Long-term phosphorus immobilization by a drinking water treatment residual

Excessive soluble P in runoff is a common cause of eutrophication in fresh waters. Evidence indicates that drinking water treatment residuals (WTRs) can reduce soluble P concentrations in P-impacted soils in the short term (days to weeks). The long-term (years) stability of WTR-immobilized P has been inferred, but validating field data are scarce. This research was undertaken at two Michigan field sites with a history of heavy manure applications to study the longevity of alum-based WTR (Al-WTR) effects on P solubility over time (7.5 yr). At both sites, amendment with Al-WTR reduced water-soluble P (WSP) concentration by >or=60% as compared to the control plots, and the Al-WTR-immobilized P (WTR-P) remained stable 7.5 yr after Al-WTR application. Rainfall simulation techniques were utilized to investigate P losses in runoff and leachate from surface soils of the field sites at 7.5 yr after Al-WTR application. At both sites, amendment with Al-WTR reduced dissolved P and bioavailable P (BAP) by >50% as compared to the control plots, showing that WTR-immobilized P remained nonlabile even 7.5 yr after Al-WTR amendment. Thus, WTR-immobilized P would not be expected to dissolve into runoff and leachate to contaminate surface waters or groundwater. Even if WTR-P is lost via erosion to surface waters, the bioavailability of the immobilized P should be minimal and should have negligible effects on water quality. However, if the WTR particles are destroyed by extreme conditions, P loss to water could pose a eutrophication risk.     

Controlling the fate of roxarsone and inorganic arsenic in poultry litter

A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.     

Phosphorus release from a manure-impacted spodosol: effects of a water treatment residual

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.     

An alum-based water treatment residual can reduce extractable phosphorus concentrations in three phosphorus-enriched coastal plain soils

The accumulation of excess soil phosphorus (P) in watersheds under intensive animal production has been linked to increases in dissolved P concentrations in rivers and streams draining these watersheds. Reductions in water dissolved P concentrations through very strong P sorption reactions may be obtainable after land application of alum-based drinking water treatment residuals (WTRs). Our objectives were to (i) evaluate the ability of an alum-based WTR to reduce Mehlich-3 phosphorus (M3P) and water-soluble phosphorus (WSP) concentrations in three P-enriched Coastal Plain soils, (ii) estimate WTR application rates necessary to lower soil M3P levels to a target 150 mg kg(-1) soil M3P concentration threshold level, and (iii) determine the effects on soil pH and electrical conductivity (EC). Three soils containing elevated M3P (145-371 mg kg(-1)) and WSP (12.3-23.5 mg kg(-1)) concentrations were laboratory incubated with between 0 and 6% WTR (w w(-1)) for 84 d. Incorporation of WTR into the three soils caused a near linear and significant reduction in soil M3P and WSP concentrations. In two soils, 6% WTR application caused a soil M3P concentration decrease to below the soil P threshold level. An additional incubation on the third soil using higher WTR to soil treatments (10-15%) was required to reduce the mean soil M3P concentration to 178 mg kg(-1). After incubation, most treatments had less than a half pH unit decline and a slight increase in soil EC values suggesting a minimal impact on soil quality properties. The results showed that WTR incorporation into soils with high P concentrations caused larger relative reductions in extractable WSP than M3P concentrations. The larger relative reductions in the extractable WSP fraction suggest that WTR can be more effective at reducing potential runoff P losses than usage as an amendment to lower M3P concentrations.     

Drinking water treatment residuals: a review of recent uses

Coagulants such as alum [Al2(SO4)3 x 14H2O], FeCl3, or Fe2(SO4)3 are commonly used to remove particulate and dissolved constituents from water supplies in the production of drinking water. The resulting waste product, called water-treatment residuals (WTR), contains precipitated Al and Fe oxyhydroxides, resulting in a strong affinity for anionic species. Recent research has focused on using WTR as cost-effective materials to reduce soluble phosphorus (P) in soils, runoff, and land-applied organic wastes (manures and biosolids). Studies show P adsorption by WTR to be fast and nearly irreversible, suggesting long-term stable immobilization of WTR-bound P. Because excessive WTR application can induce P deficiency in crops, effective application rates and methods remain an area of intense research. Removal of other potential environmental contaminants [ClO4-, Se(+IV and +VI), As(+III and +V), and Hg] by WTR has been documented, suggesting potential use of WTR in environmental remediation. Although the creation of Al plant toxicity and enhanced Al leaching are concerns expressed by researchers, these effects are minimal at circumneutral soil pH conditions. Radioactivity, trace element levels, and enhanced Mn leaching have also been cited as potential problems in WTR usage as a soil supplement. However, these issues can be managed so as not to limit the beneficial use of WTR in controlling off-site P losses to sensitive water bodies or reducing soil-extractable P concentrations.     

