Restoring Ecosystem Function in Degraded Urban Soil Using Biosolids, Biosolids Blend, and Compost.

Many soils at former industrial sites are degraded. The objective of this research was to determine the ability of compost, biosolids, and biosolids blends to improve soil ecosystem function with minimal potential impact to surface water. Treatments rototilled into the top 12.5 cm of soil were biosolids at 202 Mg ha; biosolids at 404 Mg ha; compost at 137 Mg ha; or a blend consisting of biosolids applied at 202 Mg ha, drinking water treatment residual, and biochar. Rainfall runoff from experimental plots was collected for 3 yr. One year after soil amendments were incorporated, a native seed mix containing grasses, legumes, and forbs was planted. Soil amendments improved soil quality and nutrient pools, established a dense and high-quality vegetative cover, and improved earthworm reproductive measures. Amendments increased soil enzymatic activities that support soil function. Biosolids treatments increased the Shannon-Weaver Diversity Index for grasses. For the forbs group, control plots had the lowest diversity index and the biosolids blend had the highest diversity index. Biosolids and compost increased the number of earthworm juveniles. In general, biosolids outperformed compost. Biosolids increased N and P in rainfall runoff more than compost before vegetation was established. Several microconstituents (i.e., pharmaceutical and personal care products) were detected in runoff water but at concentrations below the probable no-effect levels and therefore should pose little impact to the aquatic environment. Future restoration design should ensure that runoff control measures are used to control sediment loss from the restored sites at least until vegetation is established.

In vitro bioaccessibility and in vivo relative bioavailability in 12 contaminated soils: Method comparison and method development.

Previous studies have established in vivo-in vitro correlations (IVIVC) between arsenic (As) relative bioavailability (RBA) and bioaccessibility in contaminated soils. However, their ability to predict As-RBA in soils outside the models is unclear. In this study, As bioaccessibility and As-RBA in 12 As-contaminated soils (22.2-4172 mg kg(-1) As) were measured using five assays (SBRC, IVG, DIN, PBET, and UBM) and a mouse blood model. Arsenic RBA in the soils ranged from 6.38 ± 2.80% to 73.1 ± 17.7% with soils containing higher extractable Fe showing lower values. Arsenic bioaccessibility varied within and between assays. Arsenic bioaccessibility was used as input values into established IVIVC to predict As-RBA in soils. There were significant differences between predicted and measured As-RBA for the 12 soils, illustrating the inability of established IVIVC to predict As-RBA in those contaminated soils. Therefore, a new IVIVC was established by correlating measured As-RBA and As bioaccessibility for the 12 soils. The strength of the predictive models varied from r(2) = 0.50 for PBET to r(2) = 0.83 for IVG, with IVG assay providing the best prediction of As-RBA. When IVIVC were compared to those of Juhasz et al. (2014a), slopes of the relationships were significantly higher possibly due to different As-RBA measurements. Our research showed that IVG has potential to measure As bioavailability in contaminated soils from China though UBM and SBRC assays were also suitable. More research is needed to verify their suitability to predict As-RBA in soils for refining health risk assessment.

Using the mehlich-3 soil test as an inexpensive screening tool to estimate total and bioaccessible lead in urban soils.

In cities nationwide, urban agriculture has been put on hold because of the high costs of soil testing for historical contaminants such as lead (Pb). The Mehlich-3 soil test is commonly used to determine plant available nutrients, is inexpensive, and has the potential to estimate trace metals in urban soil. The objectives of this study are to evaluate the ability of the Mehlich-3 to estimate total Pb and bioaccessible Pb in vacant residential lots. Total and bioaccessible Pb were determined in 68 vacant residential lots in Cleveland, OH, using standard USEPA Method 3051A and the Relative Bioaccessibility Leaching Procedure (RBALP), respectively. The Mehlich-3 soil test was used to determine extractable Pb, and the results show Mehlich-3 was strongly correlated with total and bioaccessible Pb. The Mehlich-3 soil test could be used as a screening tool to not only estimate total Pb (slope 1.73, = 0.970) but also to estimate bioaccessible Pb when using RBALP at pH 1.5 (slope 1.67, = 0.975) and RBALP at pH 2.5 (slope 1.15, = 0.938). Additional samples were collected from the Thackeray Avenue site in Cleveland, OH, to demonstrate the ability of the Mehlich-3 soil test to screen soil for Pb. The results from the Thackeray site show good agreement between Mehlich-3 and the standard USEPA methods. A screening protocol for urban vacant residential lots using the Mehlich-3 soil test is proposed.

