ ...................... 88 5 2 Relationship between P extracted from iron oxide impregnated filter paper (FeO P) and water soluble P (WSP) for E and Bh horizons of Alaquods. .......... 89 5 3 Relationship between P extracted from iron oxide impregnated filter paper (FeO P) and water soluble P (WSP) for E and Bt horizons of Paleudults. .......... 89 5 4 Relationship between water soluble P (WSP) and P saturation ratio calculated for subsurface E and Bh horizons of Alaquods ................................ .. 90 5 5 Relationship between water soluble P (WSP) and P saturation ratio calculated for the subsurface E and Bt horizons of Paleudults ........................... 91 5 6 Relationship between soil P sto rage capacity (SPSC) and water soluble P (WSP) for E and Bh horizons of Alaquods. ................................ ......................... 92 5 7 Relationship between soil P storage capacity (SPSC) and water soluble P (WSP) for E and Bt horizons of Pal eudults. ................................ ........................ 92 5 8 Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for E and Bh horizons .................... 93 5 9 Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for E and Bt horizons ..................... 93 5 10 Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for Alaquod and Paleudult ............. 94 5 11 Relationship between soil P storage capacity (SPSC) and equilibr ium phosphorus concentration (EPC 0 ) for Bh and Bt horizons. ................................ 94 5 12 Relationship between soil P storage capacity (SPSC) predicted vs. SPSC observed for Bt samples. ................................ ................................ .................... 95 5 13 Relationship between Fraction of P desorbed and P saturation ratio calculated for the Bh horizons of Alaquods ................................ ........................ 95

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10 Abstract of Dissertation Presented to the Graduate School of the Unive rsity of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy QUANTITATIVE APPROAC H FOR ASSESSMENT OF PHOSPHORUS LOSS RISK FROM ALAQUOD AND PALEUDUL T SOIL PROFILES By Debolina Chakraborty August 201 1 Chair: Vimala D. Nair Major: Soil and Water Science Phosphorus (P) transported from agricultural fields can be a major contributor to eutrophication of aquatic systems. Sandy soils have higher risk of P loss because of limited P retention capacity. Ver tical movement of P through the soil profile results in its contact with Bh horizons of Alaquods and Bt horizons of Paleudults which may act as P capacity (SPSC), based on a threshold P saturation ratio (PSR) value, to quantitatively assess P release potential from fertilizer impacted Alaquod and Paleudult soil profiles which are of e xtensive occurrence in the SE United States coastal plain. Soil samples from Alaquod an d Paleudult sites located within Florida were sampled by horizon. The SPSC calculated from P, Fe and Al using oxalate extractant was related to water soluble P and equilibrium P concentrations (EPC 0 ) obtained from traditional La n gmuir isotherms. Plant P av ailability was determined using iron oxide impregnated filter paper (FeO P). A different threshold PSR was obtained for Bh and Bt horizons compared to that of sandy surface horizons of Florida, reflecting the differences in soil components between

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11 these h orizons. Greater desorption pote ntial of Bh in comparison to Bt likely relates to weaker bonding of P with organically complexed Al. Environmental risk of P loss from Bt samples m ay also be predicted from SPSC. The result indicate s that although Bt soils have high P retentive capacity due to crystalline Fe oxides along with phyllosilicates, noncrystalline metal oxides extracted by oxalate are the components that bind P most tenaciously and that control sorption below PSR threshold. Plant P availability fr om fertilizer impacted Alaquod and Paleudult subsurface horizons as inferred from FeO P suggests deep rooted plants can remove P from subsurface horizons in phytoremediation. Water soluble P, EPC 0 and FeO P are minimum when SPSC is positive and begin to in crease when SPSC becomes zero. Results of this research support the validity of SPSC for quantitatively predicting the amount of P that can be safely added to a soil before a given horizon will likely constitute a P loss risk.

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12 CHAPTER 1 INTRODUCTION Phos phorus (P) is essential for plant growth and develop ment. However, continuous application of P and its subsequent loss to waterways accelerate s e utrophication of surface waters ( Sharpley et al., 2003; Withers and Haygarth, 2007; Filippelli, 2008). In Flori da the majority of surface horizon soils are sandy. In sandy soils the risk of P loss is higher because of limited P retention capacity of the soil ( Nair et al., 2004 ). Due to excess P loading P may move through the soil profile and can come in contact w ith subsurface horizons. Subsurface flow can also be a major pathway for P losses from agricultural soils (Sims et al., 1998; McDowell and Sharpley, 2001 ). Neg ative environmental changes such as algal blooms have been observed in Florida Bay during a 10 ye ar observation period by the US Geological Survey evaluation of the South Florida National Water Quality Program ( McPherson 1999) Alaquod s of the SE U.S. are characterized by sandy textures, fluctuating water table and the presence of a subsurface spodic horizon (Bh) below an A E horizon sequence (Soil Survey Staff, 1999). They represent the most extensive soil g reat g roup of Florida. The sandy A horizon usually has a depth of 15 to 20 cm with a small amount of organic matter. The thickness of the E horiz on typically ranges from 20 to 140 cm, depending on the soil series. The Bh horizon generally has low pH along with the accumulation of C and associated metals (mainly Al and Fe), which have relatively high affinity for P. The A and E horizons of these soi ls have negligible P retention capacity (Nair et al., 1998) When P loading is high, P may move through the soil profile coming in contact with the spodic horizon where it can be sorbed by spodic materials. Depth to the spodic horizon is important for eval uating P mobility; soils with a greater depth to

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13 spodic horizons have greater susceptibility for P loss due to lower probability of interacting with the Bh horizon before being laterally transported from the site. Paleudults of the SE c o astal Plain of U.S have sandy epipedons overlying loamy or clayey Bt horizons The E horizons of these Paleudults consist mainly of sand with coatings of silt and clay, as bound by relatively low amounts of metal oxides. P hosphorus retention by Bt horizons is mai nly influe nced by inorganic metal oxides (Zhou et al., 1997) The P retention capacity of Bt horizons is significantly higher than that of overlying A and E horizons (Harris et al., 1996). There is a need to study the chemical compositio nal differences between Alaq uod and Paleudult subsurface horizons to evaluate implications for risk of P loss as P moves through a soil profile. Phosphorus sorption isotherms are used extensively to determine the P loss risk to runoff or drainage. Langmuir isotherms are widely used f or describing P sorption by soils (Mehadi and Taylor, 1988; Taylor et al., 1996; Nair et al., 1998; Li et al., 2007). Factors such as clay content (Sanyal et al., 1993), extractable Fe and Al oxides (Li et al., 2007), organic matter (Sanyal and De Datta, 1 991; Kang et a l., 2009) and soil pH (Sato and Comerford, 2005) affect P sorption in soil. Experimentally the risk of P loss from soils can also be estimated from equilibrium P concentration (EPC 0 ) as obtained from P sorption isotherm s The parameter EPC 0 m ay be defined as the P concentration in solution at which neither adsorption nor desor ption of P occurs in soil (Nair et al., 1998 ; Zhou et al., 2005) Environmental risk of P loss from soil horizons can be easily evaluated from the phosphorus saturation r atio (PSR; Nair et al., 2004 ) and soil phosphorus storage capacity (SPSC ; Nair and Harris, 2004 ).

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14 release of P from soil to solution abruptly increases can be determined for a given population of soils. Phosphor us saturation ratio may be calculated using extractants such as oxalate (PSR Ox ), Mehlich 1 (PSR M1 ) or Mehlich 3 (PSR M3 ) as the molar ratio of P to [Fe + Al]. A PSR valu e of 0.10 ( using oxalate P, Fe and Al in the PSR calculation) has been determined as an environmental threshold for surface horizons of relatively well drained sandy soils of Florida (Nair et al., 2004). Soil P storage capacity is a calculation of how much P can be added to a soil before reaching this critical PSR threshold Phosphorus reten tion and release characteristics from Alaquod and Paleudult profiles still need to be studied thoroughly. T here is no information available on a practical change point related to P release from subsurface horizons of Alaquods and Paleudults. The threshold value of Bh and Bt horizons will likely differ from each other and from surface horizons because of compositional difference s The research hypotheses are as follows: 1. In comparison to A and E horizons of Alaquods, Bh horizons will release P differently bec ause of compositional differences among the horizons. 2. Chemical c ompositional differences within and between Alaquod and Paleudult profiles are responsible for differences in P retention and release from horizons that occur in these soils. 3. The EPC 0 will be low when PSR values are below the change point threshold (i.e., SPSC>0 ) because both measures relate closely to the point at which high energy bonding sites for P are filled. 4. Bt horizons will have high P retention capacity but all the sorbed P may not b e retained tenaciously beyond the threshold PSR w hich is controlled by noncrystalline metal oxides. 5. Deep rooted plants can access P from subsurface horizons particularly the spodic horizon of Alaquods, and may be successfully used to reduce the risk of P loss from these soils.

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15 Based on the hypotheses the speci fic objectives of this study were as follows: 1. Compare the P re lease characteristics of A and E and subsurface (Bh) horizons of manure impacted Alaquods to allow an evaluation of the soil P stora ge capacity of the Alaquod profile and to use this information for water table management strategies with respect to P transport. 2. Determine the compositional differences between subsurface horizons of Alaquods and Paleudults and to evaluate implications fo r risk of P loss via subsurface flow in these soils. 3. Compare P release behavior as assessed using PSR and SPSC and to relate it to the compositional differences between Alaquod and Paleudult subsurface horizons. 4. Evaluate the relation between EPC 0 and SPSC which could serve as a more readily determinable substitute for predicting P loss risk 5. Evaluate the validity of SPSC in predicting the maximum safe loading of P for Bt samples (which contain appreciable crystalline Fe oxides and kaolinite clay) using kn own P additions approach. 6. Determine P availability for plant uptake from subsurface horizons of Alaquods and Paleudults and to evaluate the potential for phytoremediation for high P loaded soils.

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16 Figure 1 1 Alaquod soil profile ( Source: http://wgharris.ifas.ufl.edu/SEED/Htm.images/ mya_p.htm ) Figure 1 2 Paleudult soil profile ( Source: http://wgharris.ifas.ufl.edu/SEE D/Htm.images/ 19.htm )

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17 CHAPTER 2 REVIEW OF LITERATURE Excess Application of P The United States Environmental Protection Agency (USEPA) identified agricultural non point source pollution for the degradation of water qualit y (USEPA, 2002). One of the majo r causes of this pollution is P which moves from agricultural lands due to excessive application of fertilizers and manures. In manure application scenarios, nutrient loading is often based on crop N requirements, resulting in an excess of P in the soil du e to high P/N ratio of manure (Robinson and Sharpley, 1996) Phosphorus moves from agricultural land both in soluble form and in association with particles and colloids (Haygarth et al., 1997). Particulate and colloid P transport is associated with soil er osion arising from raindrop impact and overland flow (McDowell et al., 2003; Owens and Walling, 2002) while soluble P is transferred to water bodies (Heckrath et al., 1995) via surface or subsurface flow Phosphorus enrichment of surface water leads to eut rophication ( Mansell et al., 1991; Sharpley and Halvorson, 1994; Sims et al., 1998; Logan, 2001 ). T he concern about eutrophication of Lake Okeechobee, Florida has increased since 1970 due to increased water column total P concentrations (Havens et al., 200 3). Surface and Subsurface Loss of P Hydrology is the driving force that controls the transfer of P from lands because water provides the energy and the carrier for P movement ( Haygarth and Jarvis, 1999). Pathways for P movement can be broadly classified as surface or overland flow and subsurface flow. Loss of P in surface runoff from agricultural sources is one of the major non point source pollution of P. I n sandy soils the risk of P loss from surface applied P

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18 is higher than fine textured soils because of limited P retention capacity of the soil (Nair et al., 2004 ). Subsurface pathways include lateral flow through the soil, vertical drainage, and preferential flow through macropores and artificial drainage channels (Curley et al., 2010). Subsurface loss of P is substantial and it is well documented in different parts of the world, including the southeastern and Mid Atlantic States of the United States ( Sims et al., 1998), Canada (Simard et al., 1995 ); and Australia (Stevens et al., 1999; Melland et al., 2008) Subsurface P losses have often been ignored because of the greater probability of P retention by subsurface horizons. However, more recently subsurface P transfer has increasingly been addressed by the scien tific community from an environmental perspective, since small P losses via subsurfac e flow may affect water quality ( Tunney et al ., 1997 ; Turner and Haygarth, 2000 ). Soil P Distribution Soil P may exist in different pools including dissolved inorganic P, inorganic P sorbed on the soil particle surfaces, inorganic P sorbed by the slow time dependent processes and the organic P pool which includes unbound precipitates (McGechan and Lewis 2002). For the majority of the soils 30 to 65% of the total P is organic P; however high organic matter soils can contain up to 90% organic P (Harris son, 1987). Organic P is repeatedly added to the soil in the form of animal, microbial and plant detritus (Condron et al., 2005). Inorganic P exists mainly as adsorbed P and also as primary and secondary P solid phases. Soil inorganic P exists in different mineral forms. These minerals vary in solubility and ability to supply P to the soil solution depending on factors such as mineral P solubility, pH and concentration of metals like Al and Fe (Pierzynski et al., 2005) Organic P forms mainly constitute ino sitol phosphates,

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19 phospholipids, and nucleic acids and their derivatives (Stevenson, 1982). Turnover of organic P in soils is determined by the rates of immobilization and mineralization. Immobilization may be defined as the biological conversion of inorga nic P to organic P in soil; whereas release of inorganic P from organic P is referred to as mineralization. Phosphorus applied in the form of P fertilizers or crop residues, manures and sewage sludge will modify three major P pools in the soil plant sy stem : a) soil solution P b) available soil P and c) unavailable soil P (Singh et al., 2005). The quantity of P in soil solution is very low at any given time and it is in the order of <1 kg ha 1 or <1% of the total quantity of P in the soil (Pierzynski, 199 1). Labile P may be defined as the soil or sediment P that equilibrates rapidly with an aqueous solution whereas; those P forms which do not readily equilibrate may be referred as the nonlabile P (Pierzynski et al. 2005). Available P (P quantity) and P av ailability (P intensity) are mainly used to describe the total plant available P pool and the P that may be used immediately by plants (Holford, 1997). These two factors are dependent on the Buffer capacity of the soil solution is the resistance of the solution concentration to change and is an indication of the quantity of P sorbed on surface sites which will be easily desorb ed (Holford, 1997). Higher buffering capacity leads to slower P release to soil solution. Claye y soils have high buffering capacity becaus e of high surface area (McGechan and Lewis, 2002) and a lso due to the high proportions of Fe or Al oxide minerals ( Bowden et al., 1977). Extractants U sed f or P M easurement Phosphorus release from P impacted soils has been studied by several researchers using different extractants. Pote et al. (1996) observed w ater soluble P (WSP) as the most appropriate environmental estimator of P concentrations in runoff