Decreasing lead bioaccessibility in industrial and firing range soils with phosphate-based amendments

In-situ stabilization using phosphate (P) amendments, such as P-based fertilizers and rock, are a potentially cost-effective and minimally disruptive alternative for stabilizing Pb in soils. We examined the effect of time (0-365 d), in vitro extraction pH (1.5 vs. 2.3), and dosage of three P-based amendments on the bioaccessibility (as a surrogate for oral bioavailability) of Pb in 10 soils from U.S. Department of Defense facilities. Initial untreated soil bioaccessibility consistently exceeded the U.S. Environmental Protection Agency default value of 60% relative bioavailability, with higher bioaccessibility consistently observed at an in vitro extraction pH of 1.5 vs. 2.3. Although P-based amendments statistically (P < 0.05) reduced bioaccessibility in many instances, with reductions dependent on the amendment and dosage, large amendment dosages (approximately 20-25% by mass to yield 5% P by mass) were required to reduce average bioaccessibility by approximately 25%. For most amendment combinations, reductions continued to occur for periods up to 1 yr, indicating that the observed reductions were not merely experimental artifacts of the in vitro extraction procedure. Although our results indicated that reductions in Pb bioaccessibility with P amendments are technically feasible, relatively large amendment masses were required to achieve relatively modest reductions in bioaccessibility. The cost and potential environmental implications of adding such large amounts of P may limit the practicality of in situ immobilization for some Pb-contaminated soils, industrial and firing range soils in particular.     

The availability of copper in soils historically amended with sewage sludge, manure, and compost

Metals in soils amended with sewage sludge are typically less available compared with those in soils spiked with soluble metal salts. However, it is unclear if this difference remains in the long term. A survey of copper (Cu) availability was made in soils amended with sewage sludge, manure, and compost, collectively named organic amendments. Paired sets of amended and control soils were collected from 22 field trials where the organic amendments had aged up to 112 yr. Amended soils had higher total Cu concentrations (range, 2-220 mg Cu kg; median, 15 mg Cu kg) and organic C (range, 1-16 g kg; median, 4 g kg) than control soils. All samples were freshly spiked with CuCl, and the toxicity of added Cu to barley was compared between amended and control soils. The toxicity of added Cu was significantly lower in amended soils than in control soil in 15 sets by, on average, a factor of 1.4, suggesting that aged amendments do not largely increase Cu binding sites. The fraction of added Cu that is isotopic exchangeable Cu (labile Cu) was compared between control soils freshly spiked with CuCl and amended soils with both soils at identical total Cu concentrations. Copper derived from amendments was significantly less labile (on average 5.9-fold) than freshly added Cu in 18 sets of soils. This study shows that Cu availability after long-term applications of organic amendments is lower than that of freshly added Cu salts, mainly because of its lower availability in the original matrix and ageing reactions than because of increased metal binding sites in soil.     