Influence of soil geochemical and physical properties on chromium(VI) sorption and bioaccessibility.

The Department of Defense (DoD) is faced with the daunting task of possible remediation of numerous soil-Cr(VI) contaminated sites throughout the continental U.S. The primary risk driver at these sites is hand-to-mouth ingestion of contaminated soil by children. In the following study we investigate the impact of soil geochemical and physical properties on the sorption and bioaccessibility of Cr(VI) in a vast array of soils relevant to neighboring DoD sites. For the 35 soils used in this study, A-horizon soils typically sorbed significantly more Cr(VI) relative to B-horizon soils. Multiple linear regression analysis suggested that Cr(VI) sorption increased with increasing soil total organic C (TOC) and decreasing soil pH. The bioaccessibility of total Cr (CrT) and Cr(VI) on the soils decreased with increasing soil TOC content. As the soil TOC content approached 0.4%, the bioaccessibility of soil bound Cr systematically decreased from approximately 65 to 10%. As the soil TOC content increased from 0.4 to 4%, the bioaccessibility of Cr(VI) and CrT remained relatively constant at approximately 4% and 10%, respectively. X-ray absorption near edge structure (XANES) spectroscopy suggested that Cr(VI) reduction to Cr(III) was prevalent and that the redox transformation of Cr(VI) increased with increasing soil TOC. XANES confirmed that nearly all bioaccessible soil Cr was the Cr(VI) moiety. Multiple linear regression analysis suggested that the bioaccessibility of Cr(VI) and its reduced counterpart Cr(III), decreased with increasing soil TOC and increasing soil pH. This is consistent with the observation that the reduction reaction and formation of Cr(III) increased with increasing soil TOC and that Cr(III) was significantly less bioaccessible relative to Cr(VI). The model was found to adequately describe CrT bioaccessibility in soils from DoD facilities where Cr(VI) contaminated sites were present. The results of this study illustrate the importance of soil properties on Cr(VI) sorption and bioassessability and help define what soil types have the greatest risk associated with Cr(VI) exposure.

Partitioning species variability from soil property effects on phytotoxicity: ECx normalization using a plant contaminant sensitivity index.

Soil properties mitigate hazardous effects of contaminants through soil chemical sequestration and should be considered when evaluating ecological risk from terrestrial contamination. Empirical models that quantify relationships between soil properties and toxicity to ecological receptors are necessary for site-specific adjustments to ecological risk assessments. However, differential sensitivities of test organisms in dose-response studies may limit the utility of such models. We present a novel approach to toxicity estimation that partitions the effect of differential sensitivities of test organisms from that of soil chemical/physical properties. Five soils that ranged in selected properties were spiked with five concentrations of sodium arsenate. Bioassays were conducted where above ground dry matter growth and the corresponding tissue arsenic concentrations were evaluated for three terrestrial plants (Alfalfa, Medicago sativa L.; Perennial ryegrass, Lolium perrene L.; and Japanese millet, Echinochloa crusgalli L.). Estimates were combined into a plant contaminant sensitivity index (PCSI) and used to normalize phytotoxicity parameters to the most sensitive species (i.e., alfalfa) where necessary. Simple linear regression and ANCOVA indicated a 36.5% increase in the explanatory power of the modifying effects of soil properties on phytotoxicity when differential arsenate sensitivities were accounted for by PCSI (r(2) = 0.477-0.833). Normalization of ecotoxicity parameters by PCSI is a seemingly effective approach to quantify the modifying effects of soil properties on phytotoxicity endpoints when it is of interest to consider multiple plant species (or varieties within a species) with differential sensitivities to experimental contaminants.

Field test of in situ soil amendments at the Tar Creek National Priorities List Superfund site.

A range of soil amendments including diammonium phosphate fertilizer (DAP), municipal biosolids (BS), biosolids compost, and Al- and Fe-based water treatment residuals were tested on Pb-, Zn-, and Cd-contaminated yard soils and tailings at the Tar Creek NPL site in Oklahoma to determine if amendments could restore a vegetative cover and reduce metal availability in situ. For the yard soils, all amendments reduced bioaccessible (assessed with a physiologic-based extraction method) Pb, with reductions ranging from 35% (BS+Al, DAP 0.5%, DAP+Compost+Al) to 57% (Compost+Al). Plant Zn (Cynadon dactylon L.) and NH4 NO3-extractable Cd and Zn were also reduced by a number of amendments. For the tailings, all amendments excluding BS reduced bioaccessible Pb, with the largest reductions observed in the DAP 3% and DAP3%+BS treatments (75 and 84%). Plant growth was suppressed in all treatments that contained DAP for the first season, with the highest growth in the treatments that included compost and biosolids. In the second year, growth was vigorous for all treatments. Plant Zn and Cd and extractable metal concentration were also reduced. A number of treatments were identified that reduced bioaccessible Pb and sustained a healthy plant with reduced metal concentrations. For the yard soil, Compost+Al was the most effective treatment tested. For the tailings, BS+DAP 1% was the most effective treatment tested. These results indicate that in situ amendments offer a remedial alternative for the Tar Creek site.

