Phosphorus speciation in manure and fertilizer impacted Mid-Atlantic coastal plain soils.

Historical applications of manures and fertilizers at rates exceeding crop P removal in the Mid-Atlantic region (United States) have resulted in decades of increased water quality degradation from P losses in agricultural runoff. As such, many growers in this region face restrictions on future P applications. An improved understanding of the fate, transformations, and availability of P is needed to manage P-enriched soils. We paired chemical extractions (i.e., Mehlich-3, water extractable P, and chemical fractionation) with nondestructive methods (i.e., x-ray absorption near edge structure [XANES] spectroscopy and x-ray fluorescence [XRF]) to investigate P dynamics in eight P-enriched Mid-Atlantic soils with various management histories. Chemical fractionation and XRF data were used to support XANES linear combination fits, allowing for identification of various Al, Ca, and Fe phosphates and P sorbed phases in soils amended with fertilizer, poultry litter, or dairy manure. Management history and P speciation were used to make qualitative comparisons between the eight legacy P soils; we also speculate about how P speciation may affect future management of these soils with and without additional P applications. With continued P applications, we expect an increase in semicrystalline Al and Fe-P, P sorbed to Al (hydro)oxides, and insoluble Ca-P species in these soils for all P sources. Under drawdown scenarios, we expect plant P uptake first from semicrystalline Al and Fe phosphates followed by P sorbed phases. Our results can help guide management decisions on coastal plain soils with a history of P application.

The importance of consensus science to managing phosphorus in the environment: SERA-17 and the legacy of Andrew Sharpley.

Phosphorus (P) loss from agricultural systems to surface waters, and ultimately, eutrophication, presents a wicked problem requiring transdisciplinary solutions. The mission of SERA-17 (Southern Extension and Research Advisory Information Exchange Group-17) has been to address this problem by developing "Innovative Solutions to Minimize Phosphorus Losses from Agriculture." Over the course of his career, Dr. Andrew Sharpley demonstrated a rare ability to collaboratively achieve consensus around issues related to the science and management of P. The SERA-17 organization served as the central community of experts and stakeholders where that consensus was built and applied. The consensus-based approach, demonstrated by Sharpley and at the core of the SERA-17 organization, was routinely applied to key areas of P science to produce applied outcomes that have been readily adopted: advance foundational science to resolve knowledge gaps and to promote innovation; promote consistency in methods to facilitate comprehensive investigations and conclusions across a diversity of systems; engage diverse stakeholders to prioritize research, and ultimately, ensure that outcomes reflect a plurality of perspectives; and deliver pragmatic solutions that reflect the best information available at a particular time. We review the history of SERA-17 in delivering new science and management recommendations for P, with an eye to elucidating Sharpley's role and legacy in this process.

X-ray absorption near edge structure spectroscopy reveals phosphate minerals at surface and agronomic sampling depths in agricultural Ultisols saturated with legacy phosphorus.

Legacy phosphorus (P) soils have received excessive P inputs from historic manure and fertilizer applications and present unique management challenges for protecting water quality as soil P saturation leads to increased soluble P to waterways. We used P K-edge X-ray absorption near edge structure (XANES) spectroscopy to identify and quantify the dominant P minerals in four representative legacy P soils under conventional till and no-till management in Maryland, USA. Various measures of extractable soil P, including water-extractable P (20.6-54.1 mg kg-1 at 1:10 soil-to-water ratio; 52.7-132.2 mg kg-1 at 1:100 soil-to-water ratio), plant available P extracted with Mehlich 3 (692-1139 mg kg-1), and Mehlich 3P saturation ratio (0.54-1.37), were above the environmental threshold values, suggesting the accumulation of legacy P in soils. The quantification of dominant P minerals may provide insights into the potential of legacy P soils to contribute to P release for crop use and soluble P losses. Linear combination fits of XANES spectra identified the presence of four phosphate mineral groups, consisting of (i) calcium-phosphate minerals (11-59%) in the form of fluorapatite, ß-tricalcium phosphate, and brushite, followed by (ii) iron-phosphate minerals (12-49%) in the form of ludlamite, heterosite, P sorbed to ferrihydrite, and amorphous iron phosphates, (iii) aluminum-phosphate minerals (15-33%) in the form of wavellite and P sorbed to aluminum hydroxide, and (iv) other phosphate minerals (5-35%) in the form of copper-phosphate (cornetite, 5-18%) and manganese-phosphate (hureaulite, 25-35%). Organic P consisting of phytic acid was found in most soils (13-24%) and was more pronounced in the surface layer of no-till (21-24%) than in tilled (16%) fields. Of the P forms identified with XANES, we conclude that P sorbed to Fe and Al, and Ca-P in the form of brushite and ß-tricalcium phosphate will likely readily contribute to the soil WEP pool as the soil solution P is depleted by crop uptake and lost via runoff and leaching.

