Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy

Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure.     

XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter

Aluminum sulfate (alum; Al(2)(SO(4))(3).14H(2)O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted P in alum amended litters is predominantly organic ( approximately 80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.     

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 speciation in broiler litter and turkey manure produced from modified diets

Modifying poultry diets by reducing mineral P supplementation and/or adding phytase may change the chemical composition of P in manures and affect the mobility of P in manure-amended soils. We studied the speciation of P in manures produced by broiler chickens and turkeys from either normal diets, or diets with reduced amounts of non-phytate phosphorus (NPP) and/or phytase, using a combination of chemical fractionation and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. All broiler litters were rich in dicalcium phosphate (65-76%), followed by aqueous phosphate (13-18%), and phytic acid (7-20%); however, no hydroxylapatite was observed. Similarly, normal turkey manure had 77% of P as dicalcium phosphate and had no hydroxylapatite, while turkey manure from diets that had reduced NPP and phytase contained equal proportions of dicalcium phosphate (33-45%) and hydroxylapatite (35-39%). This is attributed to the higher total Ca to P ratio (>2) in modified turkey manures that resulted in transformation of more soluble (dicalcium phosphate) to less soluble P compounds (hydroxylapatite). Chemical fractionation showed that H2O-extractable P was the predominant form in broiler litter (56-77%), whereas aqueous phosphate determined with XANES was <18% indicating that H2O probably dissolved mineral forms of P (e.g., dicalcium phosphate). Results show that HCl extraction primarily removed phytic acid from broiler litters and normal turkey manure, while it removed a mixture of hydroxylapatite and phytic acid from modified turkey manures. The combination of chemical fractionation and XANES provided information about the nature of P in these manures, which may help to devise best management practices for manure use.     

The impact of alum addition on organic P transformations in poultry litter and litter-amended soil

Poultry litter treatment with alum (Al(2)(SO(4))(3) . 18H(2)O) lowers litter phosphorus (P) solubility and therefore can lower litter P release to runoff after land application. Lower P solubility in litter is generally attributed to aluminum-phosphate complex formation. However, recent studies suggest that alum additions to poultry litter may influence organic P mineralization. Therefore, alum-treated and untreated litters were incubated for 93 d to assess organic P transformations during simulated storage. A 62-d soil incubation was also conducted to determine the fate of incorporated litter organic P, which included alum-treated litter, untreated litter, KH(2)PO(4) applied at 60 mg P kg(-1) of soil, and an unamended control. Liquid-state (31)P nuclear magnetic resonance indicated that phytic acid was the only organic P compound present, accounting for 50 and 45% of the total P in untreated and alum-treated litters, respectively, before incubation and declined to 9 and 37% after 93 d of storage-simulating incubation. Sequential fractionation of litters showed that alum addition to litter transformed 30% of the organic P from the 1.0 mol L(-1) HCl to the 0.1 mol L(-1) NaOH extractable fraction and that both organic P fractions were more persistent in alum-treated litter compared with untreated litter. The soil incubation revealed that 0.1 mol L(-1) NaOH-extractable organic P was more recalcitrant after mixing than was the 1.0 mol L(-1) HCl-extractable organic P. Thus, adding alum to litter inhibits organic P mineralization during storage and promotes the formation of alkaline extractable organic P that sustains lower P solubility in the soil environment.     

Biosolids impact soil phosphorus accountability, fractionation, and potential environmental risk