Phosphate adsorption by ferrihydrite-amended soils

New technology and approaches for reducing P in runoff from high sediment yield areas are essential due to implementation of increasingly rigorous water quality standards. The objectives of this research were to characterize ferrihydrite (Fe(5)HO(8).4H(2)O) in terms of its ability to adsorb P from soil solutions and relate its P adsorptive capacity to several soil properties that influence P mobility. A naturally occurring ferrihydrite, collected as an Fe oxide sludge by-product from a water treatment facility, was equilibrated with soil samples at equivalent rates of 0, 0.34, 3.36, 16.80, and 33.60 Mg ha(-1) for a 60-d period. Individual 2-g subsamples of each soil were then equilibrated with 0, 5, 10, 20, and 40 mg kg(-1) P in 20 mL of 0.01 M CaCl(2) on a reciprocating shaker for 24 h. After 24 h, P in solution was measured by colorimetric methods, and designated as final P concentrations. The data indicated that the unamended soils with a pH of <6.0 adsorbed, in some cases, 50 times more P than soils with a pH of >7.0. The final P concentrations, averaged for all initial P concentrations and ferrihydrite rates, ranged from 0.09 to 4.63 mg kg(-1), and were most highly correlated with pH (r = 0.844; P < or = 0.01), oxalate-extractable Fe (r = -0.699; P < or = 0.10), and dithionite-extractable Fe (r = -0.639; P < or = 0.10) contents of the unamended soils. In terms of individual soils, correlation coefficients (r) for final P concentrations versus ferrihydrite amendment rates indicated a statistically significant (P < or = 0.001) negative relationship at all initial P concentrations for most A horizons. The r values for the high Fe oxide content B horizon soils did not show a statistically significant response to ferrihydrite additions. The results indicate that P adsorption, in soils amended with ferrihydrite, will be greatest under acid pH conditions below the ferrihydrite zero point of charge (pH 5.77), and low incipient Fe oxide contents.     

Controlled application rate of water treatment residual for agronomic and environmental benefits

Water treatment residuals (WTR) are useful soil amendments to control excessive soluble phosphorus (P) in soils, but indiscriminate additions can result in inadequate control or excessive immobilization of soluble P, leading to crop deficiencies. We evaluated the influence of application rates of an Al-WTR and various P-sources on plant yields, tissue P concentrations, and P uptake and attempted to identify a basis for determining WTR application rates. Bahiagrass (paspalum notatum Fluggae) was grown in a P-deficient soil amended with four P-sources at two application levels (N- and P-based rates) and three WTR rates (0, 10, and 25 g kg(-1) oven dry basis) in a glasshouse pot experiment. The glasshouse results were compared with data from a 2-yr field experiment with similar treatments that were surface applied to an established bahiagrass. Soil P storage capacity (SPSC) values increased with application rate of WTR, and the increase varied with sources of P applied. Soil soluble P concentrations increased as SPSC was reduced, and a change point was identified at 0 mg kg(-1) SPSC in the glasshouse and the field studies. A change point was identified in the bahiagrass yields at a tissue P concentration of 2.0 g kg(-1), corresponding to zero SPSC. Zero SPSC was shown to be an agronomic threshold above which yields and P concentrations of plants declined and below which there is little or no yield response to increased plant P concentrations. Applying P-sources at N-based rates, along with WTR sufficient to give SPSC value of 0 mg kg(-1) SPSC, enhanced the environmental benefits (reduced P loss potential) without negative agronomic impacts.     

Spectroscopic speciation and quantification of lead in phosphate-amended soils

The immobilization of Pb in contaminated soils as pyromorphite [Pb(5)(PO(4))(3)Cl, OH, F] through the addition of various phosphate amendments has gained much attention in the remediation community. However, it is difficult to fully determine the speciation and amount of soil Pb converted to pyromorphite by previously employed methods, such as selective sequential extraction procedures and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, which often lead to erroneous results in these non-equilibrated and heterogeneous systems. Statistical analysis by linear combination fitting (LCF) applied to X-ray absorption fine structure (XAFS) spectroscopic data of Pb-contaminated soil samples relative to known Pb reference material provides direct, in situ evidence of dominate Pb species in the amended soils without chemical or physical disruption to the Pb species as well as a weighted quantification output. The LCF-XAFS approach illustrated that pyromorphite concentration ranged from 0% (control soil) to 45% (1% phosphoric acid amendment, residence time of 32 mo) relative to the total Pb concentration. The Pb speciation in the nonamended control soil included Pb-sulfur species (galena + angelsite = 53%), adsorbed Pb (inner-sphere + outer-sphere + organic-bound = 45%), and Pb-carbonate phases (cerussite + hydrocerussite = 2%). The addition of P promoted pyromorphite formation and the rate of formation increased with increasing P concentration (up to 45%). The supplemental addition of an iron amendment as an iron-rich byproduct with triple superphosphate (TSP) enhanced pyromorphite formation relative to independent TSP amendment of like concentrations (41 versus 29%). However, the amendment of biosolids and biosolids plus TSP observed little pyromorphite formation (1-16% of total Pb), but a significant increase of sorbed Pb was determined by LCF-XAFS.     