Examining sources and pathways of phosphorus transfer in a ditch-drained field.

Understanding the processes that mobilize and transport dissolved phosphorus (P) during storms is critical to managing P in flat landscapes with open ditch drainage and legacy soil P. In this study, we used routine baseflow monitoring and intensive storm sampling at a ditch-drained site on Maryland's Lower Eastern Shore (July 2017-September 2018) to assess whether concentration-discharge (C-Q) relationships and chemical and isotopic hydrograph separation could provide insight into the processes that mobilize and transport dissolved P in ditch drainage. Using a segmented regression model, we determined that long-term C-Q relationships for dissolved P differed above and below a discharge threshold of 6.4 L s-1 . Intensive storm sampling revealed that small storms (n = 3) occurring at or below the discharge threshold generally exhibited complex hysteresis and dissolved P dilution patterns that were consistent with deeper (>122 cm) groundwater inputs with low dissolved P concentrations (0.04 mg L-1 ). In contrast, large storms occurring well above the discharge threshold (n = 4) induced rising water tables and preferential flow pathways that most likely tapped dissolved P-enriched shallow (<20 cm) soil waters (0.89 mg L-1 ), producing consistent clockwise hysteresis and dissolved P flushing patterns. Notably, chemical and isotope hydrograph separation during two of the largest storms revealed significant event water fractions (59-68%) that strongly suggested a role for the rapid delivery of dissolved P via preferential flow pathways. Findings highlight the need to mitigate vertical P stratification as a means for reducing dissolved P flushing from ditch-drained landscapes with legacy P.

Mechanisms of Phosphorus Removal by Phosphorus Sorbing Materials.

Stormwater filters are a structural best management practice designed to reduce dissolved P losses from runoff. Various industrial byproducts are suitable for use as P sorbing materials (PSMs) for the treatment of drainage water; P sorption by PSMs varies with material physical and chemical properties. Previously, P removal capacity by PSMs was estimated using chemical extractions. We determined the speciation of P when reacted with various PSMs using X-ray absorption near edge structure (XANES) spectroscopy. Twelve PSMs were reacted with P solution in the laboratory under batch or flow-through conditions. In addition, three slag materials were collected from working stormwater filtration structures. Phosphorus K-edge XANES spectra were collected on each reacted PSM and compared with spectra of 22 known P standards using linear combination fitting in Athena. We found evidence of formation of a variety of Ca-, Al-, and/or Fe-phosphate minerals and sorbed phases on the reacted PSMs, with the exact speciation influenced by the chemical properties of the original unreacted PSMs. We grouped PSMs into three general categories based on the dominant P removal mechanism: (i) Fe- and Al-mediated removal [i.e., adsorption of P to Fe- or Al-(hydro-)oxide minerals and/or precipitation of Fe- or Al-phosphate minerals]; (ii) Ca-mediated removal (i.e., precipitation of Ca-phosphate mineral); and (iii) both mechanisms. We recommend the use of Fe/Al sorbing PSMs for use in stormwater filtration structures where stormwater retention time is limited because reaction of P with Fe or Al generally occurs more quickly than Ca-P precipitation.

Assessing Coastal Plain Risk Indices for Subsurface Phosphorus Loss.