Screening of human enteric microorganisms for potential biotransformation of polycyclic aromatic hydrocarbons.

This study examined the potential for metabolism of select polycyclic aromatic hydrocarbons (PAH) by human enteric microorganisms. Experiments were performed under anaerobic conditions with various combinations of enteric microbial suspensions, PAH concentrations, nutrient mixtures, and time courses. No PAH metabolites were detected upon GC-TOF-MS analysis of samples digested by tetramethylammonium hydroxide thermochemolysis. No mineralization of (14)C-labeled phenanthrene was observed. These results suggest the lack of partial or complete metabolism of PAHs by enteric microorganisms and therefore the absence of major bioactivation pathways that would expose intestinal lining to potentially carcinogenic PAH metabolites.

Use of drinking water treatment residuals as a potential best management practice to reduce phosphorus risk index scores.

The P risk index system has been developed to identify agricultural fields vulnerable to P loss as a step toward protecting surface water. Because of their high Langmuir phosphorus adsorption maxima (P(max)), use of drinking water treatment residuals (WTRs) should be considered as a best management practice (BMP) to lower P risk index scores. This work discusses three WTR application methods that can be used to reduce P risk scores: (i) enhanced buffer strip, (ii) incorporation into a high soil test phosphorus (STP) soil, and (iii) co-blending with manure or biosolids. The relationship between WTR P(max) and reduction in P extractability and runoff P was investigated. In a simulated rainfall experiment, using a buffer strip enhanced with 20 Mg WTR ha(-1), runoff P was reduced by from 66.8 to 86.2% and reductions were related to the WTR P(max). When 25 g kg(-1) WTR was incorporated into a high STP soil of 315 mg kg(-1) determined using Mehlich-3 extraction, 0.01 M calcium chloride-extractable phosphorus (CaCl(2)-P) reductions ranged from 60.9 to 96.0% and were strongly (P < 0.01) related to WTR P(max). At a 100 g kg(-1) WTR addition, Mehlich 3-extractable P reductions ranged from 41.1 to 86.7% and were strongly (P < 0.01) related to WTR P(max). Co-blending WTR at 250 g kg(-1) to manure or biosolids reduced CaCl(2)-P by >75%. The WTR P(max) normalized across WTR application rates (P(max) x WTR application) was significantly related to reductions in CaCl(2)-P or STP. Using WTR as a P risk index modifying factor will promote effective use of WTR as a BMP to reduce P loss from agricultural land.

A method for determining the phosphorus sorption capacity and amorphous aluminum of aluminum-based drinking water treatment residuals.

A high amorphous aluminum or iron oxide content in drinking water treatment residuals (WTRs) can result in a high phosphorus (P) sorption capacity. Therefore, WTR may be used beneficially to adsorb P and reduce P loss to surface or ground water. The strong relationship between acid ammonium oxalate-extractable aluminum (Al(ox)) and Langmuir phosphorus adsorption maximum (P(max)) in WTR could provide a useful tool for determining P(max) without the onus of the multipoint batch equilibrations necessary for the Langmuir model. The objectives of this study were to evaluate and/or modify an acid ammonium oxalate extraction of Al(ox) and the experimental conditions used to generate P adsorption isotherms to strengthen the relationship between Al(ox) and P(max). The oxalate extraction solution to WTR ratio varied from 40:1, 100:1, and 200:1. Batch equilibration conditions were also varied. The WTR particle size was reduced from <2 mm to <150 microm, and batch equilibration was extended from 17 h to 6 d. Increasing the solution to WTR ratio to 100:1 extracted significantly greater Al(ox) at levels of >50 mg Al kg(-1). No additional increase was found at 200:1. Reducing WTR particle size from <2 mm to <150 microm increased P(max) 2.46-fold. Extending the equilibration time from 17 h to 6 d increased P(max) by a mean of 5.83-fold. The resulting empirical regression equation between the optimized Al(ox) and P(max) (r(2) = 0.91, significant at the 0.001 probability level) may provide a tool to estimate the P(max) of Al-based WTR simply by measuring Al(ox). The accurate determination of WTR P(max) and Al(ox) is essential in using WTR effectively to reduce P loss in runoff or to reduce the solubility of P in agricultural soils or organic waste materials (biosolids, manure).