Biosolids land application rates are typically based on crop N requirements but can lead to soil P accumulation. The Littleton/Englewood, Colorado, wastewater treatment facility has supported biosolids beneficial-use on a dryland wheat-fallow agroecosystem site since 1982, with observable soil P concentration increases as biyearly repeated biosolids applications increased from 0, 6.7, 13, 27, to 40 Mg ha(-1). The final study year was 2003, after which P accountability, fractionation, and potential environmental risk were assessed. Between 93 and 128% of biosolids-P added was accounted for when considering conventional tillage soil displacement, grain removal, and soil adsorption. The Fe-P fraction dominated all soil surface P fractions, likely due to an increase in amorphous Fe-oxide because Fe2(SO4)3 was added at the wastewater treatment facility inflow for digester H2S reduction. The Ca-P phase dominated all soil subsurface P fractions due to calcareous soil conditions. A combination of conventional tillage, drought from 1999 to 2003, and repeated and increasing biosolids application rates may have forced soil surface microorganism dormancy, reduction, or mortality; thus, biomass P reduction was evident. Subsurface biomass P was greater than surface biomass, possibly due to protection against environmental and anthropogenic variables or to increased dissolved organic carbon inputs. Even given years of biosolids application, the soil surface had the ability to sorb additional P as determined by shaking the soil in an excessive P solution. Biosolids-application regulations based on the Colorado Phosphorus Index would not impede current site practices. Proper monitoring, management, and addition of other best management practices are needed for continued assurance that P movement off-site does not become a major issue.     

Phosphorus fractions in manure from growing pigs receiving diets containing micronized peas and supplemental enzymes

Different livestock feeds manipulations have been reported to reduce the total P concentration in manure. Information on the influence of these dietary manipulation strategies on the forms of P in manure is, however, limited. This study was, therefore, conducted to investigate the effect of diet manipulation through feed micronization and enzyme supplementation on the forms of P in swine manure. Eight growing pigs were fed four diets: barley-raw pea (BRP), barley-micronized pea (BMP), barley-raw pea with enzyme (BRPE), and barley-micronized pea with enzyme (BMPE) in a 4 x 4 Latin square design. Because we are interested in the effect of enzyme cocktail and pea micronization on manure P, we did not reduce the non-phytate P with enzyme addition in this study. The fecal material and urine were collected and analyzed for total P. Fecal material was fractionated to determine the total P in H2O-, NaHCO3-, NaOH-, and HCl-extractable fractions. The total P in the residual fractions was also determined. About 98% of the total P excreted by the pigs was found in the fecal material. Inclusion of micronized pea in pig diet did not have any significant effect (p > 0.1) on either the total P or the different P fractions in the manure. The labile P (the sum of H2O-P and NaHCO3-P) was significantly reduced (p < 0.05) by the addition of enzyme to swine diets. Pigs fed the BRPE and BMPE had 14 and 18% lower labile P, respectively, compared with pigs fed the BRP. Enzyme addition to pig diets reduced not only the total P in manure, but also the labile P fraction, which is of great environmental concern. Thus, the potential of P loss to runoff and the subsequent eutrophication can be reduced by enzyme addition to pig diets.     

Speciation of phosphorus in phosphorus-enriched agricultural soils using X-ray absorption near-edge structure spectroscopy and chemical fractionation

Knowledge of phosphorus (P) species in P-rich soils is useful for assessing P mobility and potential transfer to ground water and surface waters. Soil P was studied using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy (a nondestructive chemical-speciation technique) and sequential chemical fractionation. The objective was to determine the chemical speciation of P in long-term-fertilized, P-rich soils differing in pH, clay, and organic matter contents. Samples of three slightly acidic (pH 5.5-6.2) and two slightly alkaline (pH 7.4-7.6) soils were collected from A or B horizons in two distinct agrosystems in the province of Québec, Canada. The soils contained between 800 and 2100 mg total P kg(-1). Distinct XANES features for Ca-phosphate mineral standards and for standards of adsorbed phosphate made it possible to differentiate these forms of P in the soil samples. The XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphates were the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near-edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insights on additional forms of P such as organic pools that were not accounted for by the XANES analyses.     