Phosphorus (P) Index evaluations are critical to advancing nutrient management planning in the United States. However, most assessments until now have focused on the risks of P losses in surface runoff. In artificially drained agroecosystems of the Atlantic Coastal Plain, subsurface flow is the predominant mode of P transport, but its representation in most P Indices is often inadequate. We explored methods to evaluate the subsurface P risk routines of five P Indices from Delaware, Maryland (two), Virginia, and North Carolina using available water quality and soils datasets. Relationships between subsurface P risk scores and published dissolved P loads in leachate (Delaware, Maryland, and North Carolina) and ditch drainage (Maryland) were directionally correct and often statistically significant, yet the brevity of the observation periods (weeks to several years) and the limited number of sampling locations precluded a more robust assessment of each P Index. Given the paucity of measured P loss data, we then showed that soil water extractable P concentrations at depths corresponding with the seasonal high water table (WEP) could serve as a realistic proxy for subsurface P losses in ditch drainage. The associations between WEP and subsurface P risk ratings reasonably mirrored those obtained with sparser water quality data. As such, WEP is seen as a valuable metric that offers interim insight into the directionality of subsurface P risk scores when water quality data are inaccessible. In the long term, improved monitoring and modeling of subsurface P losses clearly should enhance the rigor of future P Index appraisals.

Nutrient leaching from mixed-species Florida residential landscapes.

Nutrient losses from residential lawns and landscapes can negatively impact water quality. Information about nutrient leaching from established residential landscapes containing a mixture of woody ornamental plants and turfgrass is limited. The objective of our study was to determine the effect of vegetation cover (turfgrass vs. woody ornamental) on nutrient leaching from established landscapes. Nine drainage lysimeters were planted with three vegetation treatments with the following coverage: (i) 60% turfgrass, 40% ornamental; (ii) 75% turfgrass, 25% ornamental; and (iii) 90% turfgrass, 10% ornamental. Daily leachate samples were collected and combined to produce weekly flow-weighted samples for 1 yr. Leachate samples were analyzed for total Kjeldahl N (TKN), nitrate (+ nitrite)-N (NO), ammonium-N (NH-N), and dissolved reactive phosphorus (DRP). The ratio of actual evapotranspiration (ET) to reference evapotranspiration (ET) was similar among treatments. However, drainage from the 90% turfgrass lysimeters was periodically higher than from the 60 and/or 75% turfgrass treatments. In most cases, leachate N and P concentrations and loads followed the same trend as drainage. The addition of shrubs in the 60 and 75% turfgrass treatments reduced leachate when rainfall was low and irrigation was the main water input. We suggest that established woody ornamental plants are more effective at absorbing water and nutrients than turfgrass due, in part, to increased root biomass and deeper rooting of established woody plants, which allows for more efficient uptake of soil water and nutrients. The use of woody plants in residential landscapes can reduce nutrient leaching in urban areas.

Nutrient Leaching during Establishment of Simulated Residential Landscapes.

Research evaluating nutrient losses during the establishment of plant material in mixed residential landscapes is limited. The objectives of this study were to determine the effect of vegetative cover type, compost application, and tillage on nutrient losses during the establishment of landscape plants. Twenty-four small plots constructed with subsoil fill were planted with St. Augustinegrass [ (Walter) Kuntze] and mixed ornamental species in a randomized complete block design. Plots received composted dairy manure solids at a rate of 0 or 50.8 m ha- in combination with shallow tillage or aeration. Cumulative leachate loads and flow-weighted mean concentrations of NH-N, NO + NO-N, and dissolved reactive P (DRP) were calculated periodically and annually to assess nutrient leaching from landscape plots. Higher cumulative leachate volume, inorganic N and DRP loads, and mean NO + NO-N and DRP concentrations were observed under ornamental cover during one or more study periods, which we attribute to differences in root density and shoot biomass between mixed ornamental species and turfgrass during establishment. Greater cumulative leachate inorganic N loads were reported from composted soils than from unamended soils or soils receiving only tillage or aeration. Inorganic N and DRP loads were similar in magnitude to reported leaching losses from agricultural systems. Better management of nutrients and water in woody ornamental plant beds during plant establishment is needed due to differences in plant growth habits compared with turfgrass. Nutrient content of organic amendments should be considered when applying these materials as a soil conditioner in new residential landscapes.

Evaluation of phosphorus indices after twenty years of science and development.