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.     

Phosphorus sequestration by chemical amendments to reduce leaching from wastewater applications

Phosphorus-immobilizing amendments can be useful in minimizing P leaching from high P soils that may be irrigated with wastewater. This study tested the P-binding ability of various amendment materials in a laboratory incubation experiment and then tested the best amendment in a field setup using drainage lysimeters. The laboratory experiment involved incubating 100-g samples of soil (72 mg kg(-1) water-extractable phosphorus, WEP) with various amendments at different rates for 63 d at field moisture capacity and 25 degrees C. The amendments tested were alum [Al2SO4)3.14H2O], ferric chloride (FeCl3), calcium carbonate (CaCO3), water treatment residual (WTR), and sugarbeet lime (SBL). Ferric chloride and alum at rates of 1.5 and 3.9 g kg(-1), respectively, were the most effective amendments that decreased WEP to 20 mg kg(-1), below which leaching has previously been shown to be low. Alum (1.3 kg m(-2)), which is less sensitive to redox conditions, was subsequently tested under field conditions, where it reduced WEP concentration in the 0- to 0.15-m layer from 119 mg kg(-1) on Day 0 to 36.1 mg kg(-1) (85% decrease) on Day 41. Lysimeter breakthrough tests using tertiary-treated potato-processing wastewater (mean total phosphorus [TP] = 3.4 mg L(-1)) showed that alum application reduced leachate TP and soluble reactive phosphorus (SRP) concentrations by 27 and 25%, respectively. These results indicate that alum application may be an effective strategy to immobilize P in high P coarse-textured soils. The relatively smaller decreases in TP and SRP in the leachate compared to WEP suggest some of the P may be coming from depths below 0.2 m. Thus, to achieve higher P sequestration, deeper incorporation of the alum may be necessary.     

Enhanced transformation of lead speciation in rhizosphere soils using phosphorus amendments and phytostabilization: an x-ray absorption fine structure spectroscopy investigation

To formulate successful phytostabilization strategies in a shooting range soil, understanding how heavy metals are immobilized at the molecular level in the rhizosphere soil is critical. Lead (Pb) speciation and solubility in rhizosphere soils of five different plant species were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. The EXAFS analysis indicated that Pb occurred as PbCO (37%), Pb sorbed to organic matter (Pb-org: 15%), and Pb sorbed to pedogenic birnessite and/or ferrihydrite (Pb-ox: 36%) in the bulk soil. Comparison of the EXAFS spectra between bulk and rhizosphere soils demonstrated notable differences in fine structure, indicating that Pb species had been modified by rhizosphere processes. The estimated proportion of PbCO (25%) in the buckwheat soil was smaller than the other rhizosphere soils (35-39%). The addition of P significantly reduced Pb solubility in the bulk and rhizosphere soil except in the rhizosphere of buckwheat, for which the Pb solubility was 10-fold greater than in the other P-amended soils. This larger solubility in the buckwheat rhizosphere could not be explained by the total Pb speciation in the soil but was presumably related to the acidifying effect of buckwheat, resulting in a decrease of the soil pH by 0.4 units. The reduced Pb solubility by P amendment resulted from the transformation of preexisting PbCO (37%) into Pb(PO)Cl (26-32%) in the bulk and rhizosphere soils. In the P-amended rhizosphere soils, Pb-org species were no longer detected, and the Pb-ox pool increased (51-57%). The present study demonstrated that rhizosphere processes modify Pb solubility and speciation in P-amended soils and that some plant species, like buckwheat, may impair the efficiency of Pb immobilization by P amendments.     

