A desorption-dissolution model for metal release from polluted soil under reductive conditions

Various natural or provoked situations can cause significant variations in redox conditions that can induce reductive dissolution of soil components. When this happens, heavy metals that may be bound to solid phases are released. A surface desorption-dissolution model, which takes into account the effect of reductive conditions on surface site density, was established. This model is based on conventional reactions of surface hydroxyl groups, surface complexation reactions with cations and double-layer theory. The solid dissolution rate was taken into account, by following changes in total surface site number (i.e., cation exchange capacity [CEC]) under reductive conditions. This term was introduced in an electrostatic desorption model. Curves obtained by this calculation provided a good fit of experimental data as shown by statistical parameters. Experimental data corresponded to Pb and Cd released from a cultivated soil under reductive conditions induced by sodium ascorbate.     

Removal of trichloroethylene from soil using the hydration of calcium oxide

Quicklime addition to soil at a remediation site was observed to sufficiently reduce TCE levels, but the cause of the removal could not be confirmed with the field data collected. Potential mechanisms for CaO treatment of trichloroethylene (TCE) in soil include degradation and volatilization. Since earlier studies found TCE degradation to occur during the hydration of CaO under conditions where volatilization was limited, research was conducted on mechanisms of TCE removal from soil by CaO application under conditions where volatilization was allowed to occur. TCE volatilization in soil treated with 0%, 5%, 10%, and 20% CaO doses was measured in experiments where the degree of volatilization could be tracked. The total TCE removal from soil spiked with TCE at CaO doses from 5% to 20% ranged from 97% to 99% of the initial TCE mass. Volatilization accounted for 64.4-92.5% of the TCE removal, with unrecovered TCE and TCE degradation accounting for the remaining fraction. The greater heat encountered with higher CaO doses helped minimize obstacles to TCE volatilization, such as high soil organic and clay content. Treatment with a 20% CaO dose, however, led to the formation of byproducts such as dichloroacetylene. TCE degradation to dichloroacetylene at the 20% CaO dose ranged from 2.7% to 6.4% of the initial TCE. Volatilization was concluded to be the dominant process for TCE removal from soil during CaO treatment.     

Screening of factors influencing Cu(II) extraction by soybean oil-based organic solvents using fractional factorial design

This study aimed to identify the significant factors that give large effects on the efficiency of Cu(II) extraction from aqueous solutions by soybean oil-based organic solvents using fractional factorial design. Six factors (mixing time (t), di-2-ethylhexylphosphoric acid concentration ([D2EHPA]), organic to aqueous phase ratio (O:A), sodium sulfate concentration ([Na(2)SO(4)]), equilibrium pH (pH(eq)) and tributylphosphate concentration ([TBP])) affecting the percentage extraction (%E) of Cu(II) were investigated. A 2(6-1) fractional factorial design was applied and the results were analyzed statistically. The results show that only [D2EHPA], pH(eq) and their second-order interaction ([D2EHPA] × pH(eq)) influenced the %E significantly. Regression models for %E were developed and the adequacy of the reduced model was examined. The results of this study indicate that fractional factorial design is a useful tool for screening a large number of variables and reducing the number of experiments.     

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.     

Predicting soil fumigant air concentrations under regional and diverse agronomic conditions