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20 compared with other soil test method s developed for crop pr oduction. Several researchers (Graetz and Nair, 1995; Silveira et al., 2006) have also observed continuous releases of P from manure impacted soils during sequential leaching. However, t he small amount of soil P extracted by th is method may not reflect all forms of labile P and thus has limited the use of water as an extractant (Elrashidi et al., 2001 ). Many soil test extractants like Mehlich 1, Mehlich 3, Bray 1 and Bray 2 use strong acids like HCl, H 2 SO 4 and HNO 3 to dissolve Fe, Al or Ca phosphates to de termine the labile P. Mehlich (1953) introduced a double acid combination, the Mehlich 1 solution which constitutes 0.05 M HCl and 0.0 1 25 M H 2 SO 4 for extracting P along with metals from acid soils in the southeastern part of the U nited States Mehlich modi fied his initial soil test P (STP) by developing a multi element extractant, the Mehlich 3 which may be used on a wider range of soils Mehlich 3 is a more powerful extractant than Mehlich 1 and can be used in acid and neutral soil s with much greater effic iency (Elrashidi et al., 2001). It contains ammonium fluoride, ammonium nitrate, acetic and nitric acids, and the chelating agent EDTA. Acetic acid acts as a buffer and maintains the pH of the solution at 2.5. Ammonium nitrate helps to extract basic cation s such as calcium, magnesium, sodium and potassium Nitric acid extracts a portion of calcium phosphates and its acid component helps in extraction of basic and micronutrient cations. Fluoride extract s Al and Fe phosphates, and EDTA m ainly acts as a chelat ing agent (NCDACS, 2007 ). Fluoride ion is also used in Bray 1 (0.03 M NH 4 F +0.025 M HCl) and Bray 2 ( 0.03 M NH 4 F +0.1 M HCl) extractants to replace P sorbed at metal hydroxide surfaces through ligand exchange reactions and to initiate complex formation wit h metals in solution to prevent metal phosphate precipitation (Fox et al., 1990)

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21 Oxalate extraction uses 0.1 M oxalic acid and 0.175 M ammonium oxalate solution. It was designed to remove P associated with amorphous oxides of Al and Fe in non calcareous s oils (Hooda et al., 2000). Protonation and complexation is the main mechanism for the dissolution of Fe and Al phosphate bonds (Cornell and Schwertmann, 1996). Oxalate anions replace P sorbed at metal hydroxide surfaces through ligand exchange reactions an d prevent metal phosphate precipitation by complexing metals in solution (Fox et al., 1990). Olsen extractant is a buffered alkaline solution of 0.5 M sodium bicarbonate solution at a pH of 8.5. Olsen extractant was developed mainly for calcareous soils bu t it works well on acid soils also (Smyth and Sanchez, 1982). Due to the high pH of the extractant, OH ions reac t with Al and Fe and solubilize P from Al P and Fe P (Tyner and Davide, 1962). In calcareous soils it functions by replacing adsorbed P with HC O 3 which reacts with Ca as CaCO 3 and thus solubilizes Ca P (Beegle, 2005). Adsorption of P Transport of P with water in soils is dependent mainly on the extent of P sorbed by soil components. Adsorption is the process by which reactive chemicals (ionic P H 2 PO 4 HPO 4 2 ) are removed from so lution and become attach ed to surfaces (McGechan and Lewis, 2002). Phosphorus sorption consists of a fast reversible true sorption process on soil particle surfaces and a slow almost irreversible process consisting of diffusion, precipitation and deposition which is described as the slo w sorption process. Iron and aluminum oxides and hydroxides in acidic soils and calcium in calcareous or alkaline soils have been identified as the principal soil constituents in phosphat e adsorption ( Hemwall, 1957). A small portion of the P which is sor bed can be desorbed easily. A m ajor portion of the P added is rapidly fixed and thus not easily

PAGE 22

2 2 desorbed Hysteresis is mainly due to the differences in the rates of adsorption and desorpti on and does not necessarily constitute truly irreversible adsorption ( Rhue and Harris, 1999 ). Ho wever, in sandy soils, with low concentrations of Fe and Al, little P will be held by the soils and P can be more easily lost from the soil Hysteresis is a fun ction of the P loading rate, solid phase physicochemical characteristics, and residen ce time (Reddy and Delaune, 2008 ). Precipitation of P as insoluble compounds (va n Riemsdijk et al., 1984), a change from monodentate to bidentate forms (less reversible) o f sorbed P (Munns and Fox, 1976) and slow diffusion of P into soil solids (Ryden et al., 1977) are the possible mechanisms associated with hysteresis. Ph osphorus sorption isotherms (e.g. Langmuir and Freundlich ) are widely used to determine potential risk of P loss to runoff or drainage (Sui and Thompson, 2000) Langmuir isotherms are widely used for describing phosphate sorption by soils (Mehadi and Taylor, 1988; Taylor et al., 1996; Nair et al., 1998; Li et al., 2007 ). Langmuir adsorption equation can be expressed as: ( 2 1 ) where o the total amount of P sorbed S o = originally sorbed P o n the solid phase C= concentration of P after 24 h equilibration S max = P sorption maximum k = a constant related to the bonding energy The Freundlich equation can be represented as

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23 ( 2 2 ) w here K and n are constants for a given soil. C is the equilibrium P concentration. The Langmuir model has an advantage over the Freundlich model in environmental applications because the soils max imum sorption capacity and the bonding energy constant can be det ermined ( Graetz and Nair, 2000). Phosphorus sorption isotherms are time consuming and complicated for routine use by soil test laboratories (Sharpley et al., 1994). However, Bache and William s (1971) suggested a single equilibration using a high concentration of P (single point isotherm) to determine the P sorption capacity of soils rapidly and e asily with reasonable accuracy. This was also confirmed by Mozaffari and Sims (1994) for surface an d subsurface horizons of four Atlantic Coastal Plain soils. For Florida soils a single point isotherm using a 100 mg L 1 P solution gave a linear relationship with S max for both upland (Nair et al., 1998) and wetland (Reddy et al., 1998) soils providing a means of determining S max without isotherm development. There are close positive relationships between P sorption an d the abundance of crystalline and amorphous iron and aluminum oxides in many soils from different envi ronments ( Nair et al., 1998; Sanyal e t al., 1993; Zhou et al., 1997; Agbenin, 2003; Wiriyakitnateekul et al., 2005; Wisawapipat et al., 2009 ). P hosphorus sorption in Fe humic substance mixture was six to seven times higher in comparison to amorphous Fe oxides which may be due to the ternary c omplex formation between Fe humic substances and phosphate (Gerke and Hermann, 1992). Yuan and Lavkulich (1994)

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24 observed s ignificant correlations between P sorption and oxalate extractable Al and Fe in Spodosols from British Columbia. Positive relationship between C content of sp odic horizons and P sorption had been observed by Nair et al. (1998). This relationship was due to the indirect effect of C through complex formation with cations such as Fe and Al associated with organic matter. Various pools of Fe and Al associated with P retention are measured by selective dissolution with different extractan ts. Ammonium oxalate extracts both noncrysta lline inorganic and organically complexed Fe and Al (McKeague and Day, 1966; Jackson et al., 1986 ). Citrate bicar bonate dithionite (CBD) primarily extracts free Fe oxides. The d ifference between CBD and oxalate extractable Fe and Al is due to the dissolution of crystalline Fe oxides (McKeague et al., 1971). Sodium pyrophosphate extracts organically complexed Fe and A l in soils (McKeague, 1967; Wada and Higashi, 1976) though it can extract some noncrystalline inorganically complexed forms of these metals as well (Kaiser and Zech, 1996). S everal researchers have suggested CuCl 2 or KCl as an alternative extractant for Al bound to soil organic matter (Oates and Kamprath, 1983a; Hargrove and Thomas, 1984). Juo and Kamprath (1979) found that 1.6 to 12 times more Al was extracted by 0.5 M CuCl 2 than 1 M KCl. The ites is greater for Cu and it can easily replace Al bound to organic matter (Matus et al., 2008). CuCl 2 is not efficient to remove Al significantly from aluminosilicate minerals, however, it is efficient in extracting some poor ly ordered Al associated with soil mineral (Oates and Kamprath, 1983b).

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25 Another very important soil property for P sorption is the soil clay content (Loganathan et al., 1987; Bennoah and Acqu aye, 1989 ; Sanyal et al., 1993 ). Clayey soils with iron oxide s ha ve high P retention capacity in comparison to the sandy and loamy Ultisols and loamy Oxisols (Sanchez and Logan, 1992). Large surface area and presen ce of P sorbing minerals contribute for the greater P adsorption capacity for these soils compared to the c oarse textured soils (Loganathan et al., 1987). Soil pH has a role i n P sorption ; P sorption generally decreases with increasing pH. At h igher pH, common mineral surface s become negative resulting in electrostatic repulsion and decrease in P sorption (Hayn es, 1982; Oh et al., 1999; Sato and Comerford, 2005). With increasing pH, hydroxyl ions compete with phosphate ions for specific sorption sites on mineral surfaces (Smyth and Sanchez, 1980). Also, at high pH, Al hydroxide polymers can neutralize sites wher e more reactive Al surfaces were present (Sanchez and Uehara, 1980). Desorption of P Desorption is fundamental in controlling the soil solution P concentration and hence the bioavailability of soil P (Sato and Comerford, 2006). P hosphorus desorption can b e determined by dilution, sequential extraction, or anion exchange resin extraction techniques (Brewster et al., 1975; Bhatti and Comerford, 2002). D ilution metho d is the process of P desorption from the solid phase by shaking the soil sample for a fixed e quilibration time with a range of soil:solution ratios with single (Barrow, 1979) or successive (Sharpley et al., 1981) extractions. In sequential method an extracting solution is added to the soil at constant soil:solution ratio, and the sample is shaken at a fixed equil ibration time. This procedure is repeated until P desorption is exhausted or a pattern of P release is recognized ( Bhatti and Comerford, 2002 ). Anion exchange resin

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26 (AER ) extraction is performed in a similar manner as the sequential extract ion where bags filled with AER are used to remove P from solution (Yang and Skogley, 1992; Delgado and Torrent, 1997). The difficulty of this method was to separate the soil from the resin after each desorption step T he use of nylon netting bags to hold t he resin helped to retrieve and extract P from the resin (Saggar et al., 1990) To overcome the difficulties with AER, Fe oxide impregnated filter paper may be used to determine plant P availability, P desorption kinetics and P dynamics in the field (Chard on et al., 1996 ). In comparison to the common acid or base extractants used, P extracted by Fe oxide impregnated filter paper ( FeO P ) may be successfully used to estimate the labile P pool as this method does not depend on the destructive dissolution of so il components or reaction products (Menon et al., 1989; Klatt et al., 2003 ). The FeO coating acts as a P sink and initiate adsorption mechanism similar to the one which occur s at the interface of soil and root surface (Myers et al., 1997). Determination o f E nvironmental P R isk Many point and nonpoint sources of P have the potential to induce eutrophication in surface water. Regulation for further P application and proper management of P in order to avoid wa ter quality problems is essential. Soil test phosp horus (STP) measurements were mainly used for soil fertility and agricultural productivity; but later they were used to determine the risk of soil P to be transported to surface and groundwater (Sharpley et al., 2003; Sotomayor Ramirez et al., 2004). Howe ver, different soils have different critical STP value s above which the release of P from soil increases significantly (Hesketh and Brookes, 2000). Experimentally the risk of P loss from soils can be estimated from equilibrium P concentrations (EPC 0 ) as o btained from P sorption isotherm s The parameter EPC 0 may

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27 be defined as the P concentration in solution at which neither adsorpt ion nor desorption of P occurs in soil ( Pierzynski et al., 1994; Nair et al., 1998). The potential for desorption of PO 4 3 from soils can be estimated from EPC 0 (Fang et al., 2002; McDowell and Sharpley, 2003). Soils with high EPC 0 values have a greater tendency to desorb dissolved P into runoff waters (Sharpley et al., 1994). Exchange of P between soils/sediments and the water col umn through the sorption process can also be defined by EPC 0 (Kerr et al., 2011) Phosphate ( PO 4 3 ) w ill sorb on solid surfaces to re establish the equilibrium condition when the concentration of PO 4 3 in solution increases above equilibrium concentration. However, PO 4 3 would be desorbed from the solid sediment phase when the concentration in solution decreases (House and Denison 2000, 2002; Jarvie et al. 2005). Phosphorus saturation ratio (PSR), which is the molar ratio of P to [Fe + Al], is often used as an environmental indicator of P loss from soils (Maguire and Sims, 2002; Nair and Harris, 2004). Phosphorus saturation ratio can be calculated from P, Fe and Al extracted with oxalate ( PSR Ox ), Mehlich 1 (PSR M1 ) or Mehlich 3 (PSR M3 ) solution (Nair et al., soluble P (WSP) abruptly starts to increase with increasing PSR is evident from WSP PSR relationships and can be used for management purposes to estimate the potential risk of P loss from soils. The change point refer s to a threshold PSR value above which further P added may be lost easily through runoff or leaching (Casson et al., 2006). Above the change point PSR of 0.1 (using oxalate P, Fe and Al in the PSR calculations ) there is a higher risk of P loss from Florida soils (Nair et al., 2004).