Metal bioavailability and speciation in a wetland tailings repository amended with biosolids compost,wood ash,and sulfate

Lead poisoning of waterfowl from direct ingestion of wetland mine tailings has been reported at the Coeur d'Alene River basin in Idaho. A greenhouse study was conducted to evaluate the effects of surface applications of amendments on lead bioavailability in the tailings. Treatments included sediment only, and sediment with three different surface amendments: (i) biosolids compost plus wood ash, (ii) compost + wood ash + a low SO4(2-) addition as K2SO4, and (iii) compost + wood ash + a high SO4(2-) addition. Measured variables included growth and tissue Pb, Zn, and Cd concentration of arrowhead (Sagittaria latifolia Willd.) and cattail (Typha latifolia L.) and soil pH, redox potential (Eh), pore water Pb, Pb speciation by X-ray absorption spectroscopy, and in vitro Pb bioavailability. The compost + ash amendment alleviated phytotoxicity for both plant species. Bioavailability of Pb as measured by a rapid in vitro extract decreased by 24 to 34% (over control) in the tailings directly below the amendment layer in the compost + SO4 treatments. The ratio of acid volatile sulfide (AVS) to simultaneously extracted metals (SEM) also indicated a reduction in Pb bioavailability (1:40 control, 1:20 compost, 1:8 compost + low SO4, and 1:3 compost + high SO4). Extended X-ray adsorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy data indicated that lead sulfide was greater after 99 d in the treatments that included additions of sulfate. These results indicated that, under reducing conditions, surface amendments of compost + wood ash (with or without sulfate) decreased the bioavailability of Pb in metal-contaminated mine tailings.     

Phosphorus speciation of sequential extracts of organic amendments using nuclear magnetic resonance and X-ray absorption near-edge structure spectroscopies

The chemical forms of phosphorus in organic amendments are essential variables for proper management of these amendments for agro-environmental purposes. This study was performed to elucidate the forms of phosphorus in various organic amendments using state-of-the-art spectroscopic techniques. Anaerobically digested biosolids (BIO), hog (HOG), dairy (DAIRY), beef (BEEF), and poultry (POULTRY) manures were subjected to sequential extraction. The extracts and residues after extraction were analyzed by solution (31)P nuclear magnetic resonance (NMR) and synchrotron-based P 1s X-ray absorption near-edge structure (XANES) spectroscopies, respectively. Most of the total P analyzed by inductively coupled plasma- optical emission spectroscopy in the sequential extracts of organic amendments was orthophosphate, except POULTRY, which was dominated by organic P. The labile P fraction in all the organic amendments, excluding POULTRY, was mainly orthophosphate from readily soluble calcium and some aluminum phosphates. In the poultry litter, Ca phytate was the main P species controlling P solubility. The recalcitrant fraction of BIO was mainly associated with Al and Fe. Those of HOG, DAIRY, and POULTRY were calcium phytate, which were identified only as organic species in the XANES spectra. The combination of the three techniques-sequential chemical extraction, solution (31)P NMR spectroscopy, and P 1s XANES-provided molecular characterization of P in organic amendments that would not have been possible with just one or a combination of any two of these techniques. Therefore, P speciation of organic amendments should use solid-phase and aqueous speciation techniques as deemed feasible.     

In situ speciation studies of copper-humic substances in a contaminated soil during electrokinetic remediation

Speciation of copper-humic substances (HS) in the electrokinetic remediation (EKR) of a contaminated soil was studied by in situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies. The least-square fits of the XANES spectra suggested that the main Cu species in the contaminated soil were Cu-HS (50%), CuCO(3) (28%), Cu(2)O (11%), and CuO (11%). The Cu-HS in the contaminated soil possessed equatorial and axial Cu-O bond distances of 1.94 and 2.17 A with coordination numbers (CNs) of 3.6 and 1.4, respectively. In the EKR process, the axial Cu-O bond distance in the Cu-HS complexes was increased by 0.15 A, which might be due to a ligand exchange of the Cu-HS with H(2)O molecules in the electrolyte. After 180 min of EKR, about 50% of the Cu-HS complexes (or 24% of total Cu) in the soil were dissolved and formed [Cu(H(2)O)(6)](2+) in the electrolyte, 71% (or 17% of total Cu in the soil) of which were migrated to the cathode under the electric field (5 V/cm). This work exemplifies the use of in situ EXAFS and XANES spectroscopies for speciation studies of Cu chelated with HS in the contaminated soil during EKR.     