Sustainable land application: an overview.

Man has land-applied societal nonhazardous wastes for centuries as a means of disposal and to improve the soil via the recycling of nutrients and the addition of organic matter. Nonhazardous wastes include a vast array of materials, including manures, biosolids, composts, wastewater effluents, food-processing wastes, industrial by-products; these are collectively referred to herein as residuals. Because of economic restraints and environmental concerns about land-filling and incineration, interest in land application continues to grow. A major lesson that has been learned, however, is that the traditional definition of land application that emphasizes applying residuals to land in a manner that protects human and animal health, safeguards soil and water resources, and maintains long-term ecosystem quality is incomplete unless the earning of public trust in the practices is included. This overview provides an introduction to a subset of papers and posters presented at the conference, "Sustainable Land Application," held in Orlando, FL, in January 2004. The USEPA, USDA, and multiple national and state organizations with interest in, and/or responsibilities for, ensuring the sustainability of the practice sponsored the conference. The overriding conference objectives were to highlight significant developments in land treatment theory and practice, and to identify future research needs to address critical gaps in the knowledge base that must be addressed to ensure sustainable land application of residuals.

Trace element chemistry in residual-treated soil: key concepts and metal bioavailability.

Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are important sinks for trace elements in soil-residual systems. The pH of the soil-residual system is often the most important chemical property governing trace element sorption, precipitation, solubility, and availability. Trace element phytoavailability in residual-treated soils is often estimated using soil extraction methods. However, spectroscopic studies show that sequential extraction methods may not be accurate in perturbed soil-residual systems. Plant bioassay is the best method to measure the effect of residuals on phytoavailability. Key concepts used to describe phytoavailability are (i) the salt effect, (ii) the plateau effect, and (iii) the soil-plant barrier. Metal availability in soil from metal-salt addition is greater than availability in soil from addition of metal-containing residuals. Plant metal content displays plateaus at high residual loadings corresponding to the residual's metal concentration and sorption capacity. The soil-plant barrier limits transmission of many trace elements through the food chain, although Cd (an important human health concern) can bypass the soil-plant barrier. Results from many studies that support these key concepts provide a basis of our understanding of the relationship between trace element chemistry and phytoavailability in residual-treated soils. Research is needed to (i) determine mechanisms for trace element retention of soil-residual systems, (ii) determine the effect of residuals on ecological receptors and the ability of residuals to reduce ecotoxicity in metal-contaminated soil, and (iii) predict the long-term bioavailability of trace elements in soil-residual systems.

Validation of the in vitro gastrointestinal (IVG) method to estimate relative bioavailable lead in contaminated soils.

The effect of the dosing vehicle (e.g., dough) on the ability of an in vitro gastrointestinal (IVG) method to predict relative bioavailable Pb associated with soil ingestion was evaluated. Bioaccessible Pb determined by the IVG method was compared with relative bioavailable Pb measured from dosing trials using juvenile swine for 18 contaminated soils ranging from 1270 to 14200 mg Pb kg(-1). Bioaccessible Pb was measured in the IVG gastric extraction (GE) and intestinal extraction (IE) solutions. Mean bioaccessible Pb values were 32.2% for GE without dough, 23.0% for GE with dough, 1.06% for IE without dough, and 0.56% for IE with dough. It is possible that phytic acid associated with the dough addition decreased bioaccessible Pb. In vivo relative bioavailable Pb ranges for different swine tissues were 1 to 87% for blood, 0 to 110% for liver, 1 to 124% for kidney, and 0.04 to 94% for bone. Strong linear relationships between IVG GE Pb with dough (r > 0.76, P < 0.0002), IVG IE Pb with dough (r > 0.56, P < 0.015), and IVG GE Pb without dough (r > 0.81, P < 0.0001) and in vivo bioavailable Pb as estimated with blood, kidney, liver, and bone were found. Inexpensive in vitro methods may be useful in providing an estimate of the variability in relative bioavailable Pb at a single study site. The IVG method can be used to estimate relative bioavailable Pb, As, and Cd in contaminated soil.