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28 Neither STP nor PSR provides information on how much more P can be added to a certain volume or mass of soil before the soil begins to release P. The latter information is provided by the soil phosphorus storage capacity (SPSC) proposed by Nair and Harris (2004), calculated using P, Fe and Al extracted with oxalate solution. SPSC depends on a threshold PSR as determined for a specific range of soils and it is a function of Al and Fe concentrations. The relationship between SPSC and WSP indicated that when SPSC is positive, the soil is a P sink, and when it is negative the soil is a potential P source (Chrysostome et al., 2007 )

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29 CHAPTER 3 SOIL PHOSPHORUS STOR AGE CAPACITY IN MANU RE IMPACTED ALAQUODS: IMPLICATIONS FOR WAT ER TAB LE MANAGEMENT With excessive use of fertilizers and manures soil phosphorus (P) in agricultural lands has increased, leading to eutrophication of surface water. In sandy soils the risk of P loss from surface applied P is higher than from fine textured soil s because of limited P retention capacity of the soil (Nair et al., 2004). Phosphorus saturation ratio (PSR), which is the molar ratio of P to [Fe + Al], is often used as an environmental indicator of P loss from soils (Maguire and Sims, 2002; Nair and Har ris, 2004). The change point refers to a threshold PSR value above which further P added may be lost easily through runoff or leaching (Casson et al., 2006). A PSR valu e of 0.10 has been determined (using either oxalate or Mehlich 1 P, Fe and Al in the PSR calculations), as an environmental threshold for surface horizons of relatively well drained sandy soils of Florida (Nair et al., 2004). There is a need to determine the threshold PSR for Bh horizon because of the inherent differences between the componen ts of this horizon and those of surface horizons. Soil t est phosphorus (STP) and P saturation ratio (PSR) are often used as environmental risk assessments However, neither STP nor PSR provide information about how much P can be added to a certain mas s or volume of soil with minimal environmental risk. This information is provided by soil phosphorus storage capacity (SPSC) proposed by Nair and Harris (2004) Validity of the SPSC is contingent upon thorough extraction of the main forms of Al and Fe with whi ch P is associated in the sample, as essentially accomplished by the oxalate extractant. Both M1 (Chrysostome et al., 2007) and M3 (Kang et al., 2009) do not extract Fe and Al with the same efficiency as does the oxalate solution. Differences in Fe and Al concentrations between

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30 extractants in the calculation of SPSC require a conversion factor for calculating the true capacity of the soils to retain additional P when a soil test solution is used as the extractant. The value of the conversion factor is likel y different for sandy A and E horizons, and for Bh horizons due to compositional differences among soil horizons. The conversion factor for SPSC calculated with M1 data is 1.3 for the A and E horizons of Alfisols, Entisols, Spodosols, and Ultisols (Nair et al., 2010); the conversion factor using M3 is 1.1 calculated from data of Chrysostome et al. (2007) using a threshold PSR of 0.08 (Nair et al., 2004). Based on SPSC, best management practices (BMPs) such as addition of Fe and Al amendments (to increase th e P storage capacity of surface soils that have low P retention) or water table control (to utilize additional storage capacity of horizons for minimizing P loss) may be implemented. The objective of this chapter was to compare the P re lease characterist ics of A and E and subsurfac e (Bh ) horizons of Alaquod profile of dairy and beef manure impacted soils. The specific objectives were to : d d etermine a conversion factor enabling determination of SPSC for spodic horizons using practical soil tests (M1 and M3); e valuate the use of SPSC for water table management of dairy and beef manure impacted soils. Materials and Methods Soil Sampling Thirty Alaquod profiles from three beef (B1, B2 and B3) and three dair y (D1, D2 and D3) manure application sites (five profiles from each site) were sampled by horizon to a meter depth (Figure 3 1 ), for a total of 192 soil samples. Two of the sites (B1 and located at

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31 Alachua and Hardee County, FL, respectively. The third beef site (B2), located in Osceola County, FL, is a private ranch that has been in operation since the 1940s. All dairy sites were located in Okeechobee County, FL. The dairy sites comprise d of pasture (grazing area) and forage (forage production area) components for D1, holding (area where cattle are held and fed overnight) and pasture components for D2 and intensive (small area closest to the barn) component for D3. Forty nine archived spo dic horizon samples from si x other locations two beef (O1 and O2) and four dairy (O3, O4, O5 and O 6) operations were also included in this study resulting in a total of 241 soil samples. The archived soils were from Okeechobee County, FL. Archived soils from four dairy components (intensive, holding, pasture and forage) differentially impacted by manure were used in this study. The archived beef sites were pasture locations at the beef ranches Total P in the archived soils at dairy sites varied as intens ive> holding> pasture> forage with mean values of 2330, 870, 255, and 45 mg kg 1 for intensive, holding, pasture, and forage components, respectively; mean TP for the beef pastures of archived samples was 45 mg kg 1 (Graetz et al., 1999). C hemical Analys es S amples were thoroughly mixed and air dried before analyses. Soil pH was determined using 1:2 soil and water suspension. Water soluble P was determined using 1:10 soil to water ratio. The extraction was done by shaking 2 g soil with 20 mL of double deio nized water in a reciprocating shaker at about 100 excursions min 1 for 1 h Total P of soil samples was determined using the igniti on method ( Andersen, 1976). Water soluble P and total P concentrations were determined using an autoanalyzer (USEPA, 1983; Method 365 1) by the Murphy

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32 an d Riley ( 1962) procedure Mehlich 1 extractable P (M1 P), Fe (M1 Fe), Al (M1 Al), Ca (M1 Ca) and Mg (M1 Mg) were obtained by extracting with a double acid solution (0.05 M HCl + 0.0125 M H 2 SO 4 ) at a 1:4 soil to solution ratio for 5 min (Me hlich, 1953). Meh lich 3 extractable P (M3 P), Fe (M3 Fe), and Al (M3 Al) were obtained by extracting soil with 0.2 M CH 3 COOH + 0.25 M NH 4 NO 3 + 0.015 M NH 4 F + 0.13 M HNO 3 + 0.001 M EDTA for 5 min at a 1:8 soil to solution ratio (Mehlich, 1984). Oxalate extractable P (Ox P), Fe (Ox Fe), and Al (Ox Al) were determined by extracti on with 0.1 M oxalic acid + 0.175 M ammonium oxalate solution at a 1:50 soil to solution ratio equilibrated for 4 h at a pH of 3.0 (McKeague and Day, 1966). All metals and P in M1, M3 and Ox solution were determined by inductively coupled argon plasma spectroscopy (Thermo Jarrel Ash ICAP 61E, Thermo Elemental, Franklin, MA). Calculations P hosphorus saturation ratio was calculated for each sample using oxalate (PSR Ox ), Mehlich 1 (PSR M1 ) or Mehlich 3 (PS R M3 ) solution as the molar ratio of P to [Fe + Al]. Soil P storage capacity w as calculated based on oxalate extractions because oxalate extracts most of the reactive Al and Fe present in the soil and proportionately represents its P sorption capacity (Klei nman et al., 2003). (Nair and Harris, 2004) ( 3 1 ) SPSC can also be determined using P, Fe and Al from a soil tes t solution such as M1 and M3. ( 3 2 ) ( 3 3 )

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33 where X and Y are conversion factors needed when calculating SPSC using M1 and M3 parameters, respectively. The SPSC in equations ( 3 2 ) and ( 3 3 ) without the correction term is refer The Fe, Al and P (used in the calculation of PSR and SPSC) in equations ( 3 1 ) to ( 3 3 ) are expressed in moles. The SPSC in equations ( 3 1 ) to ( 3 3 ) are expressed in mg kg 1 Soil P storage capacity may be expressed on a per mass basis (e.g., mmol kg 1 mg kg 1 kg ha 1 ) or on a per volume basis (e.g., mg cm 3 mg m 3 kg ha 1 ) to a specified depth. Statistical Analyses The data were analyzed using the General Linear Model procedure in the statistical package SAS (SAS Institute, 2001). Differences between means of soil parameters were compared using Fishers LSD. The relationship between PSR and WSP wa s modeled as a segmented line [ e quation ( 3 4 ) ] with the parameters estimated using nonlinear least squares. The change point (d) in the fitted segmented line model was directly estimated The joining of the two line segments at the change point is ensured by estimating the slope of the left hand line as a function of the change point and ot her model parame ters [ e quation ( 3 5 ) ] Standard errors were estimated from the Fisher information matrix and confidence intervals we re constructed using these standard errors and an appropriate t distribution critical value. Computations for the change point or threshold PSR were determined using a NLIN procedure in SAS, similar to the one adopted in a previous study (Nair et al., 2004). ( 3 4 )

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34 ( 3 5 ) where a 0 b 0 a 1 and b 1 are model parameters, and d, the change point as determ ined using the segmented line mode l Results and Discussion Soil Characterization The pH of the surface horizons ranged from 4.4 to 8.0 (Table 3 1 ). Manure application resulted in highest Ca and Mg concentrations in surface compared to subsurface horizons Mean value of Ca and Mg in surface horizons were 1069 and 175 mg kg 1 respectively. However, Ca and Mg values were still elevated in subsurface horizons of sites D2 and D3 suggesting movement of manure constituents through the soil profile Water solubl e P (WSP) was linearly related to TP for both surface (R 2 = 0.77) and spodic (R 2 = 0.78) horizons. However, WSP values were <8% and < 5% of TP for most of the surface and spodic horizons, respectively (data not shown). Low WSP of the spodic horizons sugg ests that the risk of P loss from these horizons was less than that of surface horizons. Higher concentration of Al in the spodic horizons in comparison to surface horizons (Table s 3 1 and 3 2) suggests that Al associated P can be a major form of P associa tion in the spodic horizons. Many significant correlations have been observed between P sorption and oxalate extrac table Fe and Al in acid soils (V an der Zee and van Riemsdijk, 1986) including Spodosols (Yuan and Lavkulich, 1994 ; Villapando and Graetz, 20 01 ). The oxalate solution extract s Fe and Al from amorphous inorganic substances as well as from horizons of accumulation of Fe and Al organic matter complexes (McKeague, 1967). Thus this extractant is very effective for spodic horizons where most of the F e and Al

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35 are associated with organic matter. Oxalate P represents over 80% of TP for most of the soils. Mehlich 1 and Mehlich 3 extracted less P in comparison to oxalate from most of the soils (Tables 3 1 and 3 2). The extraction efficiency of P along with the metals were oxalate> Mehlich 3> Mehlich 1 for both surface and spodic horizons. Phosphorus Saturation Ratio Change Points and SPSC for Soil Horizons For surface horizons a change point PSR of 0.10 using Ox or M1 P, Fe and Al, and 0.08 using M3 P, Fe and Al were used for calculating the SPSC of the soils (Nair et al., 2004). Most of the surface horizons had PSR values in excess of the threshold PSR. These horizons have little P retention capacity due to low Fe and Al content (Table s 3 1 and 3 2 ) and thus have a high risk of P loss. Further land application of manure (high P/N ratio; Robinson and Sharpley, 1996), based on crop N requirements will aggravate the risk of P loss from the soil. The threshold PSR for the spodic horizons was different from surface horizons in the case of all three extractants: Ox, M1 and M3 (Fig ures 3 2 3 3 and 3 4 ). The change point was 0.05 (95% confi dence limit: 0 to 0.10) for PSR O x ; 0.08 (95% confidence limit: 0 to 0.16) for PSR M1 ; and 0.09 (95% confidence limit: 0 to 0 .19) for PSR M3 Parameter estimates including standard errors and R 2 values for the fitted nonlinear relations hip models are given in Table 3 3. Discrete PSR thresholds for spodic horizons relative to other horizons of Florida soils documents that soil com ponents influence change point behavior. The metals (dominantly Al) in the Alaquods of Florida are mainly organically complexed as a result of podzolization; which is consistent with findings of Zhou et al. (1997) showing that sorption of P by Bh horizon c omponents is less tenacious than for the case of inorganically complexed metal components (e.g., metal oxides) that are prevalent in most other horizons. We calculated the threshold PSRs for the spodic

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36 horizons with and without the archived soils and no st atistical differences were indicated. Though spodic horizons have a higher P retentive capacity than surface horizons (Tables 3 1 and 3 2), once the P sorbing sites get saturated due to excess P loading, spodic horizons will release P and hence will be a P source It has been shown that subsurface flow can be a major pathway for P losses from certain agricultural soils (Sims et al., 1998 ). In the rainy season when the water table is shallow, P from the Bh horizon can diffuse to the E horizons in these poorl y drained soils and may flow laterally to the surface water body, further worsening the situation. Although oxalate solution was chosen as the extractant to calculate the PSR and SPSC of these soils, it requires more time and resources than soil test proce dures such as M1 and M3 that are routinely performed in most soil labs. It is possible to calculate the SPSC using data from a soil test extractant via a conversion factor developed from the population of soils that fall within a range for which a PSR thre shold has been verified. The relationship between SPSC and the capacity factor (SPSC formula but using soil test dat a) for Bh horizon soils (Figure s 3 5 and 3 6 ) suggests that SPSC can be calculated using M1 and M3 P, Fe and Al using a value of X=1.8 in e quation ( 3 2 ) and Y=1.3 in e quation ( 3 3 ) Thus, considering the change point PSR and the conversion factor of spodic horizons, SPSC can be calculated from Ox, M1 and M3 extractant for Bh horizons from the following equations respectively: ( 3 6 ) ( 3 7 )

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37 ( 3 8 ) Water soluble P increases linearly when SPSC is negative for A and E, R 2 = 0.82 (Figure 3 7 ) and Bh horizons, R 2 =0.79 (Figure 3 8 ). This observation confirms the relation of SPSC with WSP as noted by Chrysostome et al. (2007) in a laboratory study. In the current study, the majority of the surface horizon soils are P sour ces. Mean SPSC of Bh horizons (95 mg kg 1 ) was significantly higher than that of A horizons ( 360 mg kg 1 ) due to much lower metal content and greater P loading. The majority of spodic horizons studied had a positive SPSC value indicating that a greater pr oportion of these horizons act as P sinks compared to surface horizons. For both surface and spodic horizons when SPSC values are negative, considerable amounts of P are released from the soils. Along with surface runoff, vertical leaching of P to shallow water table is a problem. By using the SPSC approach, the risk of a given soil horizon releasing excess P and hence contributing to P loss can be determined and this information can be used in making management decisions. As SPSC is additive, the overall P storage capacity of an entire soil profile can be calculated from the SPSC values of individual surface and subsurface horizons (Table 3 2). Applications Safe Soil Phosphorus Storage Capacity Sandy eluvial horizons tend to have little P retent ion capacity because of a low abundance of P retaining mineral components; this is especially true of the A and E horizons of Florida Alaquods (Harris et al., 1996). Lateral transport of P from sandy surface horizons to streams is enhanced by high water ta bles (Mansell et al., 1991). Spodic horizons tend to have a high initial SPSC compared to A and E horizons and

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38 hence can serve as a significant P sink until they reach their PSR change point threshold. Thus, lowering the water table below the upper boundar y of the spodic would tend to increase P retention in the soil by maximizing P contact with the spodic until SPSC becomes zer o (Figure 3 9A ) However, there could be little or no advantage of a lowered water table once the spodic reaches zero SPSC and nega tive SPSC would mean that the spodic would have potential to serve as a P source (Figure 3 9B ). A management strategy that accounted for and utilized the positive SPSC of the spodic while not exceeding it wou ld be environmentally optimal. Such a strategy w ould also require accounting for other factors such as diffusion rate, thickness of saturated zone above the spodic upper boundary, water flow dynamics, etc ., as might be accommodated in a hydrologic model. Summary Results confirm that Bh horizons, domin ated by organically complexed metals, exhibit a discrete PSR change point threshold similar to that of other sandy coastal plain soil horizons. Soil P storage capacity can be calculated for Bh horizons beyond which the continued loading of P w ould render t he Bh a P source. soil assessment enables determination of the absolute amount of P that could be loaded prior to the Bh releasing P at an environmentally unacceptable level. This information is pertinent to water management in that maintai ning a water table significantly above the Bh upper boundary would short circuit its potential for reducing off site movement of agriculturally applied P in cases where the Bh has significant P storage capacity.