The P Index was proposed as a nutrient management tool in 1992 and has been implemented as such for the past decade. However, lack of water quality improvement in agricultural watersheds and discrepancies in P loss ratings between P indices have raised questions about continued use of the P Index. In response to these concerns, a symposium was held as part of the 2011 ASA, CSSA, SSSA annual meetings. This symposium produced a special collection of seven papers describing the role of P indices in P management, evaluation of P indices, new models for assessing P loss, methods to improve P indices, and changes in producer behavior resulting from P Index use. The objectives of this introductory paper are to provide background on the P Index concept, overviews of the special collection papers, and recommendations for future P Index evaluation and development research. The papers in this special collection conclude that P indices can provide accurate assessments of P loss but must be evaluated appropriately. Evaluation will require compiling large regional P loss datasets at field and small watershed scales. Simulation models may be used to generate P loss estimates; however, models must be calibrated and validated to ensure their accuracy. Further development of P indices will require coordinated regional efforts to identify common P Index frameworks and standardized interpretations. Stringent P Index evaluations will expand the utility of P indices for critical source area identification and strategic best management practice implementation by regulatory, education, and scientific communities alike.

Phosphorus runoff from waste water treatment biosolids and poultry litter applied to agricultural soils.

Differences in the properties of organic phosphorus (P) sources, particularly those that undergo treatment to reduce soluble P, can affect soil P solubility and P transport in surface runoff. This 2-yr field study investigated soil P solubility and runoff P losses from two agricultural soils in the Mid-Atlantic region after land application of biosolids derived from different waste water treatment processes and poultry litter. Phosphorus speciation in the biosolids and poultry litter differed due to treatment processes and significantly altered soil P solubility and dissolved reactive P (DRP) and bioavailable P (FeO-P) concentrations in surface runoff. Runoff total P (TP) concentrations were closely related to sediment transport. Initial runoff DRP and FeO-P concentrations varied among the different biosolids and poultry litter applied. Over time, as sediment transport declined and DRP concentrations became an increasingly important component of runoff FeO-P and TP, total runoff P was more strongly influenced by the type of biosolids applied. Throughout the study, application of lime-stabilized biosolids and poultry litter increased concentrations of soil-soluble P, readily desorbable P, and soil P saturation, resulting in increased DRP and FeO-P concentrations in runoff. Land application of biosolids generated from waste water treatment processes that used amendments to reduce P solubility (e.g., FeCl(3)) did not increase soil P saturation and reduced the potential for DRP and FeO-P transport in surface runoff. These results illustrate the importance of waste water treatment plant process and determination of specific P source coefficients to account for differential P availability among organic P sources.

Evaluating phosphorus release from biosolids and manure-amended soils under anoxic conditions.

The solubility of P in biosolids and manures has been shown to influence the potential for dissolved P losses in runoff and leachate when these materials are land applied. As a result, some Mid-Atlantic US states have developed P source coefficients (PSCs) to account for differences in P solubility between fertilizers, manures, and biosolids in P risk assessment tools. The reliability of these PSCs has not been evaluated under anoxic conditions, where environmental changes may affect the P solubility of biosolids or manures. The objective of this study was to assess the effects of anoxic conditions on the release of P from a range of Mid-Atlantic soils amended with manures and biosolids. The concentration of dissolved P released into solution (0.01 mol L(-1) NaCl) from the Pamunkey, Berks, and Manor soils was significantly lower under reducing conditions than under oxidized conditions (median DeltaP = -0.70, -0.49, and -0.07 mg L(-1), respectively; all significant at the 0.001 probability level). There was no significant P source effect on dissolved P released into solution after anoxic incubation of soils. Calculated solubility diagrams and increases in oxalate-extractable Fe and P sorption index under reducing conditions for all soils suggest the precipitation of (i) an Fe(II)-oxide that increased the P sorption capacity of the soils or (ii) an Fe(II)-phosphate that decreased the solubility of P. We propose that current PSCs do not need alteration to account for differences in P solubility of organic sources under reducing conditions under relatively static conditions (e.g., seasonable high water table, periodically submerged soils, stagnant drainage ditches).

Selection of a water-extractable phosphorus test for manures and biosolids as an indicator of runoff loss potential.

