Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

Remediating munitions-contaminated soil with zerovalent iron and cationic surfactants

Soils contaminated from military operations often contain mixtures of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and TNT (2,4,6-trinitrotoluene) rather than a single explosive. Differences among explosives in solubility and reactivity make developing a single remediation treatment difficult. When Fe(0) was used to treat a munitions-contaminated soil, we observed high rates of destruction for RDX and TNT (98%) but not HMX. Our objective was to determine if HMX destruction by Fe(0) could be enhanced by increasing HMX solubility by physical (temperature) or chemical (surfactants) means. To determine electron acceptor preference, we treated RDX and HMX with Fe(0) in homogeneous solutions and binary mixtures. Increasing aqueous temperature (20 to 55 degrees C) increased HMX solubility (2 to 22 mg L(-1)) but did not increase destruction by Fe(0) in a contaminated soil slurry that also contained RDX and TNT. Batch experiments using equal molar concentrations of RDX and HMX demonstrated that RDX was preferentially reduced over HMX by Fe(0). By testing various surfactants, we found that the cationic surfactants (HDTMA [hexadecyltrimethylammonium bromide], didecyl, and didodecyl) were most effective in increasing HMX concentration in solution. Didecyl and HDTMA were also found to be highly effective in facilitating the transformation of HMX by Fe(0). Using HDTMA or didecyl solutions (3%, w/v) containing solid-phase HMX, we observed that 100% of the added HMX was transformed by Fe(0) in the didecyl matrix and 60% in the HDTMA matrix. These results indicate that cationic surfactants can increase HMX solubility and facilitate Fe(0)-mediated transformation kinetics but HMX destruction rates will be slowed when RDX is present.     

Mercury speciation in highly contaminated soils from chlor-alkali plants using chemical extractions

A four-step novel sequential extraction procedure (SEP) was developed to assess Hg fractionation and mobility in three highly contaminated soils from chlor-alkali plants (CAPs). The SEP was validated using a certified reference material (CRM) and pure Hg compounds. Total, volatile, and methyl Hg concentrations were also determined using single extractions. Mercury was separated into four fractions defined as water-soluble (F1), exchangeable (F2) (0.5 M NH4Ac-EDTA and 1 M CaCl2 were tested), organic (F3) (successive extractions with 0.2 M NaOH and CH3COOH 4% [v/v]), and residual (F4) (HNO3 + H2SO4 + HClO4). The soil characterization revealed extremely contaminated (295 +/- 18 to 11 500 +/- 500 mg Hg kg(-1)) coarse-grained sandy soils having an alkaline pH (7.9-9.1), high chloride concentrations (5-35 mg kg(-1)), and very low organic carbon content (0.00-18.2 g kg(-1)). Methyl Hg concentrations were low (0.2-19.3 microg kg(-1)) in all soils. Sequential extractions indicated that the majority of the Hg was associated with the residual fraction (F4). In Soils 1 and 3, however, high percentages (88-98%) of the total Hg were present as volatile Hg. Therefore, in these two soils, a high proportion of volatile Hg was present in the residual fraction. The nonresidual fraction (F1 + F2 + F3) was most abundant in Soil 1 (14-42%), suggesting a higher availability of Hg in this soil. The developed and validated SEP was reproducible and efficient for highly contaminated samples. Recovery ranged between 93 and 98% for the CRM and 70 and 130% for the CAP-contaminated soils.     

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.     

Apatite and phillipsite as sequestering agents for metals and radionuclides

Laboratory and greenhouse studies were conducted to quantify apatite and phillipsite (zeolite) sequestration of selected metal contaminants. The laboratory batch study measured the sorption of aqueous Co2+, Ba2+, Pb2+, Eu3+, and UO2(2+). Apatite sorbed more Co2+, Pb2+, Eu3+, and UO2(2+) from the spike solution than phillipsite, resulting in distribution coefficients (Kd values) of >200,000 L kg(-1). Phillipsite was more effective than apatite at sorbing aqueous Ba2+. Results from the laboratory study were used to design the greenhouse study that used a soil affected by a Zn-Pb smelter from Pribram, Czech Republic. Two application rates (25 and 50 g kg(-1)) of phillipsite and apatite and two plant species, maize (Zea mays L.) and oat (Avena sativa L.), were evaluated in this study. There was little (maize) to no (oat) plant growth in the unamended contaminated soil. Apatite and, to a slightly lesser extent, phillipsite additions significantly enhanced plant growth and reduced Cd, Pb, and Zn concentrations in all analyzed tissues (grain, leaves, and roots). The sequestering agents also affected some essential elements (Ca, Fe, and Mg). Phillipsite reduced Fe and apatite reduced P and Fe concentrations in oat tissues; however, the level of these elements in oat leaves and grains remained sufficient. Sequential extractions of the soil indicated that the Cd, Pb, and Zn were much more strongly sorbed onto the amended soil, making the contaminants less phytoavailable.     