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39 Table 3 1 Mean and SD by site (D = dairy; B = beef) and horizon for selected chemical properties of soils studied. Site Horizon Statistics pH WSP TP M1 P M1 Al M1 Fe M1 Ca M1 Mg M3 P M3 Al M3 Fe ---------------------------------------------------------mg kg 1 --------------------------------------------------------------D1 A Mean 5.7 62 185 80 41 10 531 151 116 90 77 SD 1.8 106 223 127 24 5 596 176 130 48 30 E Mean 5.8 8 27 10 9 4 62 18 11 34 16 SD 1.6 15 28 17 7 2 77 22 21 13 10 Bh/Bh1 Mean 5.5 6 186 35 566 6 198 35 6 9 1915 27 SD 1 .1 10 160 33 404 3 169 40 60 90 3 Lower Bh # Mean 5.6 5 59 17 275 7 36 12 43 1220 32 SD 1 .0 11 52 40 1740 3 52 25 69 309 8 D2 A Mean 6.9 7 69 33 44 18 522 81 43 74 80 SD 1.4 10 42 35 6 6 211 104 36 10 16 E Mean 7.1 1 15 4 11 6 81 6 5 13 20 SD 2 .1 2 5 10 6 1.3 31 7 4 17 2 Bh/Bh1 Mean 6 .0 1 73 3 578 11 346 10 11 1886 33 SD 0.5 1 12 1 244 7 191 4 1 206 21 Lower Bh Mean 6 .0 0 56 2 379 15 44 3 10 1314 56 SD 1.3 0 34 1 224 4 24 1 5.4 325 38 D3 A Mean 7.3 40 1610 558 40 11 3275 387 1233 90 134 SD 0.5 13 202 967 31 9 2844 337 166 29 9 E Mean 8 .0 11 94 42 10 2 202 37 70 12 8 SD 0.3 3 56 32 4 1 130 19 45 6 8 Bh/Bh1 Mean 7.6 27 499 271 448 2 787 347 387 646 9 SD 1 .0 5 93 78 130 1 211 42 57 272 10 Lower Bh Mean 7.3 4 65 8 581 12 121 176 30 1169 25 SD 0.5 1 30 10 107 10 65 94 16 254 14

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40 Table 3 1 Continued Site Horizon Statistics pH WSP TP M1 P M1 Al M1 Fe M1 Ca M1 Mg M3 P M3 Al M3 Fe -----------------------------------------------------mg kg 1 ---------------------------------------------------------------------B1 A Mean 4.9 15 94 24 78 14 732 104 29 103 126 SD 0.3 10 130 19 38 9 323 64 20 91 34 E Mean 4.7 4 54 16 137 10 290 57 20 271 65 SD 0.4 4 42 13 107 7 189 38 14 227 34 Bh/Bh1 Mean 4.4 0 82 9 663 7 111 31 11 1017 25 SD 0.3 0 66 14 476 5 64 14 15 588 19 Lower Bh Mean 4.4 0 43 2 530 4 42 17 5 930 7 SD 0.3 0 33 2 282 2 28 7 4 380 8 B2 A Mean 5.5 20 198 97 75 16 704 85 106 109 130 SD 0.8 17 374 123 32 11 542 87 143 79 77 E Mean 6 .0 5 49 16 24 7 144 19 17 36 34 SD 0.8 6 30 22 26 5 117 19 23 53 32 Bh/Bh1 Mean 5.7 6 153 59 907 31 263 32 62 1116 126 SD 0.7 9 78 77 545 41 262 39 70 534 103 Lower Bh Mean 5.6 1 83 18 836 27 137 24 24 1140 83 SD 0.7 3 51 31 524 38 139 34 34 570 91 B3 A Mean 5.8 17 72 27 37 19 556 124 31 69 119 SD 0.4 11 65 15 12 15 122 63 11 16 51 E Mean 6 .2 1 4 1 10 4 50 6 2 14 9 SD 0.4 2 5 3 8 2 53 8 3 14 6 Bh/Bh1 Mean 5 .1 5 88 46 672 19 136 26 56 802 110 SD 0.4 4 22 33 643 20 53 12 34 580 119 Lower Bh Mean 5 .3 1 31 15 500 9 63 17 19 619 37 SD 0.2 1 26 14 535 4 20 11 13 439 21 WSP, water soluble phosphorus; TP, total phosphorus; M1 P, Al, Fe, Ca and Mg, Mehlich 1 extractable phosphorus, aluminum, iron, calcium and magnesium, re spectively; M3 P, Al and Fe, Mehlich 3 extractable phosphorus, aluminum and iron, respectively. # Horizons include Bh2 and other subjacent horizons to a depth of 1 m.

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41 Table 3 2 Mean and SD by site (D = dairy; B = beef ) and horizon for oxalate extractable P and metals, data used in PSR and SPSC calculations for the soils studied. Site Horizon Statistics Ox P Ox Al Ox Fe Ox Fe + Al PSR ox SPSC SPSC total -----------------mg kg 1 -------------------Moles --------kg ha 1 --------D1 A Mean 14 6 a 92 c 89 a 5 c 0.83 a 297 b SD 192 39 45 2 1.2 0 511 E Mean 19 a 61 c 24 b 2 c 0.14 b 42 ab SD 34 32 34 1 0.21 84 Bh/Bh1 Mean 184 a 3568 a 66 ab 133 a 0.04 b 28 ab SD 114 1048 20 39 0.02 200 Lower Bh # Mean 49 a 1481 b 72 ab 56 b 0 .02 b 286 a SD 60 678 32 34 0.03 210 25 D2 A Mean 54 a 85 b 135 b 6 b 0.31 a 61 b SD 45 6 9 1 0.3 0 76 E Mean 6 b 15 b 33 c 1 b 0.17 ab 8 b SD 4 18 31 1 0.13 14 Bh/Bh1 Mean 70 a 3985 a 245 a 152 a 0.01 b 350 ab SD 12 90 5 260 38 0 .01 9 Lower Bh Mean 38 ab 3317 a 272 a 128 a 0.01 b 1053 a SD 17 2631 166 100 0 .02 1209 1334 D3 A Mean 1300 a 248 bc 394 a 16 bc 2.50a 6206 c SD 424 134 19 5 0.5 0 4255 E Mean 77 c 13 c 9 c 1 c 3.90 a 234 b SD 25 3 1 1 2 .00 43 Bh/Bh1 Mean 488 b 1112 b 17 c 41 b 0.50 b 974 b SD 92 603 11 22 0.4 0 173 Lower Bh Mean 56 c 2059 a 40 b 76 a 0.02 b 156 a SD 35 609 15 23 0.01 93 7258 B1 A Mean 66 a 255 b 245 a 14 b 0.15 a 34 b SD 37 66 96 3 0.07 41 E Mean 42 ab 329 b 84 b 14 b 0.10 b 9 ab SD 29 210 45 7 0.08 93 Bh/Bh1 Mean 57 ab 1417 a 32 c 53 a 0.03 c 19 ab SD 43 996 25 37 0.02 17 Lower Bh Mean 28 b 1013 a 9 c 38 a 0.02 c 47 a SD 24 531 12 20 0.01 44 41

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42 Ta ble 3 2. Continued Site Horizon Statistics Ox P Ox Al Ox Fe Ox Fe + Al PSR ox SPSC SPSC total ---------------mg kg 1 --------------------Moles ----------kg ha 1 ----------B2 A Mean 155 a 212 b 223 a 12 b 0.39 a 270 b SD 136 79 137 5 0.27 304 E Mean 41 b 68 b 38 b 3 b 0.52 a 69 a SD 26 56 37 3 0.26 48 Bh/Bh1 Mean 147 a 1935 a 256 a 76 a 0.12 b 35 a SD 79 1435 273 54 0.12 193 Lower Bh Mean 76 b 1821 a 189 ab 71 a 0.07 b 85 a SD 42 1435 272 54 0.11 279 289 B3 A Mean 63 ab 118 b 167 a 7 b 0.24 a 101 b SD 68 33 122 3 0.2 0 151 E Mean 2 c 53 b 2 c 2 b 0.03 b 15 a SD 2 17 4 1 0.05 8 Bh/Bh1 Mean 80 a 1006 a 121 ab 39 a 0.09 b 12 a SD 27 902 146 32 0.06 43 Lower Bh Mean 28 b 746 ab 36 b 28 ab 0.03 b 33 a SD 22 707 30 26 0.03 42 65 Mean values of soil characteristics within a column followed by the same letter are not significantly different (p < 0.05), u sing the least significant difference procedure. Ox P, Al and Fe, oxalate extractable phosphorus, aluminum and iron, respectively PSR ox P saturation ratio using oxalate extract calculated as molar ratio of P to [Fe + Al]; SPSC, soil phospho rus storage capacity. SPSC for A E and Bh horizons calculated using oxalate ex traction according to e quation ( 3 1 ) with change point PSR of 0.1 and 0.05 respectively. Total SPSC for A, E, Bh and Lower Bh horizon where the soil profile is of 1 m depth. High PSR value indicates that these soils have very low P retention capacity due to excess P loading or lack of metal oxides in the surface horizons. # Horizons include Bh2 and other subjacent horizons to a depth of 1 m.

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43 Table 3 3 Estimated model parameters and statistics (with standard errors in parentheses) *** Significant at the 0.001 probability level. Model Fitted equ ations Model R 2 Oxalate WSP = 0.089 (2.04) + 10.44 (86.85) (0.029) 0.82*** WSP = 4.23 (1.51) + 104.2 (4.33) PSR; PSR >0.05 (0.029) Mehlich 1 WSP = 0.066 (0.877) + 24.21 (42.62) (0.054) 0.88 *** WSP = 4.61 (1.55) + 83.82 (3.01) P SR; PSR >0.08 (0.054) Mehlich 3 WSP = 0.329 (0.679) + 63.20 (24.90) (0.069) 0.93*** WSP = 3.41 (1.43) + 96.50 (2.86) PSR; PSR >0.09 (0.069)

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44 Figure 3 1 L ocation of the study sites

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45 Figure 3 2 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in an oxalate extract (PSR O x ). Threshold PSR O x value (0.05) is significant at the 0.001 probability level. Open squares are soils in the current study; open circles repr esent data from archived soils

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46 Figure 3 3 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in Mehlich 1 extract (PSR M1 ). Threshold PSR M1 value (0.08) is significant at the 0.001 probability level. Open squares are soils in the current study; open circles represent data from archived soils

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47 Figure 3 4 Relationship between water soluble P (WSP) and P saturation ratio (PSR) calculated for the spodic horizon using P, Fe and Al in Mehlich 3 extract (PSR M3 ). Threshold PSR M3 value (0.09) is significant at the 0.001 probability level. Open squares are soils in the current study; open circles repr esent data from archived soils

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48 Fig ure 3 5 Relationship between soil phosphorus storage capacity (SPSC) and Capacity Factor for spodic horizons calculated using Mehlich 1 extractable P, Al and Fe. Open squares are soils in the current study; open circles represent data from archived soils Figure 3 6 Relationship between soil phosphorus storage capacity (SPSC ) and Capacity Factor for spodic horizons calculated using Mehlich 3 extractable P, Fe and Al. Open squares are soils in the current s tudy; open circles represent data from archived soils y = 1.8x 14.6 R = 0.87 n=174 2000 1500 1000 500 0 500 1000 1000 500 0 500 SPSC, mg kg 1 Capacity Factor M1 mg kg 1 y = 1.3x 74.9 R = 0.94 n=174 2000 1500 1000 500 0 500 1000 1000 500 0 500 SPSC, mg kg 1 Capacity Factor M3 mg kg 1

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49 Figure 3 7 Soil phosphorus storage capacity (SPSC) vs. water soluble P (WSP) of A and E horizons (using 0.10 as the change point P saturation ratio) of manure impacted soils. Open and closed marker s represent positive and negative SPSC respectively. The R 2 value is for soils having negative SPSC Figure 3 8 Soil phosphorus storage capacity (SPSC) vs. water soluble P (WSP) of spodic horizons (using 0.05 as the change point P saturation ratio, Fig 3.2). Open and closed markers represent positive and negative SPSC respectively. The R 2 value is for soils having negative SPSC y = 5.9x + 7.61 R 2 = 0.82 P source n=50 400 300 200 100 0 100 200 0 10 20 30 40 50 60 SPSC, mg kg 1 WSP, mg kg 1 P sink n=20 y = 8.5x 37 R 2 = 0.79 P source n=41 800 600 400 200 0 200 400 600 0 20 40 60 80 100 SPSC, mg kg 1 WSP, mg kg 1 P sink n=81

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50 Figure 3 9 Schematic diagram of a soil profile illustrating the movement of P to surface and subsurface water bodies and the effect of water table manipulations when A ) spodic is a P sink (SPSC>0); B ) spodic is a P source (SPSC<0)

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51 C HAPTER 4 COMPOSITIONAL DIFFER ENCES BETWEEN ALAQUO DS AND PALEUDULTS AFFECTING PHOSPHORUS SORPTION DESORPTION BEHAVIOR Alaquods and Paleudult s with sandy A and E horizons occur extensively in the coastal plain of the SE United States. Compositional differences between Alaquod E and Bh, and Paleudult E and Bt horizons are factors affecting subsurface P transport in these soils. The risk of P l oss from Alaquod and Paleudult subsurface horizons is related to the P retention characteristics of the horizons. Knowledge of the P retention characteristics between Alaquod and Paleudult subsurface horizons is still limited. Zhou et al. (1997) compared P sorption desorption characteristics of Bh and Bt horizons using selective chelation to determine the effect of organo metallic materials in Bh samples. This present study expands upon their work with a profile perspective considering paired subsurface E B h and E Bt horizons of Alaquods and Paleudults, respectively. The objective of this chapter was to relate P sorption characteristics to compositional differences in Alaquod and Paleudult subsurface horizons and to evaluate implications for risk of P loss via subsurface flow in these soils. The specific objectives were to : evaluate the differences in metal complexation (organic vs. inorganic) and crystallinity that are related to P retention of Alaquod E and Bh, and Paleudult E and Bt horizons using oxa late, pyrophosphate and CBD extractions and x ray diffraction techniques; compare P sorption and release properties of Bh and Bt horizons and relate them to the equilibrium P concentrations and compositional differences; interpret implications for subsurfa ce movement of P from Alaquod and Paleudult profiles due to excess P application.

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52 Materials and Methods Alaquod profiles from three sites (S1, S2 and S3) and Paleudult profiles from three different sites (S4, S5 and S6) located within Florida (Figure 4 1) were sampled by horizon. Horizons greater than 25 cm thick were subdivided for sampling purposes. Surface horizons were not considered in this study since they constitute a relatively thin part of the soil profile and have minimal contribution for P loss f rom the soil profile. This study focused on subsurface horizons of Alaquod (E and Bh) and Paleudult (E and Bt) soil profiles. A total of 81 samples for Alaquod (E: 33 and Bh: 48) and 99 (E: 35 and Bt: 64) for Paleudult were analyzed for this study. Chemic al Analyses Samples were thoroughly mixed, air dried and passed through a 2 mm sieve before analyses. Soil pH was determined using 1:2 soil to water suspension. Oxalate extractable Fe (Ox Fe) and Al (Ox Al) for soils were determined using 0.1 M oxalic acid + 0.175 M ammonium oxalate solution, equilibrated at a pH of 3.0 (McKeague and Day, 1966). Citrate bicarbonate dithionite (CBD) extractable Fe (CBD Fe) and Al (CBD Al) were determined following the procedure of Mehra and Jackson (1960). Pyrophosphate ext ractable Fe (Pyro Fe) and Al (Pyro Al) for soils were determined using 0.1 M Na pyrophosphate (McKeague, 1967). Iron and Al concentrations in oxalate, CBD and pyrophosphate extractions were determined using inductively coupled argon plasma spectroscopy (Th ermo Jarrel Ash ICAP 61E, Thermo Elemental, Franklin, MA). Total carbon of the air dried samples was determined by an automated combustion procedure using a CNS Analyzer (Carlo Erba, Milan, Italy).