SOFEA (SOil Fumigant Exposure Assessment system; Dow AgroSciences, Indianapolis, IN) is a new stochastic numerical modeling tool for evaluating and managing human inhalation exposure potential associated with the use of soil fumigants. SOFEA calculates fumigant concentrations in air arising from volatility losses from treated fields for large agricultural regions using multiple transient source terms (treated fields), geographical information systems (GIS) information, agronomic specific variables, user-specified buffer zones, and field reentry intervals. A modified version of the USEPA Industrial Source Complex Short Term model (ISCST3) is used for air dispersion calculations. Weather information, field size, application date, application rate, application type, soil incorporation depth, pesticide degradation rates in air, tarp presence, field retreatment, and other sensitive parameters are varied stochastically using Monte Carlo techniques to mimic region and crop specific agronomic practices. Regional land cover, elevation, and population information can be used to refine source placement (treated fields), dispersion calculations, and risk assessments. This paper describes the technical algorithms of SOFEA and offers comparisons of simulation predictions for the soil fumigant 1,3-dichloropropene (1,3-D) to actual regional air monitoring measurements from Kern, California. Comparison of simulation results to daily air monitoring observations is remarkable over the entire concentration distribution (average percent deviation of 44% and model efficiency of 0.98), especially considering numerous inputs such as meteorological conditions for SOFEA were unavailable and approximated by neighboring regions. Both current and anticipated and/or forecasted fumigant scenarios can be simulated using SOFEA to provide risk managers and product stewards the necessary information to make sound regulatory decisions regarding the use of soil fumigants in agriculture.     

Effects of soil variability and weather conditions on pesticide leaching--a farm-level evaluation

In line with European regulations, Dutch law imposes an environmental threshold of 0.1 microg L(-1) on pesticide concentrations in ground water. During registration, the risk of exceeding this threshold is assessed through simulations for one or a few standard scenarios that do not reflect spatial variability under field conditions. The introduction of precision agriculture, where soil variability is actively managed, can increase control over pesticide leaching. This study presents a step-wise evaluation of the effects of soil variability and weather conditions on pesticide leaching. The evaluation was conducted on a 100-ha arable farm and aimed at identifying opportunities for precision management. As a first step, a relative risk assessment identified pesticides presenting a relatively high risk to the environment. Second, the effect of weather conditions was analyzed through 20 years of simulations for three distinct soil profiles. Results were summarized in cumulative probability plots to provide a probabilistic characterization of historical weather data. The year matching 90% probability (1981) served as a reference to simulate pesticide leaching from 612 soil profiles. After interpolation, areas where concentrations exceeded the environmental threshold were identified. Out of a total of 19 pesticides, isoproturon [N-dimethyl-N'-(4-(1-methylethyl)phenyl)urea], metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one], and bentazon [2,1,3-benzothiadiazin-4(3H)-one, 3-isopropyl-, 2,2-dioxide] showed the highest risk for leaching. Leaching was strongly affected by soil variability at the within-field, field, and farm levels. Opportunities for precision management were apparent, but depended on the scale level at which environmental thresholds were implemented. When legislation is formulated in this issue, the presented step-wise evaluation can serve as a basis for identification and precision management of high-risk pesticides.     

Temporal and spatial development of surface soil conditions at two created riverine marshes

The amount of time it takes for created wetlands to develop soils comparable to natural wetlands is relatively unknown. Surface soil changes over time were evaluated in two created wetlands (approximately 1 ha each) at the Olentangy River Wetland Research Park in Columbus, Ohio. The two wetlands were constructed in 1993 to be identical in size and geomorphology, and maintained to have the same hydrology. The only initial difference between the wetlands was that one was planted with native macrophytes while the other was not. In May 2004, soil samples were collected (10 yr and 2 mo after the wetlands were flooded) and compared to samples collected in 1993 (after the wetlands were excavated but before flooding) and 1995 (18 mo after the wetlands were flooded). In all three years, soils were split into surface (0-8 cm) and subsurface (8-16 cm) depths and analyzed for soil organic matter, total C, total P, available P, exchangeable cations, and pH. Soils in the two wetlands have changed substantially through sedimentation and organic accretion. Between 1993 and 1995, soils were most influenced by the deposition of senescent macroalgae, the mobilization of soluble nutrients, and the precipitation of CaCO(3). Between 1995 and 2004, soil parameters were influenced more by the deposition of organic matter from colonized macrophyte communities. Mean percent organic matter at the surface increased from 5.3 +/- 0.1% in 1993, 6.1 +/- 0.2% in 1995, to 9.5 +/- 0.2% in 2004. Mean total P increased from 493 +/- 18 microg g(-1) in 1993, 600 +/- 23 microg g(-1) in 1995, to 724 +/- 20 microg g(-1) in 2004. Spatial analyses of percent organic matter (a commonly used indicator of hydric soil condition) at both wetlands in 1993, 1995, and 2004 showed that soil conditions have become increasingly more variable. High spatial structure (autocorrelation) between data points was detected in 1993 and 2004, with data in 2004 exhibiting a much higher overall variance and narrower range of spatial structure than in 1993.     