Laboratory characterization of phosphorus in fresh and oven-dried organic amendments

This study was performed to determine the forms of P and to examine the influence of oven-drying on P forms in different organic amendments. Samples of biosolids, beef and dairy cattle manures, and hog manures from sow and nursery barns were used in this study. Both fresh and oven-dried amendments were analyzed for inorganic (Pi), organic (Po), and total phosphorus using a modified Hedley fractionation technique. Water extracted about 10% of total biosolids P and 30 to 40% of total hog and cattle manure P. The amount of P extracted by NaHCO3 ranged from 21 to 32% of total P in all organic amendments except in the dairy cattle manure with 45% of total P. The labile P fraction (sum of H2O- and NaHCO3-extractable P) was 24% of biosolids P, 60% of hog manure P, and 70% of dairy cattle manure P. The residual P was about 10% in biosolids and cattle manures and 5 to 8% in hog manures. Oven-drying caused a transformation in forms of P in the organic amendments. In hog manures, H2O-extractable Po was transformed to Pi, while in the dairy manure NaHCO3-extractable P was converted to H2O-extractable Pi with oven-drying. Therefore, caution should be exercised in using oven-drying for studies that evaluate forms of P in organic amendments. Overall, these results indicate that biosolids P may be less susceptible to loss by water when added to agricultural land.     

Degree of phosphorus saturation thresholds in manure-amended soils of alberta

The risk of P losses from agricultural land to surface and ground water generally increases as the degree of soil P saturation increases. A single-point soil P sorption index (PSI) was validated with adsorption isotherm data for determination of the P sorption status of Alberta soils. Soil P thresholds (change points) were then examined for two agricultural soils after eight annual applications of different rates of cattle manure and for three agricultural soils after one application of different rates of cattle manure. Linear relationships were found between soil-test P (STP) levels up to 1000 mg kg(-1) and desorbed P in the five Alberta soils. Weak linear relationships were also found between STP and runoff dissolved reactive phosphorus (DRP) in three of these soils. Change points for the degree of P saturation (DPS) were detected in four of the five soils at 3 to 44% for water-extractable P (WEP) and at 11 to 51% for CaCl(2)-extractable P (CaCl(2)-P). Change points were not found for DPS or runoff DRP. Overall DPS thresholds for the five soils combined were 27% for WEP and 44% for CaCl(2)-P at a critical desorbable-P value of 1 mg L(-1). The corresponding STP levels (44 mg kg(-1) for WEP and 71 mg kg(-1) for CaCl(2)-P) are similar to agronomic thresholds for crops grown on Alberta soils. Soluble P losses in overland flow and leaching may be greater in soils with DPS values that exceed these thresholds than in soils with lower DPS values.     

Solid phosphorus phase in aluminum- and iron-treated biosolids

Stabilization of phosphorus (P) in sewage sludge (biosolids) to reduce water-soluble P concentrations is essential for minimizing P loss from amended soils and maximizing the capacity of the soil to safely serve as an outlet for this waste material. The chemical form at which P is retained in biosolids stabilized by Al(2)(SO(4))(3) x 18H(2)O (alum) or FeSO(4) x 7H(2)O (FeSul) was investigated by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS) and by X-ray diffraction (XRD). Both treatments resulted in the formation of a Ca-P phase, probably brushite. Phosphorus was further retained in the alum-treated biosolids by precipitation of an Al-P phase with an Al/P molar ratio of about 1:1, while in the FeSul-treated biosolids, P was retained by both precipitation with Fe/P molar ratios of 1:1 or 1.5:1, and by adsorption onto newly formed Fe hydroxides exhibiting an Fe/P molar ratio of up to 11:1. All of these mechanisms efficiently reduced P solubility and are crucial in biosolids environmentally safe agronomic beneficial use for this waste product; however, each P phase formed may react differently in the amended soil, depending on soil properties. Thus, the proper P stabilization method would depend on the target soil.     