Biotic and abiotic degradation of CL-20 and RDX in soils

The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes. Both abiotic and biological processes significantly degraded CL-20 in all soils examined. Apparent abiotic, first-order degradation rates (k) for CL-20 were not significantly different between soil-free controls (0.018 < k < 0.030 d(-1)) and biologically attenuated soil controls (0.003 < k < 0.277 d(-1)). The addition of glucose to biologically active soil microcosms significantly increased CL-20 degradation rates (0.068 < k < 1.22 d(-1)). Extents of mineralization of (14)C-CL-20 to (14)CO(2) in biologically active soil microcosms were 41.1 to 55.7%, indicating that the CL-20 cage was broken, since all carbons are part of the heterocyclic cage. Under aerobic conditions, abiotic degradation rates of RDX were generally slower (0 < k < 0.032 d(-1)) than abiotic CL-20 degradation rates. In biologically active soil microcosms amended with glucose aerobic RDX degradation rates varied between 0.010 and 0.474 d(-1). Biodegradation was a key factor in determining the environmental fate of RDX, while a combination of biotic and abiotic processes was important with CL-20. Our data suggest that CL-20 should be less recalcitrant than RDX in aerobic soils.     

Remediating RDX-contaminated ground water with permanganate: laboratory investigations for the Pantex perched aquifer

Ground water beneath the U.S. Department of Energy Pantex Plant is contaminated with the high explosive RDX (hexahydro-1,3,5-trinitro-1,3,5 triazine). The USDOE Innovative Treatment and Remediation Demonstration (ITRD) program identified in situ oxidation by permanganate as a technology fit for further investigation. We evaluated the efficacy of KMnO(4) to transform and mineralize RDX by determining degradation kinetics and carbon mass balances using (14)C-RDX. Aqueous RDX solutions (2-5 mg L(-1)) and RDX-contaminated slurries (50% solids, w/v) were treated with KMnO(4) at 1000, 2000, 4000, and 20000 mg L(-1). Treating an aqueous RDX solution of 2.8 mg L(-1) with 20000 mg KMnO(4) L(-1) decreased RDX to 0.1 mg L(-1) within 11 d while cumulative mineralization proceeded for 14 d until 87% of the labeled carbon was trapped as (14)CO(2). Similar cumulative mineralization was obtained when Pantex aquifer material was included in the solution matrix. Other experiments using 4000 mg KMnO(4) L(-1) showed that initial RDX concentrations (1.3-10.4 mg L(-1)) or initial pH (4-11) had little effect on reaction rates. Attempts to identify RDX degradates and reaction products showed that N(2)O was a product of permanganate oxidation and constituted 20 to 30% of the N balance. Time-course measurements of a (14)C-RDX solution treated with KMnO(4) revealed few (14)C-labeled degradates but through liquid chromatography-mass spectrometry (LC-MS) analysis, we present evidence that 4-nitro-2,4-diaza-butanol is formed. Aquifer microcosm studies confirmed that the transformation products not mineralized by KMnO(4) were much more biodegradable than parent RDX. These results indicate permanganate can effectively transform and mineralize RDX in the presence of aquifer material and support its use as an in situ chemical oxidation treatment for the Pantex perched aquifer.     

Occurrence and rates of terminal electron-accepting processes and recharge processes in petroleum hydrocarbon-contaminated subsurface

The occurrence and rates of terminal electron acceptor processes, and recharge processes in the unsaturated zone of a boreal site contaminated with petroleum hydrocarbons in the range C(10) to C(40) were examined. Soil microcosms were used to determine the rates of denitrification, iron (Fe) reduction, sulfate (SO(4)) reduction, and methanogenesis in two vertical soil profiles contaminated with oil, and in a noncontaminated reference sample. Furthermore, the abundances of the 16S rRNA genes belonging to Geobacteracaea in the samples were determined by real-time quantitative polymerase chain reaction (PCR). Analyses of ground water chemistry and soil gas composition were also performed together with continuous in situ monitoring of soil water and ground water chemistry. Several lines of evidence were obtained to demonstrate that both Fe reduction and methanogenesis played significant roles in the vertical profiles: Fe reduction rates up to 3.7 nmol h(-1) g(-1) were recorded and they correlated with the abundances of the Geobacteracaea 16S rRNA genes (range: 2.3 x 10(5) to 4.9 x 10(7) copies g(-1)). In the ground water, ferrous iron (Fe(2+)) concentration up to 55 mg L(-1) was measured. Methane production rates up to 2.5 nmol h(-1) g(-1) were obtained together with methane content up to 15% (vol/vol) in the soil gas. The continuous monitoring of soil water and ground water chemistry, microcosm experiments, and soil gas monitoring together demonstrated that the high microbial activity in the unsaturated zone resulted in rapid removal of oxygen from the infiltrating recharge thus leaving the anaerobic microbial processes dominant below 1.5 m depth both in the unsaturated and the saturated zones of the subsurface.     