Evaluation of chemical immobilization treatments for reducing heavy metal transport in a smelter-contaminated soil.

Three chemical immobilization materials, agricultural limestone (AL), mineral rock phosphate (RP), and diammonium phosphate (DAP), were evaluated using solute transport experiments to determine their ability to reduce subsurface heavy metal transport in a smelter contaminated soil. Percent reductions in metals transported were based on comparison with cumulative totals of metal species eluted through 60 pore volumes from an untreated soil. Reductions of metal eluted from the AL treatment were 55% for Cd, 45.2% for Pb, and 21.9% for Zn. Rock phosphate mixed with soil at 60 and 180 g kg(-1) was generally ineffective for reducing Cd, Pb, and Zn elution with <27% reduction for Cd, Pb, and Zn. Rock phosphate placed under contaminated soil as a reactive barrier (i.e. layered RP) at 180 g kg(-1) reduced Cd 53% and Zn 24%, and was the most efficient treatment for reducing Pb (99.9%) transport. DAP treatments were superior to all other materials for reducing Cd and Zn elution with reduction >77% for Zn and >91% for Cd from the 90 g DAP kg(-1) treatment. Increasing DAP from 10 to 90 g kg(-1) increased total arsenic released from 0.13 to 29.5 mg kg(-1) and total P eluted from 2.31 to 335 mg. DAP at 10 g kg(-1) was the most effective treatment for immobilizing the combination of Cd, Pb, and Zn, with reductions of 94.6, 98.9, and 95.8%, respectively.

Chemical extraction methods to assess bioavailable arsenic in soil and solid media.

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.

Redox effects on resin extraction of herbicides from soil.

Relative soil aeration affects the surfaces upon which pesticides adsorb and non-ionic resins offer a means of observing and evaluating this factor. A non-ionic resin extractor, developed for pesticide extraction under reducing conditions, was used to adsorb a fraction of the reversibly adsorbed (active portion) herbicides. The extractor consists of cleaned XAD-2 resin encased in a dialysis membrane composed of regenerated cellulose. Anaerobiosis was achieved by incubating soil suspensions with glucose under a 95% N(2)-5% H(2) environment until the redox potential reached -150 mV. Nine soils with a range of physical and chemical characteristics were examined for atrazine, metribuzin, and alachlor content. Amounts of atrazine, metribuzin, and alachlor extracted from soil ranged to 100, 140, and 75 ng g(-1), respectively. Resin extractions (RE) conducted under aerobic conditions recovered about 25-50% of the pesticide extractable with conventional solid phase solvent extraction at 60 degrees C (SPE(60)). Under anaerobic conditions, equal amounts of atrazine were extracted with RE and SPE(60). Slightly less metribuzin was recovered under anaerobic extraction with the exception of those soils lacking detectable amounts by SPE(60). Larger amounts of alachlor were extracted with resins under anaerobic conditions than under aerobic conditions but the amounts were not correlated with those determined by SPE(60). Large amounts of soil organic matter were solublized under anaerobiosis and smaller molecular weight material was extracted with the herbicides. The nature and amounts of co-extracted organic matter varied among soils. RE directly from soil suspensions enabled simultaneous determination of all three herbicides.

Bioavailability of biosolids molybdenum to soybean grain.

Legumes grown in biosolids-amended soils and then fed to ruminants can represent problematic sources of molybdenum (Mo), but few field data are available to quantify the risk. We used a set of fields amended to high cumulative biosolids Mo loads (>18 kg ha(-1)) over 27 yr to generate additional data. Soybean [Glycine max (L.) Merr.] was grown on 29 fields (pH values>6.8) amended to a wide range of soil Mo loads. Soybean grain harvested from each field was analyzed for Mo and the concentrations regressed against soil Mo loads estimated from actual soil Mo concentrations in the 0- to 15-cm depth. Slopes of such linear regressions represent uptake coefficients (UC values) used by the USEPA to assess risk of biosolids Mo to ruminants fed forage grown on biosolids-amended land. The UC value for all 29 fields was estimated as 1.66, which agrees with the few soybean grain data in the literature. The UC value, however, is well below a conservative UC value of 4, recently recommended for all fresh legume materials fed to cattle. Soybean grain can contain high concentrations of Mo (>10 mg kg(-1)) and have low (<2:1) Cu to Mo ratios, which can exacerbate molybdenosis problems in cattle. However, soybean grain normally constitutes only -10% of dairy cattle diet, and other constituents (e.g., corn grain, stover, mineral supplements) are sufficient, or can be manipulated, to control molybdenosis.