Polyvalent cation effects on myo-inositol hexakis dihydrogenphosphate enzymatic dephosphorylation in dairy wastewater

Information is needed on organic polyphosphates such as myo-inositol 1,2,3,5/4,6-hexakis dihydrogenphosphate or phytate (IP6) contribution to the sources and sinks of dissolved phosphorus (PO4-P) in the soil-manure-water system. Effects of Na+, Ca2+, Al3+, and Fe3+ and cation to IP6-P mole ratios on the enzymatic dephosphorylation of IP6 were studied to determine controlling mechanisms of dephosphorylation and persistence in manure. Phytate- and PO4-P were analyzed by high-performance liquid chromatography. Phytate dephosphorylation by Aspergillus ficuum (Reichardt) Henn. phytase EC 3.1.3.8 decreases by 50 +/- 3.6 and 40 +/- 4% at pH 4.5 and 6, respectively, as Ca2+ concentrations increase and cation to IP6-P mole ratios reach 6:6. Polyanionic IP6 has a high affinity for Al3+ and Fe3+ and reductions in dephosphorylation average 27 and 32% at a cation to IP6-P mole ratio of 1:6 for Al3+ and Fe3+, respectively, while reaching more than 99% at a mole ratio of 6:6. A phytase-hydrolyzable phosphorus (PHP) fraction is native to ruminant animal manure and is proportional to total solids (TS) concentration in 1 to 100 g L(-1) suspensions. Added phytase, in effect, increases water-extractable P content of manure and the risk of environmental P dispersion. As the bioavailability and ecological effect of IP6-P appear to be regulated not only by pH-controlled enzyme activity but also by the associated counterions, the differential protective effects of cations influence the accuracy of manure PHP fraction estimates and increase phytate resistance to enzymatic dephosphorylation that may lead to its persistence in manure.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

Phosphorus and nitrogen runoff from a forested watershed fertilized with biosolids

Municipal biosolids are typically not used on the steepest of forested slopes in the U.S. Pacific Northwest. The primary concern in using biosolids on steep slopes is movement of biosolids particles and soluble nutrients to surface waters during runoff events. We examined the pattern and extent of P and N runoff from a perennial stream draining a small, forested 21.4-ha watershed in western Washington before and after biosolids application. In this study, we applied biosolids at a rate of 13.5 Mg ha(-1) (700 kg N ha(-1) and 500 kg P ha(-1)) to 40% of the watershed following nearly 1.5 years of pre-application water sampling and 1.5 years thereafter. There was no evidence of direct runoff of P or N from biosolids into surface water. Elevated surface water discharge did not change the concentration of PO4-P, biologically available phosphorus (BAP), bioavailable particulate phosphorus (BPP), or total P nor did it affect the concentration-discharge relationship. Some instances of total P concentrations exceeding the USEPA surface water standard of 0.1 mg L(-1) were observed following biosolids application. However, total P in 27 Creek was predominately in particulate form and not labile, suggesting that detritus moving into the main creek channel and ephemeral drainage courses may be the principal P source. Ammonium N concentrations in runoff water were consistent before and after biosolids application, ranging from below detection limits (0.01 mg L(-1)) to 0.1 mg L(-1); no concentration-discharge relationship existed. Biosolids application changed the 27 Creek concentration-discharge relationship for NO3(-)-N. Before application, no relationship existed. Beginning nine months after biosolids application, increases in discharge were positively related to increases in NO3(-)-N concentrations. Nitrate concentrations in runoff following biosolids application were approximately 10 times less than the USEPA drinking water standard of 10 mg L(-1).     