Land application of domestic effluent onto four soil types: plant uptake and nutrient leaching

Land application has become a widely applied method for treating wastewater. However, it is not always clear which soil-plant systems should be used, or why. The objectives of our study were to determine if four contrasting soils, from which the pasture is regularly cut and removed, varied in their ability to assimilate nutrients from secondary-treated domestic effluent under high hydraulic loadings, in comparison with unirrigated, fertilized pasture. Grassed intact soil cores (500 mm in diameter by 700 mm in depth) were irrigated (50 mm wk(-1)) with secondary-treated domestic effluent for two years. Soils included a well-drained Allophanic Soil (Typic Hapludand), a poorly drained Gley Soil (Typic Endoaquept), a well-drained Pumice Soil formed from rhyolitic tephra (Typic Udivitrand), and a well-drained Recent Soil formed in a sand dune (Typic Udipsamment). Effluent-irrigated soils received between 746 and 815 kg N ha(-1) and 283 and 331 kg P ha(-1) over two years of irrigation, and unirrigated treatments received 200 kg N ha(-1) and 100 kg P ha(-1) of dissolved inorganic fertilizer over the same period. Applying effluent significantly increased plant uptake of N and P from all soil types. For the effluent-irrigated soils plant N uptake ranged from 186 to 437 kg N ha(-1) yr(-1), while plant P uptake ranged from 40 to 88 kg P ha(-1) yr(-1) for the effluent-irrigated soils. Applying effluent significantly increased N leaching losses from Gley and Recent Soils, and after two years ranged from 17 to 184 kg N ha(-1) depending on soil type. Effluent irrigation only increased P leaching from the Gley Soil. All P leaching losses were less than 49 kg P ha(-1) after two years. The N and P leached from effluent treatments were mainly in organic form (69-87% organic N and 35-65% unreactive P). Greater N and P leaching losses from the irrigated Gley Soil were attributed to preferential flow that reduced contact between the effluent and the soil matrix. Increased N leaching from the Recent Soil was the result of increased leaching of native soil organic N due to the higher hydraulic loading from the effluent irrigation.     

Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.     

An empirical model of soil chemical properties that regulate methane production in Japanese rice paddy soils

To understand which soil chemical properties are the best predictors of CH4 production in rice paddy soils, a model was developed with empirical data from nine types of rice soils collected around Japan and anaerobically incubated at 30 degrees C for 16 wk in laboratory conditions. After 1, 2, 4, 8, and 16 wk of incubation, CO2, CH4, and Fe(II) were measured to understand soil organic matter decomposition and iron (Fe) reduction. Available N (N ava) was also measured at the end of incubation. The results showed that decomposable C and reducible Fe are two key parameters that regulate soil CH(4) production (P CH4). There was a significant relationship between decomposable C and available N (N ava) (r2 = 0.975**). Except for a sandy soil sample, a significant relationship between total Fe (Fe total) and reducible Fe was found. From this experiment, a simple model of soil CH4 production was developed: P CH4 = 1.593N(ava) - 2.460Fe total/1000 (each unit was mg kg(-1) soil). After simulated CH4 production by two soil chemical properties as above, there was a significant consistency between model simulation and actual measurement (r2 = 0.831**).     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

In vitro methane removal by volcanic pumice soil biofilter columns over one year

Soil methane (CH(4)) biofilters, containing CH(4)-oxidizing bacteria (methanotrophs), are a promising technology for mitigating greenhouse gas emissions. However, little is known about long-term biofilter performance. In this study, volcanic pumice topsoils (0-10 cm) and subsoils (10-50 cm) were tested for their ability to oxidize a range of CH(4) fluxes over 1 yr. The soils were sampled from an 8-yr-old and a 2-yr-old grassed landfill cover and from a nearby undisturbed pasture away from the influence of CH(4) generated by the decomposing refuse. Methane was passed through the soils in laboratory chambers with fluxes ranging from 0.5 g to 24 g CH(4) m(-3) h(-1). All topsoils efficiently oxidized CH(4). The undisturbed pasture topsoil exhibited the highest removal efficiency (24 g CH(4) m(-3) h(-1)), indicating rapid activation of the methanotroph population to the high CH(4) fluxes. The subsoils were less efficient at oxidizing CH(4) than the topsoils, achieving a maximum rate oxidation rate of 7 g CH(4) m(-3) h(-1). The topsoils exhibited higher porosities; moisture contents; surface areas; and total C, N, and available-P concentrations than the subsoils, suggesting that these characteristics strongly influence growth and activity of the CH(4)-oxidizing bacteria. Soil pH values and available-P levels gradually declined during the trial, indicating a need to monitor chemical parameters closely so that adjustments can be made when necessary. However, other key soil physicochemical parameters (moisture, total C, total N) increased over the course of the trial. This study showed that the selected topsoils were capable of continually sustaining high CH(4) removal rates over 1 yr, which is encouraging for the development of biofilters as a low-maintenance greenhouse gas mitigation technology.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