The correlation of runoff phosphorus (P) with water-extractable phosphorus (WEP) in land-applied manures and biosolids has spurred wide use of WEP as a water quality indicator. Land managers, planners, and researchers need a common WEP protocol to consistently use WEP in nutrient management. Our objectives were to (i) identify a common WEP protocol with sufficient accuracy and precision to be adopted by commercial testing laboratories and (ii) confirm that the common protocol is a reliable index of runoff P. Ten laboratories across North America evaluated alternative protocols with an array of manure and biosolids samples. A single laboratory analyzed all samples and conducted a separate runoff study with the manures and biosolids. Extraction ratio (solution:solids) was the most important factor affecting WEP, with WEP increasing from 10:1 to 100:1 and increasing from 100:1 to 200:1. When WEP was measured by a single laboratory, correlations with runoff P from packed soil boxes amended with manure and biosolids ranged from 0.79 to 0.92 across all protocol combinations (extraction ratio, filtration method, and P determination method). Correlations with P in runoff were slightly lower but significant when WEP was measured by the 10 labs (r=0.56-0.86). Based on laboratory repeatability and water quality evaluation criteria, we recommend the following common protocol: 100:1 extraction ratio; 1-h shaking and centrifuge 10 min at 1500xg (filter with Whatman #1 paper if necessary); and determining P by inductively coupled plasma-atomic emission spectrometry or colorimetric methods.

Characterization of phosphorus species in biosolids and manures using XANES spectroscopy.

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.

Phosphorus restrictions for land application of biosolids: current status and future trends.

The application of biosolids (sewage sludge) to agricultural soils provides P in excess of crop needs when applied to meet the N needs of most agronomic crops. These overapplications can result in the buildup of P in soils to values well above those needed for optimum crop yields and also may increase risk of P losses to surface and ground waters. Because of concerns regarding the influence of P on water quality in the USA, many state and federal agencies now recommend or require P-based nutrient management plans for animal manures. Similar actions are now under consideration for the land application of biosolids. We reviewed the literature on this subject and conducted a national survey to determine if states had restrictions on P levels in biosolids-amended soils. The literature review indicates that while the current N-based approach to biosolids management does result in increases of soil P, some properties of biosolids may mitigate the environmental risk to water quality associated with land application of P in biosolids. Results of the survey showed that 24 states have regulations or guidelines that can be imposed to restrict land application of biosolids based on P. Many of these states use numerical thresholds for P in biosolids-amended soils that are based on soil test phosphorus (STP) values that are much greater than the values considered to be agronomically beneficial. We suggest there is the need for a comprehensive environmental risk assessment of biosolids P. If risk assessment suggests the need for regulation of biosolids application, we suggest regulations be based on the P Site Index (PSI), which is the method being used by most states for animal manure management.

On-farm assessment of biosolids effects on soil and crop tissue quality.

Agronomic use of biosolids as a fertilizer material remains controversial in part due to public concerns regarding the potential pollution of soils, crop tissue, and ground water by excess nutrients and trace elements in biosolids. This study was designed to assess the effects of long-term commercial-scale application of biosolids on soils and crop tissue sampled from 18 production farms throughout Pennsylvania. Biosolids application rates ranged from 5 to 159 Mg ha(-1) on a dry weight basis. Soil cores and crop tissue samples from corn (Zea mays L.), soybean (Glycine spp.), alfalfa (Medicago sativa L.), orchardgrass (Dactylis spp.) hay, and/or sorghum [Sorghum bicolor (L.) Moench] were collected for three years from georeferenced locations at each farm. Samples were tested for nutrients, trace elements, and other variables. Biosolids-treated fields had more post-growing season soil NO3 and Ca and less soil K than control fields and there was some evidence that soil P concentrations were higher in treated fields. The soil concentrations of Cu, Cr, Hg, Mo, Mn, Pb, and Zn were higher in biosolids-treated fields than in control fields; however, differences were < or = 0.06 of the USEPA Part 503 cumulative pollutant loading rates (CPLRs). There were no differences in the concentrations of measured nutrients or trace elements in the crop tissue grown on treated or control fields at any time during the study. Commercial-scale biosolids application resulted in soil trace element increases that were in line with expected increases based on estimated trace element loading. Excess NO3 and apparent P buildup indicates a need to reassess biosolids nutrient management practices.