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53 Mineralogical Analysis Samples were saturated with Na to p romote dispersion, washed free of salt, and sieved to remove material > 50m in size. Clay (< 2m) was separated from silt by centrifugation (Soukup et al., 2008). Clay mounts were prepared for x ray diffraction 0.45 m membrane filter mount technique (Harris and White, 2008) by which Mg and K saturated clay suspensions were collected on a filter under suction and transferred to glass slides. The Mg saturated clay was solvated with glycerol prior to the XRD scan. Samples were scanned at 2 controlled x ray diffractometer equipped with stepping motor and graphite crystal monochromator. Phosphorus Sorption Thirty three Bh samples and 45 Bt samples were selected from the soils collected to give a wide r ange of Fe and Al contents for intensive P sorption characterization. Phosphorus sorption isotherms were determined using 2.0 g air dried soil in a 50 mL equilibration tube to which 20 mL of 0.01 M KCl solutions containing 0, 0.1, 1, 5, 10, 25, 50 and 100 mg P L 1 as KH 2 PO 4 were added (Nair et al., 1998). The equ ilibration was carried out in a reciprocating shaker at about 100 excursions min 1 for 24 h at 25 1 C The soil suspension was centrifuged and the supernatant was filtered through a 0.45 Murphy and Riley (1962). A single point P sorption isotherm was also conducted accompanying the batch equilibrium sorption experiment with all the soil samples. T wo gram of soil was equilibrated with 20 mL of KCl solution at saturated P conditions (1000 mg P kg 1 ) for 24 h at 25 1 C. The soil suspension was similarly centrifuged, filtered and analyzed for soluble reactive P. The amount of P sorbed by the soils w as calculated

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54 from the difference between the P concentration in the equilibrium solution and the initial P added to the soil. Phosphorus Desorption The amount o f P sorbed by the soil after 24 h equilibrium represented the starting value for adsorbed P. A fter removing the supernatants, each tube containing a wet soil sample was weighed to estimate the volume of the residual solution and the P entrapped in it. These P saturated soils were then subjected to desorption with 20 mL of 0.01 M KCl (that contained no P) equilibrated in a reciprocating shaker for 24 h (Dunne et al., 2006). Phosphorus in the extracts was analyzed as mentioned above. Calculations Adsorption parameters were calculated using the Langmuir adsorption equation: ( 4 1 ) w here o the total amount of P sorbed, mg kg 1 1 S o = originally sorbed P on the solid phase, mg kg 1 C= concentration of P after 24 h equilibration, mg L 1 S max = P sorption maximum, mg kg 1 k= a constant related to the bonding energy, L mg 1 P. Initially sorbed P (S o ) was estimated using the least square fit method which is based o n the linear relationship between S' and C at low equilibrium P concentrations. The relationship can be described by ( 4 2 )

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55 where K' = the linear adsorption coefficient, and all other parameters are as defined earlier (Graetz and Nair, 1995). 0 ) represents the concentration of P in solution where adsorption equals desorption and was the value of C when S' = 0 ( Nair et al., 1998). Maximum buffering capacity (MBC) of soils is the index of soil resistance to the change of P concentration in soil solution with the addition or removal of P (Sui and Thompson, 2000). From the sorption parameters S max and k, MBC of soils were determined as MBC = S max k (Holford, 1979). The value of M BC is the slope of the isotherm as and dictate s the steepness of isotherm at low concentrations (Zhang et al., 2009). Statistical Analyses Empirical relationships between P sorption parameters and soil properties were assessed using correlation and regression analyses in Excel 2007. T he data was analyzed using the General Linear Model procedure in the statistical package SAS (SAS Institute, 2001). Differences between means of soil parameters for soil groups were compared using Fishers LSD. Results and D iscussion Soil Characterization S oil pH values ranged from 4.4 to 6.5. Noncrystalline Al content was much higher in Bh than in other horizons as inferred from oxalate extraction (Table 4 1; Figure 4 2). Among all the horizons studied, E horizons of Alaquods had lowest Al concentration. Th e E and Bt horizons of Paleudults were intermediate in Al content, with Bt being significantly higher in Al than the E. The E horizons of Paleudults have significantly greater Fe and Al oxide content than Alaquod E horizons. For Paleudults, CBD Fe was hi ghly correlated to CBD Al for E (R 2 = 0.698, p <0.001) and Bt (R 2 =0.719, p<0.001)

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56 horizons. These results suggest that the source of CBD Al in E and Bt horizons of Paleudults is mainly the Al which is substituted for Fe in the Fe oxides. Values for CBD Al we re generally lower than Ox Al, but trends among horizons were essentially identical. For Paleudults, CBD Fe is significantly higher than Ox Fe ( p < 0.0001). T he ratio of mean Ox Fe and CBD Fe for E and Bt horizons of Paleudults are 0.49 and 0.07 respective ly. These ratios suggest the dominance of crystalline Fe oxides in Bt horizons. Pyrophosphate has been shown to be most effective in extracting organically bound Al and Fe (McKeague et al., 1971), though it can extract some noncrystalline inorganically co mplexed forms of these metals as well (Kaiser and Zech, 1996). Oxalate and pyrophosphate extractable Fe and Al, show a 1:1 relationship for Bh horizons where Fe and Al is predominantly complexe d with organic matter (Figure 4 3 ). For Bt horizons, oxalate is more efficient as an extractant than pyrophosphate, which is consistent with low C content (Table 4 1) and predominance of inorganic Fe and Al oxides. Carbon content is strongly related to oxalate extractable Al for Bh horizons, b ut n ot for other horizon s (Figure 4 4). No significant relation was obtained between C content and extractable Fe for any of the horizons. For Bh samples the metal/C ratios were <0.10, consistent with the conclusion of Higashi et al. (1981) that soil organic matter can bind Fe an d Al at metal/C ratio up to 0.12. Phosphorus Sorption and Desorption Phosphorus sorption capacity (P sorp ) determined from single point isotherms (1000 mg P kg 1 ) show that none of the E horizons of Alaquods has measurable P retentive capacity (Table 4 2) Harris et al. (1996) suggested that lack of aluminosilicate and

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57 metal oxide clay in the albic E horizons which is mainly dominated by clean quartz grains accounts for its low P retention capacity. However, the E horizons of Paleudults sorb considerable a mount of P which is consistent with the finding of Rhue et al. (2006). These horizons are expected to retain more P due to presence of sand grain coatings (Harris et al., 1996). These coatings typically contain minerals (kaolinite, HIV, gibbsite, Fe oxyhyd roxides, etc) with much greater surface area and P retention capacity than quartz sand (Harris et al., 1989). Quartz dominated the clay fraction of E horizons of Alaquods whereas E horizons of Paleudults have quartz and kaolinite in the clay fraction (Figu res 4 5 and 4 6). Bh and Bt horizons have high P retention capacity as indicated by P sorp (Table 4 2). The P sorp values ranged from 137 to 846 mg kg 1 for Bh horizons and from 119 to 897 mg kg 1 for Bt horizons. These P sorption trends are consistent with those reported by Harris et al. (1996) and Zhou et al. (1997). For Bh and Bt samples, P sorption behavior was further described by the Langmuir isotherm (Table 4 3). Mean values of Langmuir sorption maxima (S max ) for the Bh and Bt horizons are 353 and 514 mg kg 1 respectively. The clay fractions of Florida Alaquod Bh horizons are typically dominated by quartz, HIV and kaolinite (Harris and Carlisle, 1987), as was the case for the Bh of the representat ive Alaquod of this study (Figure 4 5). Particle size dis tribution was not determined for Bh horizons of this study but they were sands by field textural assessment. The clay fractions of Florida Paleudult Bt horizons are typically dominated by kaolinite (Harris et al., 1989), as was the case for the Bt of the r epresentati ve Pa leudult of this study (Figure 4 6). Phosphorus sorption capacity (P sorp ) follows a 1:1 relationship with the S max values for Bh (R 2 = 0.978, p<0.001) and Bt (R 2 =0.982, p<0.001) horizons. Total C content was related to S max

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58 (R 2 =0.62) for Bh b ut not for Bt (R 2 =0.12) samples. The equilibrium P concentration (EPC 0 ) of Bh samples were high er than the Bt samples. Low EPC 0 values for most of the Bt horizon in this study suggest that these horizons have not yet been significantly impacted by P enrich ment and can act as sinks for P moving from overlying horizons. The mean values of the initially sorbed P, S o for Bh and Bt horizons were 3.4 and 0.24 mg kg 1 respectively. Langmuir constant k, was low for Bh samples in comparison to Bt (Table 4 3). Max imum buffering capacity (MBC) was high for high P sorbing samples. MBC will have a greater tendency to maintain the original aqueous P concentration during the inflow of higher P concentrations (Zhang et al., 2009). The proportion of P desorbed from Bh horizons were greater in comparison to Bt horizons (Table 4 3; Figure 4 7) corroborating results of Zhou et al. (1997). P desorbed expressed as a fraction of sorbed P (DEF) ranges from 2 to 57 % with a mean of 19 % for Bh horizons whereas for Bt horizons it ranges from 1 to 10 % with a mean of 5 %. Disparity in desorption is likely attributable to a) greater amounts of Fe oxides and other clay sized minerals in Bt compared to Bh, as documented by Florida soil characterization data ( http://flsoils.ifas.ufl.edu/); b) organic vs. inorganic metal complexation in Bh vs. Bt as indicated by s trong Al C relation for Bh (Figure 4 4); c) we aker bonding of P with organically complexed Al in Bh horizons as indicated by low Langmuir k. Only Bh samples with the highest oxalate extractable Al showed high resistance to P desorption (Figure 4 8). Correlation of Phosphorus Sorption Parameters with Soil Properties The P sorption maxima obtained from the Langmuir equation, S max correlated well with all forms of Al for Bh (Table 4 4) and Bt (Table 4 5) horizons. The positive

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59 correlations of S max with all forms of Al (Ox Al, CBD Al and Pyro Al) (Tabl e 4 4) but not with Fe in Bh confirms the importance of Al for P retention in these horizons. For Bt horizons, S max was significantly correlated with CBD Fe (r=0.474, p<0.01) but not with any other forms of Fe (Ox Fe or Pyro Fe) (Table 4 5). Clay content a nd S max were related for Bt samples (R 2 = 0.70). This implies that, for Bt samples inorganic metal oxides along with phyllosilicates, predominantly kaolinite contribute to P sorption. Langmuir sorption maxima S max negatively correlated with pH for both Bh a nd Bt horizons. This may be due to the fact that with increasing pH, mineral surfaces become increasingly negative resulting in greater electrostatic repulsion and decrease in P sorption (Haynes, 1982; Oh et al., 1999; Sato and Comerford, 2005). Total C co rrelated significantly with the Langmuir sorption parameters for Bh but not for Bt samples. Positive relationship between C content of spodic horizons and P sorption had also been observed by Nair et al. (1998). This relationship was due to the indirect ef fect of C through complex formation with cations such as Fe and Al associated with organic matter. Phosphorus bonding constant (k) and MBC were positively correlated with all forms of Al and Fe for Bh horizons and with all forms of Al, along with CBD Fe fo r Bt horizons. St rong relationship between k and MBC was obtained for Bh (R 2 = 0.87) and Bt (R 2 =0.94) samples. A negative correlation of k with S o for Bh horizons (r= 0.663, p<0.001) is consistent with the theory that the more saturated the sorption complex is, the lower the energy of subsequent sorption (Villapando and Graetz, 2001). Positive correlation between EPC 0 and S 0 was obtained for both Bh and Bt horizons. Equilibrium

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60 P concentration EPC 0 was negatively correlated with all forms of Al for Bh horizo ns and with Ox Al for Bt horizons. P desorbed expressed as a fraction of sorbed P (DEF) was negatively correlated to all forms of Al for Bh. For Bt, DEF was not correlated with any form of Al (Table 4 5) but was negatively correlated with oxalate Fe; we e xpected negative correlation with DEF for both Fe and Al and have no explanation for these results. Positive correlation of DEF with S o for Bh horizons (r=0.432, p<0.05) suggests increased desorbability of newly sorbed P by the soils in the presence of P o riginally sorbed on the solid phase (Villapando and Graetz, 2001). Environmental Implications The environmental risk of P loss is related to the compositional difference of horizons within the soil profile. Since E horizons of Alaquods have negligible P re tentive capacity, they do not significantly retard the movement of agricultural P to Bh horizons or to streams and ditches v ia sh allow subsurface flow (Figure 4 9A ) as was suggested by Nair et al. (1995). Thus Bh horizons may easily get saturated with P du ring dry seasons when water tables are below their upper boundaries. These P enriched Bh horizons can subsequently release P at environmentally hazardous rates when water tables reach seasonally high levels, further fostering lateral P mo ve ment to surface water (Figure 4 9B ). On the other hand, in Paleudult soil profiles, the E horizons can retain relatively large amounts of P, retarding its vertical tran sport to the Bt horizon (Figu re 4 9C ). Lateral subsurface P transport would also be retarded by the rete ntive E horizons of Paleudults though shallow subsurface water flow is less of a factor with Paleudults relative to Alaquods due to better drainage of the former. Also the risk of P release is less for Bt than Bh due to greater resistance to P desorption These

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61 pedological, compositional, and hydrologic distinctions between Paleudults and Alaquods result in there being a greater risk of P loss for the latter under comparable P loadings. Summary Sandy Bh horizons have high P adsorption capacity due to t he predominance of organically complexed metals, mainly Al. However, Bh horizons are more susceptible to P loss from excess P loading because of a greater tendency to desorb P relative to Bt horizons. The greater desorption potential of Bh horizons likely relates to weaker bonding of P with organically complexed Al as inferred from low Langmuir k. Phosphorus sorption in Bt horizons is influenced by noncrystalline inorganic metal oxides along with crystalline Fe and phyllosilicates, predominantly kaolinite. Difference in crystalline and noncrystalline inorganic component between Bh and Bt horizons contributes significantly for the difference in P sorption desorption behavior of these horizons. Compositional differences between Alaquod and Paleudult subsurfac e horizons, in conjunction with pedological and hydrologic distinctions between these Great Groups, result in greater environmental risk of P loss for Alaquods under equal P loadings.