RDX loss in a surface soil under saturated and well drained conditions

On military training ranges, low-order, incomplete detonations deposit RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) into surface soils. In this study, we evaluated RDX biodegradation in surface soils obtained from a military training range in Alaska. Two factors were compared: (i) soil water potential during the incubations; and (ii) the use of acetonitrile (ACN) as an RDX carrier to spike samples. Organic solvents have been used in laboratory studies to dissolve slightly water-soluble contaminants before addition to soil. We added ACN to obtain final soil ACN concentrations of 0 mg kg(-1) (0%), 1000 mg kg(-1) (0.1%) and 10 000 mg kg(-1) (1%). We then compared RDX attenuation in the soil under saturated and unsaturated conditions. RDX fell below the limit of detection within 3 wk of study initiation under the saturated condition. A maximum degradation rate of 0.15 mg RDX L(-1) d(-1) was measured. Under the unsaturated condition, 42% of the original RDX was still present at study termination (5 wk). The addition of acetonitrile at 0.1 or 1.0% had no affect on RDX loss in the saturated soil. In the unsaturated soil, however, ACN at 1.0% inhibited RDX loss by as much as 25%. These findings indicate that soil water potential and carrier solvent concentrations can impact the rate and extent to which RDX is attenuated in a surface soil.     

A novel technique for the pre-concentration and extraction of inositol hexakisphosphate from soil extracts with determination by phosphorus-31 nuclear magnetic resonance

Inositol hexakisphosphate (IP6) is often the dominant form of soil organic phosphorus (P), but is rarely investigated because of the analytical difficulties encountered in its extraction, separation, and detection in environmental samples. In particular, recent advances in the study of soil organic P with 31P nuclear magnetic resonance (NMR) have been of limited use for the study of IP6, because the technique does not discriminate between IP6 and other forms of P. This was addressed by developing a novel analytical procedure using the retentive properties of gel-filtration gels for IP6, which allows the combined selective extraction and pre-concentration of IP6 from soil extracts with determination by 31P NMR. While the technique is still in the developmental stage, the results demonstrate that the gel does not interfere with 31P NMR analysis and retains IP6 to concentrations well above those required to give clear spectral signals. The technique has considerable potential for application to the study of IP6 in soil extracts and water samples and, with development, could help to answer fundamental questions regarding the dynamics of organic P in the environment.     

In situ stabilization of soil lead using phosphorus

In situ stabilization of Pb-contaminated soils can be accomplished by adding phosphorus. The standard remediation procedure of soil removal and replacement currently used in residential areas is costly and disruptive. This study was carried out to evaluate the influence of P and other soil amendments on five metal-contaminated soils and mine wastes. Seven treatments were used: unamended control; 2,500 mg of P/kg as triple superphosphate (TSP), phosphate rock (PR), acetic acid followed by TSP, and phosphoric acid (PA); and 5,000 mg of P/kg as TSP or PR. A significant reduction in bioavailable Pb, as determined by the physiologically based extraction test (PBET), compared with the control upon addition of P was observed in all materials tested. Increasing the amount of P added from 2,500 to 5,000 mg/kg also resulted in a significantly greater reduction in bioavailable Pb. Phosphate rock was equally or more effective than TSP or PA in reducing bioavailable Pb in four out of five soils tested. Preacidification produced significantly lower bioavailable Pb compared with the same amount of P from TSP or PR in only one material. Reductions in Pb bioavailability as measured by PBET were evident 3 d after treatment, and it may indicate that the reactions between soil Pb and P occurred in situ or during the PBET. No further reductions were noted over 365 d. X-ray diffraction data suggested the formation of pyromorphite-like minerals induced by P additions. This study suggests that P addition reduced bioavailable Pb by PBET and has potential for in situ remediation of Pb-contaminated soils.     