Characterization of drinking water treatment residuals for use as a soil substitute.

The beneficial use of drinking water treatment residuals (WTRs) as a potential source of topsoil for land reclamation was evaluated. Seventeen WTRs were characterized for use as soil substitutes by comparing chemical and physical properties and plant nutrients of the WTRs with soil. A tomato (Lycopersicon esculentum) bioassay was performed to determine the ability of soil chemical tests to measure WTR phosphorus (P) adequacy. The WTR chemical and physical properties were typically adequate for crop growth. None of the WTRs were considered unsuitable as soil substitutes based on plant nutrients, with the exception of P. Tomato vegetative yield and tissue P were poor either because of phytotoxic nitrite-nitrogen (NO2-N) (> 10 mg/kg) generated during the bioassay or because of WTR P deficiency. Limited data suggest that WTRs with NO2-N less than 10 mg/kg and Olsen P greater than 50 mg/kg, water soluble P greater than 580 micrograms/L, or Mehlich III P greater than 54 mg/kg support growth but still produce inadequate tissue P in tomatoes.

Assessment of metal availability in smelter soil using earthworms and chemical extractions.

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.

Chemical immobilization of lead, zinc, and cadmium in smelter-contaminated soils using biosolids and rock phosphate.

Chemical immobilization, an in situ remediation method where inexpensive chemicals are used to reduce contaminant solubility in contaminated soil, has gained attention. We investigated the effectiveness of lime-stabilized biosolid (LSB), N-Viro Soil (NV), rock phosphate (RP), and anaerobic biosolid (AB) to reduce extractability and plant and gastrointestinal (GI) bioavailability in three Cd-, Pb-, and Zn-contaminated soils from smelter sites. Treated (100 g kg(-1) soil) and control soils were incubated at 27 degrees C and -0.033 MPa (0.33 bar) water content for 90 d. The effect of soil treatment on metal extractability was evaluated by sequential extraction, on phytoavailability by a lettuce bioassay (Lactuca sativa L.), on human GI availability of Pb from soil ingestion by the Physiologically Based Extraction Test. The largest reductions in metal extractability and phytoavailability were from alkaline organic treatments (LSB and NV). Phytotoxic Zn [1188 mg Zn kg(-1) extracted with 0.5 M Ca(NO3)2] in Blackwell soil (disturbed soil) was reduced by LSB, NV, and RP to 166, 25, and 784 mg Zn kg(-1), respectively. Rock phosphate was the only treatment that reduced GI-available Pb in both gastric and intestinal solutions, 23 and 92%, respectively. Alkaline organic treatments (LSB, NV) decreases Cd transmission through the food chain pathway, whereas rock phosphate decreases risk from exposure to Pb via the soil ingestion pathway. Alkaline organic treatments can reduce human exposure to Cd and Pb by reducing Zn phytotoxicity and revegetation of contaminated sites.

Use of diammonium phosphate to reduce heavy metal solubility and transport in smelter-contaminated soil.

Phosphate treatments can reduce metal dissolution and transport from contaminated soils. However, diammonium phosphate (DAP) has not been extensively tested as a chemical immobilization treatment. This study was conducted to evaluate DAP as a chemical immobilization treatment and to investigate potential solids controlling metal solubility in DAP-amended soils. Soil contaminated with Cd, Pb, Zn, and As was collected from a former smelter site. The DAP treatments of 460, 920, and 2300 mg P kg-1 and an untreated check were evaluated using solute transport experiments. Increasing DAP decreased total metal transported. Application of 2300 mg P kg-1 was the most effective for immobilizing Cd, Pb, and Zn eluted from the contaminated soil. Metal elution curves fitted with a transport model showed that DAP treatment increased retardation (R) 2-fold for Cd, 6-fold for Zn, and 3.5-fold for Pb. Distribution coefficients (Kd) increased with P application from 4.0 to 9.0 L kg-1 for Cd, from 2.9 to 10.8 L kg-1 for Pb, and from 2.5 to 17.1 L kg-1 for Zn. Increased Kd values with additional DAP treatment indicated reduced partitioning of sorbed and/or precipitated metal released to mobile metal phases and a concomitant decrease in the concentration of mobile heavy metal species. Activity-ratio diagrams indicated that DAP decreased solution Cd, Pb, and Zn by forming metal-phosphate precipitates with low solubility products. These results suggest that DAP may have potential for protecting water resources from heavy metal contamination near smelting and mining sites.