Occurrence of carbamazepine in soils under different land uses receiving wastewater

Due to its resistance to many wastewater treatment processes, the antiepileptic drug carbamazepine (CBZ) is routinely found in wastewater effluent. Wastewater irrigation is an alternative to stream discharge of wastewater effluent, which utilizes the soil as a tertiary filter to remove excess nutrients and has the potential to remove pharmaceutical compounds. Previous data suggest that CBZ is strongly sorbed to soil; however, it is unknown what its fate is for long periods of irrigation and if land use affects its distribution. Therefore, the objectives of our research were to characterize CBZ concentrations in soils that have been receiving wastewater irrigation for >25 yr under three different land uses: cropped, grassed, and forested. Triplicate soil cores were collected at each of the land uses to a depth of 120 cm. Extractions for CBZ were performed using 5-g soil samples and 20 mL of acetonitrile. The extracted solutions were analyzed on a liquid chromatograph tandem mass spectrometer. The samples were also analyzed for supporting information such as organic carbon, pH, and electrical conductivity. Results suggest that there is accumulation of the CBZ in the surface soils, which have the highest organic carbon content. Average concentrations of CBZ in the surface soils were 4.92, 2.9, and 1.92 ng g, for the forested, grassed, and cropped land uses, respectively. The majority of the CBZ was found in the upper 30 cm of the profile. Our results suggest that the soils adsorb CBZ and slow its movement into groundwater, compared to the movement of nonadsorbed chemicals.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Prediction of radionuclide aging in soils from the Chernobyl and Mediterranean areas

The aging of soil-pollutant interaction, which may lead to an increase in pollutant fixation, is the main driving force in the natural attenuation of contaminated soils. Here a test was evaluated to predict the aging of radiostrontium and radiocesium in soils from the Chernobyl and Mediterranean areas. After contamination, soils were maintained at various temperatures for up to 12 mo, with or without drying-wetting (DW) cycles. Changes in the quantity of radionuclide reversibly sorbed over time were monitored using an extraction test (1 mol L(-1) NH(4)Cl; 10 mL g(-1); 16 h). The fixed fraction could not be predicted from soil properties controlling the sorption step. Aging was not as relevant for Sr as for Cs. The time elapsed since contamination was the main factor responsible for the slight (up to 1.3-fold) decreases in Sr extraction yields. The additional effect of DW cycles was negligible. Instead, all factors accelerated Cs aging due to the enhancement of Cs trapping by clay interlayer collapse, with up to 20-fold increases in Cs fixation. The DW cycles also caused secondary effects on the Cs-specific sorption pool, which were beneficial or detrimental depending on the soil type. Extraction yields from laboratory aged samples agreed with those from field samples taken a few years after the Chernobyl accident. These results confirm the prediction capacity of the laboratory test and its usefulness in risk assessment exercises and in the design of intervention actions, particularly because neither fixation nor aging were related to the soil properties, such as clay content.     

Assessing effects of aerobic and anaerobic conditions on phosphorus sorption and retention capacity of water treatment residuals

Water treatment residuals (WTRs) are the by-products of drinking water clarification processes, whereby chemical flocculants such as alum or ferric chloride are added to raw water to remove suspended clay particles, organic matter and other materials and impurities. Previous studies have identified a strong phosphorus (P) fixing capacity of WTRs which has led to experimentation with their use as P-sorbing materials for controlling P discharges from agricultural and forestry land. However, the P-fixing capacity of WTRs and its capacity to retain sorbed P under anaerobic conditions have yet to be fully demonstrated, which is an issue that must be addressed for WTR field applications. This study therefore examined the capacity of WTRs to retain sorbed P and sorb further additional P from aqueous solution under both aerobic and anaerobic conditions. An innovative, low cost apparatus was constructed and successfully used to rapidly establish anoxic conditions in anaerobic treatments. The results showed that even in treatments with initial solution P concentrations set at 100 mg l(-1), soluble reactive P concentrations rapidly fell to negligible levels (due to sorption by WTRs), while total P (i.e. dissolved + particulate and colloidal P) was less than 3 mg l(-1). This equated to an added P retention rate of >98% regardless of anaerobic or aerobic status, indicating that WTRs are able to sorb and retain P in both aerobic and anaerobic conditions.     