In vitro pesticide degradation in turfgrass soil incubated under open and sealed conditions

Degradation of selected pesticides was conducted in a turfgrass soil from a golf course under open (i.e., allowing gas exchange with atmosphere) and sealed systems. The time required for 50% of the initial dose of fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), diazinon (O,O-dimethyl O-2-isopropyl-6-methylpyrimidin4-yl phosphorothioate), iprodione [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide], mecoprop [(RS)-2-(4-chloro-otolyloxy)propionic acid], and asulam (4-aminophenylsulfonyl-carbamate) to dissipate (half-life, t 1/2) was less than 2 wk under both conditions. The t 1/2 values of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoro-methylpyridine-3,5-dicarbothioate) were 324 and 185 d under the open and sealed conditions, respectively. The t 1/2 values of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidene-malonate), flutolanil (alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide), and benefin (N-butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine) under the open conditions were 154, 336, and 47 d, respectively. The t 1/2 values of these pesticides increased slightly under the sealed conditions. The t 1/2 values of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methycarbamate) and one of the major degradation products, N-demethyl-terbutol (2,6-di-tert-butyl-4-methylphenyl carbamate), were 182 and 291 d under the open conditions and increased by six- and threefold under the sealed conditions, respectively. The degradation system under the sealed conditions could characterize the persistence of terbutol and N-demethyl-terbutol, which were the most persistent in the field.     

Response surface optimization of acid red 119 dye from simulated wastewater using Al based waterworks sludge and polyaluminium chloride as coagulant

In this research, the performance of Polyaluminium Chloride (PAC) and Polyaluminium Chloride sludge (PACS) as coagulants for acid red 119 (AR119) dye removal from aqueous solutions were compared. The sample of PACS was collected from "Baba Sheikh Ali" water treatment plant (Isfahan, Iran) where PAC is used as a coagulant in the coagulation/flocculation process. A response surface methodology was applied to evaluate the simple and combined effects of the operating variables including initial pH, coagulant dosage and initial dye concentration and to optimize the operating conditions of the treatment process. Results reveal that the optimal conditions for dye removal were initial pH 3.42, coagulant dosage of 4.55 g dried PACS/L and initial dye concentration of 140 mg/L for PACS, while the optimal initial pH, coagulant dosage and initial dye concentration for PAC were 3.8, 57 mg/L and 140 mg/L, respectively. Under these optimal values of process parameters, the dye removal efficiency of 94.1% and 95.25% was observed for PACS and PAC, respectively. Although lower amount of PAC in comparison with PACS was needed for specific dye removal, the reuse of PACS as a low-cost material can offer some advantages such as high efficiency for AR119 dye removal and economic savings on overall water and wastewater treatment plant operation costs.     

Modeling sediment and nitrogen export from a rural watershed in eastern Canada using the soil and water assessment tool

Watershed simulation models can be used to assess agricultural nonpoint-source pollution and for environmental planning and improvement projects. However, before application of any process-based watershed model, the model performance and reliability must be tested with measured data. The Soil and Water Assessment Tool version 2005 (SWAT2005) was used to model sediment and nitrogen loads from the Thomas Brook Watershed, which drains a 7.84 km rural landscape in the Annapolis Valley of Nova Scotia, Canada. The Thomas Brook SWAT model was comprised of 28 subbasins and 265 hydrologic response units, most of them containing agricultural land use, which is the main nonpoint nitrogen source in the watershed. Crop rotation schedules were incorporated into the model using field data collected within Agriculture and Agri-Food Canada's Watershed Evaluation of Beneficial Management Practices program. Model calibration (2004-2006) and validation (2007-2008) were performed on a monthly basis using continuous stream flow, sediment, and nitrogen export measurements. Model performance was evaluated using the coefficient of determination, Nash-Sutcliff efficiency (NSE), and percent bias (PBIAS) statistics. Study results show that the model performance was satisfactory (NSE > 0.4; > 0.5) for stream flow, sediment, nitrate-nitrogen, and total nitrogen simulations. Annual corn, barley, and wheat yields were also simulated well, with PBIAS values ranging from 0.3 to 7.2%. This evaluation of SWAT demonstrated that the model has the potential to be used as a decision support tool for agricultural watershed management in Nova Scotia.     