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62 Table 4 1 Mean and SD by site and horizon for chemical properties of s oils studied Great Group Site Horizon n Statistics pH Total C Ox Fe Ox Al CBD Fe CBD Al Pyro Fe Pyro Al % --------------------------------------mg kg 1 ---------------------------Alaquod S1 E 12 mean 5.8a 0.27 b 29 a 64 a 24 a 40 a ---# ---SD (0.7) (0.29) (37) (60) (28) (43) ------Bh 16 mean 5.5a 1.6 a 217 b 2575 b 226 b 1597 b 204 2382 SD (0.6) (1.0) (364) (1650) (341) (959) (302) (1372) S2 E 8 mean 5.9a 0.06 b 3 a 48 a 2 a 28 a ------SD (0.4) (0.08) (5) (24) (4) (5) ------Bh 11 mean 4.9a 0.54 a 112 b 930 b 101 b 733 b 99 888 SD (0.3) (0.42) (93) (770) (89) (71) (56) (773) S3 E 13 mean 5.6a 0.01 b 3 a 46 a 4 a 20 a ------SD (0.1) (0.01) (8) (7) (7) (8) ------Bh 21 mean 5.7a 1. 1 a 67 b 1095 b 72 b 847 b 61 1117 SD (0.1) (0.38) (113) (437) (106) (243) (110) (533) Paleudult S4 E 8 mean 5.7a 0.12 a 241 a 446 a 437 a 325 a ------SD (0.3) (0.01) (89) (113) (473) (134) ------Bt 30 mean 4.7a 0.09 b 270 a 948 b 364 1 b 615 b 95 533 SD (0.5) (0.04) (99) (250) (2991) (244) (134) (147) S5 E 17 mean 4.9a 0.09 a 232 a 305 a 516 a 232 a ------SD (0.5) (0.05) (88) (169) (1553) (161) ------Bt 21 mean 4.5a 0.05 b 291 a 828 b 6759 b 737 b 194 600 S D (0.4) (0.03) (123) (471) (4785) (372) (208) (405) S6 E 10 mean 6.4a 0.08 a 105 a 120 a 354 a 83 a ------SD (0.7) (0.06) (54) (75) (236) (41) ------Bt 13 mean 5.9a 0.05 a 223 b 447 b 1306 b 276 b 102 246 SD (0.6) (0.02) (162) (102) (491) (71) (94) (31) Ox Fe and Al, oxalate extractable iron and aluminum, respectively; CBD Fe and Al, citrate bicarbonate dithionite extractable iron and aluminum respectively; Pyro Fe and Al, pyrophosphate extractable iron and aluminum respectively M ean values of soil characteristics within a column followed by the same letter are not significantly different (p < 0.05), using LSD # Pyrophosphate extraction was not performed for the E horizons of Alquod and Paleudult, since pyrophosphate extracts organ ically complexed Fe and Al which is expected to be negligible for these horizons.

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63 Table 4 2 Mean and standard deviation (SD) by sites and horizons of P sorption capacity (P sorp ), determined using single point (1000 mg P kg 1 ) isotherm Great Group Site Horizon n P sorp SD mg kg 1 Alaquod S1 E 12 ---# ---Bh 16 570 235 S2 E 8 ------Bh 11 116 13 S3 E 13 ------Bh 21 260 109 Paleudult S4 E 8 53 39 Bt 30 675 186 S5 E 17 124 108 Bt 21 569 227 S6 E 10 58 54 Bt 13 276 60 # No P sorption values could be obtained for the E horizons of Alaquod since they have no P retentive capacity, thus these values were either zero or negative for these soils.

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64 Table 4 3 Phosphorus sorption and desorption parameters for Bh and Bt ho rizons Site n Horizon Statistics S max S o EPC 0 k MBC DEF -----mg kg 1 -----mg L 1 L mg 1 L kg 1 % S1 10 Bh Mean 603 2.33 0.66 0.41 247 10 SD 277 5.16 1.80 0.24 219 6 S2 8 Bh Mean 151 2.08 2.09 0.04 6 16 SD 8 4.61 2.01 0.03 4 1 S3 15 Bh Mean 306 5.60 0.98 0.10 31 30 SD 141 3.11 0.62 0.07 16 16 S4 25 Bt Mean 688 0.58 0.22 1.04 716 6 SD 177 1.26 0.38 0.88 835 2 S5 10 Bt Mean 562 0.01 0.15 1.30 734 5 SD 264 0.02 0.21 0.77 688 2 S6 10 Bt Mean 295 0.12 0.40 0.92 270 3 SD 90 0.04 0.18 0.51 127 2 S max P sorption maximum; S o P originally present in the solid phase; EPC 0 equilibrium phosphorus concentration; k, P bonding constant; MBC, maximum buffering capacity; DEF, P desorbed expressed as a fraction of sorbed P.

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65 Table 4 4 Correlation of sorption parameters with selected soil variables for Bh samples studied (n=33 ) *Significant at the 0.05 probability level. **Significant at the 0.01 probability level. ***Significant at the 0.001 probability level. CBD is citrate bicarbonate dithionite; Ox is oxalate; Pyro is pyrophosphate; S max P sorption maximum; S o P originally present in the solid phase; EPC 0 equilibrium phosphorus concentration; k, P bonding constant; MBC, maximum buffering capacity; DEF, P desorbed expressed as a fraction of sorbed P. S max EPC 0 MBC k DEF CBD Fe + Al 0.912*** 0.525** 0.872*** 0.764*** 0.568*** CBD Fe 0.13 0.093 0.411* 0.537** 0.105 CBD Al 0.947*** 0.543 *** 0.862*** 0.730*** 0.591*** Ox Fe+Al 0.936*** 0.534** 0.870*** 0.746*** 0.573*** Ox Fe 0.091 0.059 0.394* 0.518** 0.069 Ox Al 0.955*** 0.544*** 0.858*** 0.718*** 0.586*** Pyro Fe+Al 0.935*** 0.573*** 0.852*** 0.741*** 0.637*** Pyro Fe 0.21 0.163 0.495** 0.611*** 0.178 Pyro Al 0.952*** 0.579*** 0.837*** 0.711*** 0.645*** pH 0.481** 0.374* 0.482** 0.470** 0.390* S o 0.619*** 0.895*** 0.611*** 0.658*** 0.432* Total C 0.743*** 0.480** 0.778*** 0.655*** 0.354*

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66 Table 4 5 Correlation of sorption parameters with selected soil variables for Bt sampl es studied (n= 45 ) *Significant at the 0.05 probability level. **Significant at the 0.01 probability level.***Significant at the 0.001 probability level. CBD is citrate bicarbonate dithionite; O x is oxalate; Pyro is pyrophosphate ; S max P sorption maximum; S o P originally present in the solid phase; EPC 0 equilibrium phosphorus concentration; k, P bonding constant; MBC, maximum buffering capacity; DEF, P desorbed expressed as a fraction of sorbe d P. S max EPC 0 MBC k DEF CBD Fe + Al 0.492 *** 0.236 0.404** 0.358* 0.127 CBD Fe 0.474** 0.222 0.371* 0.328* 0.126 CBD Al 0.557*** 0.302 0.576*** 0.516*** 0.12 Ox Fe+Al 0.822*** 0.482*** 0.725*** 0.604*** 0.059 Ox Fe 0.211 0.0 73 0.12 0.05 0.456** Ox Al 0.835*** 0.455** 0.725*** 0.595*** 0.037 Pyro Fe+Al 0.441** 0.28 0.419** 0.383* 0.051 Pyro Fe 0.203 0.018 0.231 0.14 0.234 Pyro Al 0.551*** 0.295 0.540*** 0.466 ** 0.031 pH 0.500*** 0.19 0.323* 0.328* 0.115 So 0.408** 0.453** 0.218 0.267 0.267 Total C 0.246 0.115 0.127 0.016 0.112

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67 Figure 4 1. Location of the study sites

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68 (A ) (B ) Mean values for a given component within the horizons with the same letter are not significantly different (p< 0.05), using t he least significant difference procedure. Figure 4 2. Comparison of A) oxalate extractable Al; B) CBD extracta ble Al; C ) o xalate extractable Fe; D ) CBD extractable Fe for E and Bh horizons of Alaquods and E and Bt horizons of Paleudults 0 20 40 60 80 Horizons Ox Al ( mmol kg 1 ) E of Alaquod Bh of Aalquod E of Paleudult Bt of Paleudult c a b c 0 20 40 60 80 Horizons CBD Al ( mmol kg 1 ) E of Alaquod Bh of Alaquod E of Paleudult Bt of Paleudult c c a b

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69 (C ) (D ) Figure 4 2 Continued. 0 1 2 3 4 5 6 Horizons Ox Fe ( mmol kg 1 ) E of Alaquod Bh of Alaquod E of Paleudult Bt of Paleudult c a ab b 0 20 40 60 80 100 Horizons CBD Fe ( mmol kg 1 ) E of Alaquod Bh of Alaquod E of Paleudult Bt of Paleudult a b b c

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70 Figure 4 3 Relationship between oxalate extractable Fe and Al, Ox Fe+Al and pyrophosphate extractable Fe and Al, Pyro Fe+Al for Bh and Bt horizons y = 1.08x R = 0.95 Bh y = 1.71x R = 0.62 Bt 0 50 100 150 200 250 0 50 100 150 200 Ox Fe+Al ( mmol kg 1 ) Pyro Fe+Al ( mmol kg 1 ) Bh Bt

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71 (A) (B ) Figure 4 4 Relationship between total carbon a nd oxalate extractable Al for A) E of Alaquods B) Bh of Alaquods C ) E of Pale udults and D ) Bt of Pale udults 0.00 0.05 0.10 0.15 0.20 0.25 0 50 100 150 Total carbon (%) Ox Al (mg kg 1 ) y = 0.6126ln(x) 3.28 R = 0.72 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 1500 3000 4500 6000 Total carbon (%) Ox Al (mg kg 1 )

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72 (C ) (D ) Figure 4 4 Continued 0.00 0.03 0.06 0.09 0.12 0.15 0 250 500 750 Total Carbon (%) Ox Al (mg kg 1 ) y = 323.18ln(x) + 1754 R = 0.35 0.00 0.04 0.08 0.12 0.16 0.20 0 500 1000 1500 2000 Total carbon (%) Ox Al (mg kg 1 )

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73 Figure 4 5 X ray diffraction analysis of clay fraction for the Alaquod profile. The mi nerals identified are as follows: G: Gibbsite; HIV: hydroxy interlayered vermiculi te; K: kaolinite and Q: quartz Figure 4 6 X ray diffraction analysis of clay fraction for the Paleudult profile. The minerals identified are a s follows: HIV: hydroxy interlayered vermiculite; K: kaolinite and Q: quartz HIV K K Q HIV K K G Q

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74 Figure 4 7 Relationship between P sorbed (mg kg 1 ) versus P desorbed expressed as a fraction of sorbed P, DEF (%) for Bh and Bt horizons Figure 4 8 Relationship between oxala te extractable Al, Ox Al (mmol kg 1 ) and P desorbed expressed as a fraction of so rbed P, DEF (%) for Bh horizons 0 200 400 600 800 1000 1200 0 10 20 30 40 50 60 P Sorbed (mg kg 1 ) DEF (%) Bh Bt 0 40 80 120 160 200 0 10 20 30 40 50 60 Ox Al (mmol kg 1 ) DEF (%)

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75 Figure 4 9 Schematic diagram depicting seasonal scenarios of water and P movement trends in Alaquod (A and B) and Paleudult (C ) soil profiles under comparable P loadings based on horizon and soil compositional differences documented in this study. Relative P concentrations are depicted by thickness of the line with arrow (higher for thicker line). Thickness of line depicti ng concentrat ion is arbitrary. A ) Alaquod profile with water table a t a seasonal low level (SLWT); B ) Alaquod profile with water table at a seasonally high level (SHWT); C ) Paleudult profile with water table at a seasonally high level (SHWT). These trends depict differ ences in P loss potential between Alaquods and Paleudults as wel l as seasonally for Alaquods

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76 CHAPTER 5 A COMPARISON OF P DY NAMICS BETWEEN ALAQU ODS AND PALEUDULTS: IMPLICATIONS FOR ENV IRONMENTAL RISKS AND PHYTOREMEDIATION Chapter 4 dealt with the comp ositional difference between Alaquods and Paleudults subsurface horizons. Compositional differences between subsurface horizons of Alaquods and Paleudults result in different P sorption behavior and P loss risks with excess P application. Understanding the ease with which P is released from different soils might help better assess the soils that are potentially vulnerable to P loss to nearby water body. The PSR and SPSC concepts which were used to determine environmental risk of P loss have mainly been appl ied to sandy soils; the re was a need to verify its applicability to finer textured horizons (Bt) in coastal plain soils. Plant P availability as determined from iron oxide impregnated filter paper (FeO P) may be used as an implication of plant based clean up strategy (phytoremediation) for high P loaded soils. The objective of this chapter was to relate environmental P loss risk assessed by PSR and SPSC to the compositional difference between Alaquod and Paleudult subsurface horizons. The specific objecti ves were to : compare P release behavior of Alaquod and Paleudult subsurface horizons using PSR and SPSC ; determine the effectiveness of SPSC as an alternative of EPC 0 for predicting the risk of P loss; test the applic ability of SPSC in clayey or loamy (Bt ) horizons ; evaluate the potential for phytoremediation to remove subsurface P.

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77 Materials and Methods Soil Sampling Alaquod profiles from three sites (S1, S2 and S3) and Paleudult profiles from three different sites (S4, S5 and S6) located within Florida p resented in Figure 4 1 were used for this study. As stated before, s urface horizons were not considered in this study since they constitute a relatively thin part of the soil profile and have minimal contribution for P loss from the soil profile. The total numbers of soil samples analyzed in this study were 90 (E: 34 and Bh: 56) for Alaquods and 101(E: 34 and Bt: 67) for Paleudults. Soil Characterization Samples were thoroughly mixed, air dried and passed through a 2 mm sieve before analyses. Soil pH was d etermined using 1:2 soil and water suspension. Mehlich 1 extractable P (M1 P), Fe (M1 Fe) and Al (M1 Al) were obtained by extracting soil w ith a double acid solution (0.05 M HCl + 0.0125 M H 2 SO 4 ) at a 1:4 soil to solution ratio (Mehlich, 1953). Mehlich 3 extractions for determination of P (M3 P), Fe (M3 Fe), and Al (M3 Al) were obtained by extracting with 0.2 M CH 3 COOH + 0.25 M NH 4 NO 3 + 0.015 M NH 4 F + 0.13 M HNO 3 + 0.001 M EDTA at a 1:8 soil to solution ratio (Mehlich, 1984). Oxalate extractable P (Ox P), Fe (Ox Fe), and Al (Ox Al) were determined for soils using a 0.1 M oxalic acid + 0.175 M ammonium oxalate solution, equilibrated at a pH of 3.0 (McKeague and Day, 1966). All metals and P in M1, M3 and Ox solution were determined by inductively coupled argo n plasma spectroscopy (Thermo Jarrel Ash ICAP 61E, Thermo Elemental, Franklin, MA). Plant available P: Whatman 50 filter papers were immersed in 0.65 M FeCl 3 solution overnight. They were then air dried and immersed in 2.7 M NH 4 OH f or 30 s ; rinsed a nd kep t in DDI water for 1 h (Myers et al., 1997). The filter paper can then be