Enzymatic hydrolysis of organic phosphorus in swine manure and soil

Organic phosphorus (Po) exists in many chemical forms that differ in their susceptibility to hydrolysis and, therefore, bioavailability to plants and microorganisms. Identification and quantification of these forms may significantly contribute to effective agricultural P management. Phosphatases catalyze reactions that release orthophosphate (Pi) from Po compounds. Alkaline phosphatase in tris-HCl buffer (pH 9.0), wheat (Triticum aestivum L.) phytase in potassium acetate buffer (pH 5.0), and nuclease P1 in potassium acetate buffer (pH 5.0) can be used to classify and quantify Po in animal manure. Background error associated with different pH and buffer systems is observed. In this study, we improved the enzymatic hydrolysis approach and tested its applicability for investigating Po in soils, recognizing that soil and manure differ in numerous physicochemical properties. We applied (i) acid phosphatase from potato (Solanum tuberosum L.), (ii) acid phosphatases from both potato and wheat germ, and (iii) both enzymes plus nuclease P1 to identify and quantify simple labile monoester P, phytate (myo-inositol hexakis phosphate)-like P, and DNA-like P, respectively, in a single pH/buffer system (100 mM sodium acetate, pH 5.0). This hydrolysis procedure released Po in sequentially extracted H2O, NaHCO3, and NaOH fractions of swine (Sus scrofa) manure, and of three sandy loam soils. Further refinement of the approach may provide a universal tool for evaluating hydrolyzable Po from a wide range of sources.     

Phosphorus retention mechanisms of a water treatment residual

Water treatment residuals (WTRs) are a by-product of municipal drinking water treatment plants and can have the capacity to adsorb tremendous amounts of P. Understanding the WTR phosphorus adsorption process is important for discerning the mechanism and tenacity of P retention. We studied P adsorbing mechanism(s) of an aluminum-based [Al2(SO4)3 x 14H2O] WTR from Englewood, CO. In a laboratory study, we shook mixtures of P-loaded WTR for 1 to 211 d followed by solution pH analysis, and solution Ca, Al, and P analysis via inductively coupled plasma atomic emission spectroscopy. After shaking periods, we also examined the solids fraction by X-ray diffraction (XRD) and electron microprobe analysis using wavelength dispersive spectroscopy (EMPA-WDS). The shaking results indicated an increase in pH from 7.2 to 8.2, an increase in desorbed Ca and Al concentrations, and a decrease in desorbed P concentration. The pH and desorbed Ca concentration increases suggested that CaCO3 controlled Ca solubility. Increased desorbed Al concentration may have been due to Al(OH)4 formation. Decreased P content, in conjunction with the pH increase, was consistent with calcium phosphate formation or precipitation. The system appeared to be undersaturated with respect to dicalcium phosphate (DCP; CaHPO4) and supersaturated with respect to octacalcium phosphate [OCP; Ca4H(PO4)3 x 2.5H2O]. The Ca and Al increases, as well as OCP formation, were supported by MINTEQA2 modeling. The XRD and EMPA-WDS results for all shaking times, however, suggested surface P chemisorption as an amorphous Al-P mineral phase.     

Increase in phosphorus losses from grassland in response to Olsen-P accumulation

The Olsen-P status of grazed grassland (Lolium perenne L.) swards in Northern Ireland was increased over a 5-yr period (March 2000 to February 2005) by applying different rates of P fertilizer (0, 10, 20, 40, or 80 kg P ha(-1) yr(-1)) to assess the relationship between soil P status and P losses in land drainage water and overland flow. Plots (0.2 ha) were hydrologically isolated and artificially drained to v-notch weirs, with flow proportional monitoring of drainage water and overland flow. Annually, the collectors for overland flow intercepted between 11 and 35% of the surplus rainfall. Single flow events accounted for up to 52% of the annual dissolved reactive phosphorus (DRP) load. The Olsen-P status of the soil influenced DRP and total phosphorus (TP) concentrations in land drainage water and overland flow. Annual TP loss was highly variable and ranged from 0.19 to 1.55 kg P ha(-1) yr(-1) for the plot receiving no P fertilizer and from 0.35 to 2.94 kg P ha(-1) yr(-1) for the plot receiving 80 kg P ha(-1) yr(-1). Despite the Olsen-P status in the soils ranging from 22 to 99 mg P kg(-1), after 5 yr of fertilizer P applications it was difficult to identify a clear Olsen-P concentration at which P losses increased. Any relationship was confounded by annual variability of hydrologic events and flows and by hydrologic differences between plots. Withholding P fertilizer for over 5 yr was not long enough to lower P losses or to have an adverse effect on herbage P concentrations.