Modeling phosphorus concentrations in Irish rivers using land use, soil type, and soil phosphorus data

Modeling diffuse phosphorus (P) loss may indicate management strategies to minimize P loss from agricultural sources. An empirical model predicting flow-weighted phosphorus concentrations (MRP) was derived using data collected from 35 Irish river catchments. Monitoring records of riverine P and stream flow data were used to calculate MRP values averaged for the years 1991-1994. These data were modeled using land use, soil type, and soil P data. Soil type in catchments was described using soil survey classifications weighted according to their P desorption properties from laboratory results. Soil test P concentrations for the studied watersheds were obtained from a national database. Soil P levels were weighted based on the results of field experiments measuring P losses in overland flow from fields at different soil test P levels. The 35 catchments were statistically clustered into two populations (A and B) based on differences in soil type, specifically, soil hydrology. Catchments in Cluster A had predominantly poorly drained soils and comparatively higher MRP concentrations (0.03-0.17 mg L(-1)) than Cluster B areas (0.01-0.7 mg L(-1)) with mostly well-drained soils. Regression equations derived for A and B type catchments predicted MRP values with 68 and 62% of the variation explained in the models, respectively. Data extracted for the rest of the country were applied to the models to delineate areas at risk on a national scale. While the models were only moderately accurate they highlighted the influence of land management, specifically, high production grassland receiving high P inputs, in conjunction with the effect of soil type and soil hydrology on the transport of P to surface waters.     

Solute response to changing nutrient loads in soil and walled ceramic cup samplers under continuous extraction

This report evaluates a vacuum-assisted walled percolation sampler preconditioned in soil, and examines the dynamic response of leachate solutes. The 20-cm walled percolation sampler extracted soil water under continuous tension via a ceramic cup collector embedded in a silica flour layer, whose upper surface interfaced with field soil. In the laboratory, alternating solutions with high and low NO3-N (232 or 3.6 mg L(-1)), molybdate-reactive P (MRP) (1.75 or 0.0 mg L(-1)), K+ (568 or 3.6 mg L(-1)), and Br- (9.6 or 0.0 mg L(-1)) concentrations were delivered directly to the (i) sampler ceramic cup; (ii) silica flour bed surface, or (iii) 12-mm soil layer placed over the silica flour bed. For alternating input solutions delivered to the silica-flour bed surface, (i) solute breakthrough (95% equivalency) occurred in 4 pore volumes and was the same for both the high and low concentration input phases of the application, and (ii) concentrations of NO3-N, Br-, and MRP in cumulative extracted water volumes were within 5% of those in corresponding input volumes. Alternating nutrient loads from high to low levels in the fixed flow rate input waters caused excess MRP (1.6 times that in the high concentration MRP solution) to leach from the calcareous soil. The dynamic character of P transport in K-fertilized soils deserves further study and may have important environmental implications.     