Odor and gas release from anaerobic treatment lagoons for swine manure

Odor and gas release from anaerobic lagoons for treating swine waste affect air quality in neighboring communities but rates of release are not well documented. A buoyant convective flux chamber (BCFC) was used to determine the effect of lagoon loading rate on measured odor and gas releases from two primary lagoons at a simulated wind speed of 1.0 m s(-1). Concentrations of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), sulfur dioxide (SO2), and nitric oxide (NO) in 50-L air samples were measured. A panel of human subjects, whose sensitivity was verified with a certified reference odorant, evaluated odor concentration, intensity, and hedonic tone. Geometric mean odor concentrations of BCFC inlet and outlet samples and of downwind berm samples were 168 +/- 44 (mean +/- 95% confidence interval), 262 +/- 60, and 114 +/- 38 OU(E) m(-3) (OU(E), European odor unit, equivalent to 123 microg n-butanol), respectively. The overall geometric mean odor release was 2.3 +/- 1.5 OU(E) s(-1) m(-2) (1.5 +/- 0.9 OU s(-1) m(-2)). The live mass specific geometric mean odor release was 13.5 OU(E) s(-1) AU(-1) (animal unit = 500 kg live body mass). Overall mean NH3, H2S, CO2 and SO2 releases were 101 +/- 24, 5.7 +/- 2.0, 852 +/- 307, and 0.5 +/- 0.4 microg s(-1) m(-2), respectively. Nitric oxide was not detected. Odor concentrations were directly proportional to H2S and CO2 concentrations and odor intensity, and inversely proportional to hedonic tone and SO2 concentration (P < 0.05). Releases of NH3, H2S, and CO2 were directly proportional (P < 0.05) to volatile solids loading rate (VSLR).     

Associated release of magnesium and phosphorus from active and abandoned dairy soils

Dairy manure application to soils can result in phosphorus (P)-related degradation of water quality. The P in these manure-impacted soils can be labile even years after abandonment and under conditions normally associated with high P stability. Failure of P to stabilize with time compounds the environmental consequences of dairy manure disposal, especially on sandy soils. The objectives of this study were to compare chemical characteristics of active and abandoned dairy manure-impacted soils and minimally impacted soils and to assess the continuous release of P in relation to sparingly soluble salts using repeated water extractions, X-ray diffraction, and speciation modeling of column leachates. Soil samples from Ap horizons were collected from nine highly manure-impacted (total P > 1000 mg P kg(-1) soil) areas on four active and five abandoned dairies and four minimally impacted soils (total P < 200 mg P kg(-1) soil). Soil extracts were analyzed for electrical conductivity (EC), soluble reactive phosphorus (SRP), Ca, Mg, Na, and K. The EC of the soil solutions decreased as active dairy > abandoned dairy > minimally impacted soils. Release of Mg and SRP were significantly correlated (r2 = 0.68) and did not decline after abandonment; Ca release was not correlated with SRP (r2 = 0.01), and declined significantly (p < 0.05) after abandonment. Speciation data from column leachates suggested that Mg-P phases and/or the most soluble Ca-P phases could control P solution activities. An implication of this study is that P stabilization via crystallization of calcium phosphates (even at near-neutral pH) may be preempted by Mg-P association. Thus, mechanisms to minimize P release may require P-retaining soil amendments or management of animal rations to eliminate Mg-P formation.     

Biochar produced from anaerobically digested fiber reduces phosphorus in dairy lagoons

This study evaluated the use of biochar produced from anaerobic digester dairy fiber (ADF) to sequester phosphorus (P) from dairy lagoons. The ADF was collected from a plugged flow digester, air-dried to <8% water content, and pelletized. Biochar was produced by slow pyrolysis in a barrel retort. The potential of biochar to reduce P in the anaerobic digester effluent (ADE) was assessed in small-scale filter systems through which the effluent was circulated. Biochar sequestered an average of 381 mg L P from the ADE, and 4 g L ADF was captured as a coating on the biochar. There was an increase of total (1.9 g kg), Olsen (763 mg kg), and water-extractable P (914 mg kg) bound to the biochar after 15 d of filtration. This accounted for a recovery of 32% of the P in the ADE. The recovered P on the biochar was analyzed using P nuclear magnetic resonance for P speciation, which confirmed the recovery of inorganic orthophosphate after liquid extraction of the biochar and the presence of inextractable Ca-P in the solid state. The inorganic phosphate was sequestered on the biochar through physical and weak chemical bonding. Results indicate that biochar could be a beneficial component to P reduction in the dairy system.