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78 used immediately or dried and stored for future use. The filter paper is then placed into mesh screen and sealed with a plastic clamp. In 4 oz glass bottle 5g of soil an d 30 mL of DI water was added. The mesh screen was inserted with enclosed filter paper so that it does not move during shaking (Figure 5 1) The bottle was then capped. It was then shaken for 16 h At the end of the shaking, each paper was removed from the screens. It was then rinsed with DI water Phosphorus extracted from iron oxide impregnated filter paper (FeO P) by adding 50 mL of 0.2 M H 2 SO 4 in 125 mL Erlenmey er flasks and shaking for 1 h Water soluble P (WSP) was determined using 1:10 soil to water ratio. The ex traction was done by shaking 2 g soil with 20 mL of d ouble deionized water for 1 h ignition method (Anderson, 1976). Water soluble P, FeO P and TP concentrations were determined using an autoanalyzer (USEPA, 1983; Method 365 1) by the Murphy and Riley (1 962) procedure. Sorption and desorption parameters for 33 Bh and 45 Bt samples (selected based on Fe and Al content ) were obtained from the results as presented in chapter 4 (Table 4 3). Determination of Observed and P redicted SPSC Predicted soil P storag e capacity (SPSC predicted ) was determined using 2 g of air dry soil in 50 mL centrifuge tubes to which 30 mL of P having different concentrations (0, 5, 10, 15, 20, 30, 40 and 60 mg P L 1 as KH 2 PO 4 ) were added. The tubes were then placed on a reciprocating shaker for a 24 h equilibration period. At the end of the period, the soil sampl es were allowed to settle for 1 h the supernatant filtered through a 450 nm membrane filter, and the filtrate analyzed for soluble reactive P. Difference between

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79 the P concen tration in the equilibrium solution and the initial P added to the soil is the amount of P sorbed by the soils. After removing the supernatants, each tube containing a wet soil sample was weighed to estimate the volume of the residual soluti on and the P e ntrapped in it. Twenty mL DI water was then added to the cent rifuge tubes, shaken for 1 h filtered and analyzed for WSP. From the relationship between WSP and the amount of P sorbed, SPSC predicted is determined corresponding to the point at which WSP incr eases significantly with incre ase in P sorption. The observed SPSC (SPSC observed ) for the soils were obtained using equation ( 5 3 ) Calculations PSR and SPSC of the soils were calculated based on oxalate extractions because oxalate extracts most of the re active Al and Fe present in the soil and represents its P sorption capacity (Kleinman et al., 2003). PSR = ( 5 1 ) Soil P storage capacity for E horizons of Alaquods were calculated based on threshold PSR of 0.1 as obtained from Nair et al. (2004). ( 5 2 ) where Soil PSR O x is for the specific soil based on which SPSC is calculated Soil P storage c apacity for Bh horizons of Alaquods and E and B t horizons of Paleudults were calculated as: ( 5 3 ) where Threshold PSR Ox for Bh horizons of Alaquods and E and Bt horizons of Paleudults were determined statis tically using NLIN procedure.

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80 The P, Fe and Al in equations ( 5 1 ) to ( 5 3 ) are expressed in moles. The SPSC in equations ( 5 2 ) and ( 5 3 ) are expressed in mg kg 1 Statistical Analyses Empirical relationships between soil parameters were performed using c orrelation and regression analyses in Excel 2007. Computations for the change point or threshold PSR were done using the Statistical Analysis System (SAS Institute, 2001) using a NLIN procedure, similar to the one adopted in a previous study (Nair et al., 2004). Results and D iscussion Soil Characterization Soil pH values were acidic for both Alaquod and Paleudult subsurface horizons (Table 5 1). Extraction efficiency of P follows the order: Oxalate P> M3 P> M1 P> FeO P>WSP (Table s 5 1 and 5 2) There is an increasing concern that the use of agronomic soil P tests such as, M1 and M3 for environmental purposes may not be appropriate. For instance, Sharpley et al. (2004) observed at high soil P levels, M3 P extracts some P which may not be immediately released from manured surface soil to overland flow. Potential release of P in runoff may be better estimated by extracting soil with water than other traditional soil tests (Hooda et al., 2000). Water soluble P measures the amount of P that will be released from the soil when it is in contact with water from sources like rain or irrigation. Water soluble P in this study ranged from 0.10 to 35 mg kg 1 for Alaquods and from 0 to 39 mg kg 1 for Paleudults subsurface horizons. Phosphorus extracted by iron oxide impreg nated filter paper (FeO P) was strongly related to WSP as obtained using a 1:10 soil:water ratio, for both E and Bh horizons of Alaquods (R 2 = 0.74) and E and Bt horizons of Paleudults (R 2 = 0.93) and is almost twice in magn itude to that of WSP (Figures 5 2 and 5 3 ). However FeO P provides a

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81 better estimate of plant P availability in comparison to WSP since the quantity of P extracted by water is too low and it does not simulates the adsorption mechanism prevalent in natural soil system (Menon et al., 1989 ; Myers et al., 1997 ). Environmental Risk of P R elease Environmental risk of P loss from Alaquods and Paleud ults subsurface horizons can be eva luated from PSR and SPSC The lower threshold PSR for Bh (0.05) relative to Bt (0.12) (Figures 5 4 and 5 5) likely relates to differences in soil components that affect P sorption. As observed in the previous chapter, P sorption in Bt horizons is largely controlled by noncrystalline metal oxides, crystalline Fe oxides and phyllosilicates (mainly kaolinite) which have more tenacious binding with P in comparison to organo metallic complexes that dominate Bh horizon s E horizons of Paleudult, which have appreciable P retentive capacity due to the presence of metal oxides, have a threshold value similar to th e Bt horizons. Relationship of WSP with PSR indicates that WSP is minimal below the threshold PSR and increases rapidly once the threshold PSR is crossed for both Alaquod and Paleudult profile and thus may be of environmental concern. Considerable numbers of E samples a nd majority of the Bt samples of Paleudult profiles studied have PSR below the threshold value. In contrast, an appreciable number of Bh samples had PSR greater than the threshold and thus would act as a potential source of P. Low WSP of the E horizons of Alaquods is due to the low P retentive capacity associated with the horizon as observed in the previous chapter. Phosphorus extracted from iron oxide impregnated filter paper, FeO P, increases considerably when PSR is greater than the threshold value for A laquod and Paleudult subsurface horizons and follows the same tre nd as WSP/PSR relationship (Figure s 5 4 and 5 5 ).

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82 Relationships between SPSC and WSP for Alaquod and Paleudult subsurface horizons show that as long as SPSC is positive, WSP is at a minimum; but when SPSC is negative, the release of P from the soil increases linearly (Figure s 5 6 and 5 7 ). Majority of the Bt samples have positive SPSC and hence they likely would act as P sink. Also, the appreciable P retention capacity of Paleudult E horizons further reduces the susceptibility of underlying Bt horizons to become loaded above the PSR threshold. On the other hand, the negligible P retentive capacity of Alaquod E horizons results in minimal retardation of P transport to underlying Bh horizons. Th us Bh horizons are susceptible to excess P loading and may act as a P source. Plant P availability as inferred from FeO P was propo rtion al to negative SPSC (Figures 5 8 5 9 and 5 10 ) but was consistently minimal as long as SPSC was positive. The relations hip between SPSC and FeO P suggests that considerable amount of P is available for plant uptake from subsurface horizons of Alaquods and E horizons of Paleudults The value of the s lope of the equation s describing plant P availability in figures 5 8 and 5 9 are same indicating that irrespective of the compositional difference s between subsurface horizons of Alaquods and Paleudults, plant P availability fro m both the profiles will be identical For Bh and Bt horizons P loss risk was also evaluated from EPC 0 The mean values of EPC 0 for Bh and Bt samples were 1.3 and 0.3 mg L 1 respectively. Soils exhibit their maximum buffer capacity (MBC) up to the P concentration corresponding to EPC 0 (Bridgham et al., 2001). The MBC value ranges from 3 to 625 L kg 1 for Bh and from 59 to 1667 L kg 1 for Bt. MBC of soils may be defined as the measurement of soil resistance to the change of P concentration in soil solution with the addition or removal

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83 of P (Sui and Thompson, 2000). Most of the Bt samples have high MBC as sho wn in Tabl e 4 3. Relationship between EPC 0 with SPS C (Figure 5 1 1 ) showed that as long as SPSC is positive (PSR is below the change point) the EPC 0 value is low; whereas the value increases considerably when SPSC is negative. This indicates the effectivene ss of SPSC for predicting the risk of P loss from soils. High EPC 0 values are mainly associated with samples with low Ox Al and high P loading. When the relationship between SPSC and EPC 0 is verified, EPC 0 values may be predicted from P, Fe and Al data. De termination of SPSC of any soil is much easier than determination of EPC 0 Thus the environmental risk of P loss from any soil horizon may be easily calculated using the concept of SPSC. Effectiveness of SPSC in Loamy to Clayey Soil H orizons Phosphorus st orage capacity for 9 Bt samples were thoroughly studied by determining experimentally the actual SPSC (SPSC predicted ) for each sample. A 1:1 relationship between SPSC observed and SPSC predicted was observed with a strong R 2 of 0.86 (Figure 5 1 2 ). Thus the e nvironmental risk of P loss may be predicted from SPSC for loamy to clayey Bt horizons as well as for sandy eluvial horizons of coastal plain soils. These results indicate that although crystalline Fe oxides along with phyllosilicates play a dominant role for P retention in Bt samples, the noncrystalline metal oxides extracted by oxalate are the components that bind P most tenaciously and that control sorption below the PSR threshold. Relationship of PSR and P fraction desorbed indicates two different slope s below and above the thr eshold PSR for Bh horizons (Figure 5 1 3 ). This may be due to the fact that in Bh samples P retention is predominantly controlled by organo metallic

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84 complexes with weaker P binding strength. As a result, once the threshold PSR is cr ossed P is released much easily in Bh. No relationship between PSR and P fraction desorbed was obtained for Bt where P is retained more tenaciously by the inorganically complexed metals along with other factors influencing P retention. It implies that eve n if threshold PSR is crossed for Bt soils it still has relatively high P retentive capacity and degree of hysteresis. Implications of P hytoremediation of S ubsurface P Availability of P to plants from fertilizer impacted Alaquod and Paleudult subsurface ho rizons (as well as plant uptake capacity) is pertinent to potential efficacy of phytoremediation Phytoremediation involves removal of elements from soil by plants (Salt et al. 1995). It has potential to be a safe and economical method for reducing excess P in soils and thus helps to minimize P loss through surface or subsurface flow. Since deep rooted plants can access P from subsurface horizons of Alaquods and Paleudults, soils under trees will be less susceptible to P loss in comparison to treeless past ures. Removal of P from subsurface horizons is of considerable importance particularly in sandy soils where leaching is often a major mode of transport. Nair et al. ( 2007) reported that the mean SPSC of a soil profile in a pasture with trees vs. treeless pastures up to a meter depth were 1494 and 370 kg P ha 1 Although the SPSC was positive for both the profiles, it was less positive for the treeless pasture in comparison to pasture with trees. This indicates P removal by deep rooted plants in pasture wit h trees which also in turn increases the capacity of these soils to retain more P in comparison to pasture without trees.

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85 Summary Environmental risk of P loss from soils may be more conveniently predicted by SPSC than by EPC 0 Loamy and clayey Bt horizons have higher P retentive capacity than overlying sandy eluvial horizons due to greater abundance of inorganic metal oxides along with crystalline Fe and phyllosilicates. However, the components responsible for tenaciously binding P and maintaining low P so lution concentrations are noncrystalline metal oxides. Alaquod subsurface horizons have higher risk of P loss in comparison to Paleudult subsurface horizons. Phytoremediation is a potential approach to remove P from subsurface horizons, thereby reducing P loss risk. Since deep rooted plants can access P from subsurface horizons of Alaquods it may be successfully used to reduce the risk of P loss from these soils.

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86 Table 5 1 Mean and SD by site and horizon for chem ical properties of soil s studied Site Ho rizon n Statistics pH WSP FeO P M1 P M1 Fe M1 Al M3 P M3 Fe M3 Al ------------------------------------------mg kg 1 -----------------------------------------S1 E 15 Mean 5.95 4.91 7.55 16 7 24 17 34 36 SD 0.79 5.6 0 8.55 22 5 26 23 32 53 Bh 20 Mean 5.56 2.67 5.47 35 27 961 41 94 1200 SD 0.62 6.54 11.2 56 41 516 52 101 524 S2 E 8 Mean 6.01 2.57 3.52 3 4 10 3 5 14 SD 0.43 2.02 1.44 2 2 8 3 6 14 Bh 11 Mean 4.94 2.55 8.21 27 13 583 29 64 705 SD 0.25 3.24 7.12 26 12 569 25 77 486 S3 E 11 Mean 5.55 0.13 0.66 1 2 4 3 4 8 SD 0.12 0.16 1.1 2 3 3 3 3 9 Bh 25 Mean 5.57 5.5 0 18.88 88 12 551 102 70 850 SD 0.33 4.8 0 13.87 68 19 195 76 109 328 S4 E 8 Mean 5.68 18.17 40.03 125 28 202 196 110 646 SD 0.33 4.14 11.28 35 18 43 24 40 94 Bt 36 Mean 4.69 2.62 5.76 22 8 207 23 31 1221 SD 0.56 8.11 17.63 54 4 40 40 21 572 S5 E 15 Mean 5.14 0.2 0 0.26 3 31 144 8 104 424 SD 0.55 0.4 0 0.34 2 23 76 4 47 170 Bt 21 Mean 4.46 0.02 0.11 1 9 221 2 31 1331 SD 0.36 0.06 0.17 1 6 107 2 17 1092 S6 E 11 Mean 6.42 0.41 2.41 5 5 31 13 98 194 SD 0.66 0.39 1.84 2 2 15 7 136 223 Bt 10 Mean 5.97 0.14 3.32 7 5 61 20 39 825 SD 0.59 0.22 4.68 8 3 35 20 7 149 WSP, water soluble phosphorus; FeO P,P extracted f rom iron oxide impregnated filter paper; M1 P, Al, Fe, Mehlich 1 extractable phosphorus, aluminum and iron respectively; M3 P, Al and Fe, Mehlich 3 extractable phosphorus, aluminum and iron, respectively

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87 Table 5 2 Mean and SD by site and horizon for ox alate extractable P and metals, data used in PSR and SPSC calculations and total P for the soils studied. Site Horizon n Statistics TP Ox P Ox Fe Ox Al PSR SPSC -----------------mg kg 1 ------------------mg kg 1 S1 E 15 Mean 49 41 38 68 0. 52 31 SD 30 26 37 56 0.27 24 Bh 20 Mean 117 113 214 2070 0.08 12 SD 64 68 294 1483 0.09 125 S2 E 8 Mean 5 4 6 23 0.13 1 SD 4 2 7 17 0.09 6 Bh 11 Mean 54 48 69 870 0.06 4 SD 36 34 93 770 0.05 40 S3 E 11 Mean 6 4 5 15 0.2 2 SD 2 4 8 8 0.08 1 Bh 25 Mean 128 115 85 1035 0.09 53 SD 100 89 146 397 0.07 81 S4 E 8 Mean 230 256 262 454 0.4 176 SD 75 93 89 111 0.12 83 Bt 36 Mean 263 51 270 949 0.05 134 SD 71 86 100 250 0.09 106 S5 E 15 Mean 19 20 232 309 0.04 38 SD 10 9 72 154 0.01 19 Bt 21 Mean 75 10 291 828 0.01 157 SD 43 4 123 471 0.01 79 S6 E 11 Mean 30 22 104 120 0.12 1 SD 42 9 54 75 0.03 9 Bt 10 Mean 371 41 223 447 0.06 55 SD 339 33 162 102 0.04 22 TP, total phosphorus ; Ox P, Al and Fe, oxalate extractable phosphorus, aluminum and iron, respectively; PSR, P saturation ratio using oxalate extract calculated as molar ratio of P to [Fe + Al]; SPSC, safe phosphorus s torage capacity. SPSC for Bh and Bt horizon soils calculated using o xalate ex traction according to e quation ( 5 3 )

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88 Figure 5 1 Setup of Iron oxide impregnated filter paper

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89 Figure 5 2 Relationship between P extracted from iron oxide impregnated filter paper (FeO P) and water soluble P (WSP) for E and Bh horizons of Alaquods Figure 5 3 Relationship between P extracted from iron oxide impregnated filter paper (FeO P) and water soluble P (WSP) for E and Bt horizons of Paleudults y = 2.0x + 3.1 R = 0.74 0 15 30 45 60 75 0 10 20 30 40 FeO P (mg kg 1 ) WSP (mg kg 1 ) E of Alaquod Bh of Alaquod y = 2.1x + 0.57 R = 0.93 0 15 30 45 60 75 90 0 10 20 30 40 50 60 FeO P (mg kg 1 ) WSP (mg kg 1 ) E of Paleudult Bt of Paleudult

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90 Figure 5 4 Relationship between water soluble P (WSP) and P saturation ratio calculated fo r subsurface E and Bh horizons of Alaquods using P, Fe and Al in an oxalate extract (PSR ox ).