Optimal spatial resolution for collection of ground data and multi-sensor image mapping of a soil erosion cover factor

Military training activities disturb ground and vegetation cover of landscapes and increases potential soil erosion. To monitor the dynamics of soil erosion, there is an important need for an optimal sampling design in which determining the optimal spatial resolutions in terms of size of sample plots used for the collection of ground data and the size of pixels for mapping. Given a sample size, an optimal spatial resolution should be cost-efficient in both sampling costs and map accuracy. This study presents a spatial variability-based method for that purpose and compared it with the traditional methods in a study area in which a soil erosion cover factor was sampled and mapped with multiple plot sizes and multi-sensor images. The results showed that the optimal spatial resolutions obtained using the spatial variability-based method were 12 and 20m for years 1999 and 2000, respectively, and were consistent with those using the traditional methods. Moreover, the most appropriate spatial resolutions using the high-resolution images were also consistent with those using ground sample data, which provides a potential to use the high-resolution images instead of ground data to determine the optimal spatial resolutions before sampling. The most appropriate spatial resolutions above were then verified in terms of cost-efficiency which was defined as the product of sampling cost and map error using ordinary kriging without images and sequential Gaussian co-simulation with images to generate maps.     

Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions

For immobilization technologies to be successful, the use of readily available and cost advantageous amendment is important when the remediation targets vast amounts of contaminated soils. The objectives of this study were to investigate whether the byproduct-synthesized hydroxyapatite can be used as an immobilizing amendment for dissolved Pb from a shooting range soil, and to model the kinetic data collected from dissolution experiments. A soil–solution kinetic experiment was conducted under fixed pH conditions as a function of time. A Pb-contaminated soil was reacted with various hydroxyapatite amendments to determine the dissolution rate and mineral products of soil Pb. Three types of amendments used were pure hydroxyapatite (HA), and poorly crystalline hydroxyapatites synthesized from gypsum waste (CHA), and synthesized from incinerated poultry litter (PHA). The dissolved Pb concentration decreased with the addition of amendments at pH 3–7. Both CHA and PHA were more effective than HA for attenuating Pb dissolution at pH 6 and above. According to the thermodynamic calculation at pH 6, the dissolved Pb concentration for CHA and PHA treatments was predicted to be 66% and 50% lower than that of HA treatment, respectively. A better Pb immobilization effect demonstrated by CHA and PHA resulted in their greater solubility at higher pH, which may promote the formation of chloropyromorphite precipitates. Dissolution kinetics of soil Pb was adequately explained by pseudo-first order and pseudo-second order equations in acid pH ranges. According to the ion exchange model, an adequate agreement between the experimental data and regression curves was shown in the initial 40 min of the reaction process, but the accuracy of model predictability decreased thereafter. According to kinetic models and dissolution phenomena, CHA and PHA amendments had better Pb sorption capacity with rapid kinetics than pure hydroxyapatite at weak acid to neutral pH.     

Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.     

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.     

Prediction of microbial accessibility of carbon-14-phenanthrene in soil in the presence of pyrene or benzo[a]pyrene using an aqueous cyclodextrin extraction technique

Traditionally, solvent extractions are routinely used in the assessment of contaminated land. However, vigorous solvent extractions only give total concentrations rather than that relating to the bioaccessible fraction. Recently, less harsh, aqueous-based extraction methods have been shown to be a better estimate of the microbial degradation of polycyclic aromatic hydrocarbons (PAHs). The aqueous-based hydroxypropyl-beta-cyclodextrin (HPCD) extraction technique was tested using 14C-PAHs in soils and compared against indigenous microbial mineralization (a measure of bioaccessibility) of 14C-phenanthrene in the presence of pyrene or benzo[a]pyrene (B[a]P) over a range of concentrations (0, 5, 10, or 50 mg kg(-1)) and aged for 0, 25, 50, and 100 d in four soils. At each time point, the total loss, extractability, and mineralization of 14C-phenanthrene was measured in each of the soils. The presence of the other PAHs had little effect on the behavior of 14C-phenanthrene in any of the soils. Comparisons between the amounts of 14C-phenanthrene extracted using HPCD and mineralized were made and showed that there was a correlation (1:1). This study demonstrates that HPCD extraction is able to predict the microbial accessibility fraction of 14C-phenanthrene in the presence of other PAHs in a range of soils, further supporting the applicability of this technique.