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91 Figure 5 5 Relationship between water soluble P (WSP) and P saturation ratio calculated for the subsurface E and Bt horizons of Paleudults using P, Fe and Al i n an oxalate extract (PSR ox )

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92 Figure 5 6 Relationship between soil P storage capacity (SPSC) and water soluble P (WSP) for E and Bh horizons of Alaquods. Open and closed markers represent positive and negative SPSC respectively. The R 2 value i s for soi ls with negative SPSC Figure 5 7 Relationship between soil P storage capacity (SPSC) and water soluble P (WSP) for E and Bt horizons of Paleudults. Open and closed markers represent positive and negative SPSC respectively. The R 2 value is for soils wit h negative SPSC y = 7.5x 18.2 R = 0.67 n=46 P source 300 200 100 0 100 200 300 0 10 20 30 40 SPSC (mg kg 1 ) WSP (mg kg 1 ) E of Alaquods Bh of Alaquods n=44 P sink y = 9.9x + 6.7 R = 0.74 n=24 P source 600 400 200 0 200 400 0 10 20 30 40 50 SPSC( mg kg 1 ) WSP (mg kg 1 ) E of Paleudults Bt of Paleudults n=77 P sink

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93 Figure 5 8 Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for E and Bh horizons of Alaquods. Open and closed markers represent positive and negative SPSC respective ly. The R 2 value is for soils with negative SPSC Figure 5 9 Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for E and Bt horizons of Paleudults. Open and closed markers represent pos itive and negative SPSC respectively. The R 2 value is for soils with negative SPSC y = 3.7x 1.4 R = 0.65 n=46 P source 300 200 100 0 100 200 300 0 10 20 30 40 50 SPSC (mg kg 1 ) FeO P (mg kg 1 ) E of Alaquod Bh of Alaquod y = 3.7x 4.8 R = 0.79 n=24 P source 400 300 200 100 0 100 200 300 0 20 40 60 80 100 SPSC (mg kg 1 ) FeO P (mg kg 1 ) E of Paleudult Bt of Paleudult n=77 P sink n=44 P sink

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94 Figure 5 10. Relationship between soil P storage capacity (SPSC) and P extracted from iron oxide impregnated filter paper (FeO P) for Alaquod and Paleudult subsurface hor izons (combined data) Open and closed markers represent positive and negative SPSC respectively. The R 2 value is for soils with negative SPSC. Figure 5 11 Relationship between soil P storage capacity (SPSC) and equilibrium phosphorus concen tration (EPC 0 ) for Bh and Bt horizons y = 3.8x + 1.2 R = 0.77 n=70 P source 400 300 200 100 0 100 200 300 0 20 40 60 80 100 SPSC (mg kg 1 ) FeO P (mg kg 1 ) n = 121 P sink y = 6.5x 2 71.1x 48.9 R = 0.61 n=40 P source 300 200 100 0 100 200 300 400 0 2 4 6 8 SPSC( mg kg 1 ) EPC 0 (mg L 1 ) Bh of Alaquod Bt of Paleudult n=38 P sink

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95 Figure 5 12 Relationship between soil P storage capacity (SPSC) predicted vs. SPSC observed for Bt samples Figure 5 13 Relationship between Fraction of P desorbed and P saturation ratio calculated for the Bh horizons of Alaquods using P, Fe and Al in an oxalate extract (PSR ox ) y = 0.93x + 17.81 R = 0.86 0 50 100 150 200 0 50 100 150 200 SPSC predicted (mg kg 1 ) SPSC observed (mg kg 1 ) y = 81.1x + 3.8 R = 0.28 y = 173.2x + 2.5 R = 0.32 0 10 20 30 40 50 60 70 0.00 0.05 0.10 0.15 0.20 0.25 0.30 Fraction of P desorbed (%) PSR ox PSR<0.05 PSR>0.05

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96 CHAPTER 6 CONCLUSIONS Continuo us application of P fertilizers in excess of plant requirements causes P loss to waterways resulting in accelerated eutrophication of surface wat ers. Sandy soils have higher risk of P loss because of limited P retention capacity with Fe and Al often used as a surrogate for P retention Vertical movement of P through the soil profile results in its contact with Bh horizons of Alaquods and Bt horizo ns of Paleudults which may act as P sinks. Loss of P via surface and subsurface movement is an environmental concern. Alaquods and Paleudults with sandy A and E horizons occur extensively in the c oastal plain of the SE United States. It is critical to rela te P sorption characteristics to compositional differences in Alaquod and Paleudult horizons and to evaluate implications for risk of P loss via subsurface flow in these soils. This study evaluated the P release potential from fertilizer impacted Alaquods and Paleudults of coastal plain soils. Alaquod s of the SE U.S. are characterized by sandy textures, fluctuating water table and the presence of a subsurface Bh horizons below sandy surface horizons In this study, the threshold PSR for Bh horizons was eva luated using oxalate (PSR Ox ), Mehlich 1 (PSR M1 ) and Mehlich 3 (PSR M3 ) extractants. The change point was 0.05 for PSR ox ; 0.08 for PSR M1 ; and 0.09 for PSR M3 D ifferent threshold PSR for Bh horizons in comparison to surface horizons of Florida soils suggests that change point is influenced by the soil components. For most practical purposes, a PSR of 0.1 may be used when M1 or M 3 is used as the extractant; the value falls well within the confidence intervals of 0 to 0.16 for M 1 and 0 to 0.19 for M 3.

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97 Phosphorus release characteristic s of surface and subsurface horizons of Alaquods were evaluated using SPSC V alidity of S PSC requires thorough extraction of the forms of Al and Fe with which P is associated in the sample as accomplished by oxalate extractant. C onv e rsion factors of 1.8 and 1.3 were derived for SPSC calculated with M1 and M3 data for Bh horizons to compensate for the underestimation of the remaining capacity of the soil to adsorb additional P using these extractants. SPSC of Bh horizons was significan tly higher than that of surface horizons due to much lower metal content and greater P loading of the later. The SPSC status of any horizon may be used to predict the consequences of water table management regimes with respect to P transport. For example, maintaining the water table below a positive Bh horizon could favor P retention and minimize risk of P loss from the soil. E luv ial horizons of Alaquods have negligible P retentive capacity whereas E horizons of Paleudults can retain P due to the presence o f metal oxides as indicated by oxalate pyrophosphat e and CBD extractions. Higher resistance to P desorption for Bt horizons of Paleudults relative to Bh horizons of Alaquods likely relates to the greater abundance of Fe oxides and kaolinite clay in Bt a nd the predominance of organically over inorganically complexed Al in the Bh. Differences in P sorption desorpti on behavior between Bh and Bt relate to the difference in crystalline and noncrystalline inorganic components between these horizons. The thres hold PSR (using oxalate P, Fe and Al in the PSR calculation) for Bt was found to be higher (0.12) relative to Bh (0.05). The lower PSR threshold for Bh horizons suggests that the proportion of metals serving as a high energy binding site for P is lower for organically complexed forms relative to inorganically complexed noncrystalline forms.

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98 The environmental risk of P loss is related to the compositional difference s among horizons within the soil profile. Eluvial horizons of Alaquods have negligible P reten tive capacity which accounts for the minimal retardation of P transport to underlying Bh horizons or to streams and ditches via shallow subsurface flow. O n the other hand, in Paleudult soil profiles, the E horizons can retain relatively large amounts of P which in turn reduces the susceptibility of underlying Bt horizons to become loaded above the threshold PSR Thus, it can be inferred that pedological, compositional, and hydrologic distinctions between Paleudults and Alaquods result in greater risk of P l oss from Alaquods under comparable P loadings. Since SPSC concepts have mainly been applied to sandy soils; there was a need to verify their applicability to finer textured horizons (Bt) in coastal plain soils T he predictive validity of SPSC for Bt hori zon samples was tested by a method of known P additions SPSC predictions of P sorption capacity (SPSC predicted determined experimentally) corresponded closely to the observed values (SPSC observed calculated based on oxalate extractant) with a R 2 of 0.86 and a slope of 0.93 The above findings indicate that reduction in SPSC with P application can be predicted for loamy to clayey soil horizons as well These results also indicate that although crystalline Fe oxides along with phyllosilicates play a dominant role for P retention in Bt samples, the noncrystalline metal oxides extracted by oxalate are the components that bind P most tenaciously and that control sorption below the threshold PSR. Relationship between SPSC and equilibrium P concentration ( EPC 0 ) for Bh and Bt samples show that as long as SPSC is positive (PSR is below the change point) the EPC 0 value is low; whereas the value increases considerably when SPSC is negative

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99 When the relationship between negative SPSC and EPC 0 is verified, EPC 0 values may be predicted from P, Fe and Al data that can be easily obtained from any soil testing laboratory Environmental risk of P loss from soils may be more conveniently predicted by SPSC than by EPC 0 This study also emphasized the need to develop m anagement strateg ies to remove subsurface P from Alaquods and Paleudults to minimize degradation of water quality. Iron oxide (FeO) impregnated filter paper has been successfully used as an indicator of plant P availability. It was observed that p lant P av ailability is minimal when SPSC is zero or positive and increase d with negative SPSC Plant P availability as inferred from FeO paper suggests that the P availability remains the same irrespective of compositional difference s between subsurface horizons of Alaquods and Paleudults. Availability of P to plants from fertilizer impacted Alaquod and Paleudult subsurface horizons is pertinent so that P can be removed from deeper horizons via p hytoremediation to reduce risk of subsurface P loss through leaching. Environmental risk of P loss along with plant P availability can be predict ed using the SPSC concept for sandy and loamy to clayey soil horizons. Since SPSC is additive, it is possible to predict P storage and release across soil profiles to a depth of hyd rological relevance for P transport, to include Bh or Bt horizons when present. Further study is needed on calcareous soils for applicability of th e SPSC concept when P retention is not regulated by Fe and Al in the soil The SPSC approach is more rigorous than the use of STP and therefore can be possibly be used to develop an agronomic environmental SPSC based protocol. Research to date on SPSC has been on Florida soils. It will be beneficial to test the validity of this approach for acidic soils of

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100 other regions Soil P storage capacity can serve as a more readily determinable alternative for EPC 0 since the latter is consistently low when SPSC is positive. When SPSC is positive, EPC 0 is minimal suggesting that up to the threshold PSR, P release is regulate d only by Fe and Al, and other factors such as the clay content do not play a role in P retention. However, further research is needed to establish t he relationship between SPSC and EPC 0 when SPSC is negative.

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101 LIST OF REFERENCES Agbenin, J.O. 2003. Extra ctable iron and aluminum effects on phosphate sorption in a savanna Alfisols. Soil Sci. Soc. Am. J. 67:589 595. Anderse n, J.M. 1976. An ignition method for determination of total phosphorus in lake sediments. Water Res. 10:329 331. Bache, B.W., and E.G. Wi lliams. 1971. A phosphate sorp tion index for soils. J. Soi l Sci. 22:289 301. Barrow, N.J. 1979. The desorption of phosphate from soil. J. Soil Sci. 30:259 270. Beegle, D. 2005. Assessing soil phosphorus for crop production by soil testing. p. 123 145. In J .T. Sims and A.N. Sharpley (eds.) P hosphorus: A griculture and the environment. Agron. Monogr. 46. ASA CSSA SSSA Madison, WI. Bennoah, E., and D.K.Acquaye. 1989. Phosphate sorption characters of selected major Ghanaian soils. Soil Sci. 148:114 123. Bhatt i, J.S., and N.B. Comerford. 2002. Measurement of phosphorus desorption from a spodic horizon using two different desorption methods and pH control. Commun. Soil Sci. Plant Anal. 33:845 853. Bowden, J.W., A. Posner, and J. Quirk. 1977. Ionic adsorption on v ariable charge mineral surfaces t heoretical charge development and titration curves. Aust J. Soil Res. 15:121 136. Brewster, J.L., A.N. Gancheva, and P.H. Nye. 1975. The determination of desorption isotherms for soil phosphate using low volumes of soluti on and an anion exchange resin. J. Soil Sci. 26:364 377. Bridgham, S.D., C.A. Johnston, J.P. Schubauer Berigan, and P. Weishampel. 2001. Phosphorus sorption dynamics in soils and coupling with surface and pore water in riverine wetlands. Soil Sci. Soc. Am. J. 65:577 588. Casson, J.P., D.R. Bennett, S.C. Nolan, B.M.Olson, and G.R. Ontkean. 2006. Degree of phosphorus saturation thresholds in manure amended soils of Alberta. J. Environ. Qual. 35: 2212 2221. Chardon, W.J., RG. Menon, and S.H. Chien. 1996. Iron oxide impre gnated filter paper (Pi test): A review of its development and m ethodological research. Nutr. Cycl. Agroecosys. 46:41 51. Chrysostome, M., V.D. Nair, W.G. Harris, and R.D. Rhue. 2007. Laboratory validation of soil phosphorus storage capacity pre dictions for use in risk assessmen t. Soil Sci. Soc. Am. J. 71(5): 1564 1569.

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112 BIOGRAPHICAL SKETCH De bolina Chakraborty was born in Calcutta, West Bengal, India in 1983 She r cience from the same University in 2 007. She started her doctorate program in the Soil and Water Science Department at the University of Florida in fall 2007.