Quantitative,chemical, and mineralogical characterization of flue gas desulfurization by-products

The objective of this study was to demonstrate that simple fractionation and selective dissolution techniques can be used to provide detailed chemical and mineralogical analyses of flue gas desulfurization by-products. The material studied was a mine grout prepared as a 1:1 mixture (wt./wt.) of fly ash (FA) and filter cake (FC) with hydrated lime (50 g kg(-1)) added to improve handling. The hydrated lime was composed mostly of calcite (CaCO3), portlandite [Ca(OH)2], lime (CaO), and brucite [Mg(OH)2] (515, 321, 55, and 35 g kg(-1), respectively) and had low (<6 g kg(-1)) concentrations of most trace elements. The FC contained hannebachite (CaSO3 x 0.5H2O) (786 g kg(-1)) with smaller quantities (<10 g kg(-1)) of calcite, quartz (SiO2), brucite, and gypsum (CaSO4 x 2H2O). Except for B and Cu, trace element concentrations were comparable to those in the hydrated lime. The FA contained both magnetic (222 g kg(-1)) and nonmagnetic (778 g kg(-1)) fractions. The former was composed mostly of hematite (Fe2O3), magnetite (Fe3O4), and glass (272, 293, and 287 g kg(-1), respectively), whereas the latter was enriched in glass, quartz, and mullite (Al6Si2O13) (515, 243, and 140 g kg(-1), respectively). Etching with 1% HF showed that 60 to 100% of trace elements were concentrated in the glass, although some metals (Co, Cr, and Mn) were clearly enriched in the magnetic phase. The aged grout contained 147 g kg(-1) ettringite [Ca6Al2(SO4)3(OH)12 x 26H2O] in addition to 314 g kg(-1) hannebachite and 537 g kg(-1) insoluble phases (mullite, quartz, hematite, magnetite, and glass).     

Quantifying carbon dioxide and methane emissions and carbon dynamics from flooded boreal forest soil

The boreal forest is subject to natural and anthropogenic disturbances, but the production of greenhouse gases as a result of flooding for hydroelectric power generation has received little attention. It was hypothesized that flooded soil would result in greater CO(2) and CH(4) emissions and carbon (C) fractionation compared with non-flooded soil. To evaluate this hypothesis, soil C and nitrogen (N) dynamics, CO(2) and CH(4) mean production rates, and (13)C fractionation in laboratory incubations at 14 and 21 degrees C under non-flooded and flooded conditions and its effect on labile and recalcitrant C sources were determined. A ferro-humic Podzol was collected at three different sites at the Experimental Lakes Area, Canada, with a high (19,834 g C m(-2)), medium (18,066 g C m(-2)), and low (11,060 g C m(-2)) soil organic C (SOC) stock. Soil organic C and total N stocks (g m(-2)) and concentrations (g kg(-1)) were significantly different (p < 0.05) among soil horizons within each of the three sites. Stable isotope analysis showed a significant enrichment in delta(13)C and delta(15)N with depth and an enrichment in delta(13)C and delta(15)N with decreasing SOC and N concentration. The mean CO(2) and CH(4) production rates were greatest in soil horizons with the highest SOC stock and were significantly higher at 21 degrees C and in flooded treatments. The delta(13)C of the evolved CO(2) (delta(13)C-CO(2)) became significantly enriched with time during decomposition, and the greatest degree of fractionation occurred in the organic Litter, Fungal, and Humic forest soil horizons and in soil with a high SOC stock compared with the mineral horizon and soil with a lower SOC stock. The delta(13)C-CO(2) was significantly depleted in flooded treatments compared with non-flooded treatments.     

Soil and surface runoff phosphorus relationships for five typical USA midwest soils

Excessively high soil P can increase P loss with surface runoff. This study used indoor rainfall simulations to characterize soil and runoff P relationships for five Midwest soils (Argiudoll, Calciaquaoll, Hapludalf, and two Hapludolls). Topsoil (15-cm depth, 241-289 g clay kg(-1) and pH 6.0-8.0) was incubated with five NH4H2PO4 rates (0-600 mg P kg(-1)) for 30 d. Total soil P (TPS) and soil-test P (STP) measured with Bray-P1 (BP), Mehlich-3 (M3P), Olsen (OP), Fe-oxide-impregnated paper (FeP), and water (WP) tests were 370 to 1360, 3 to 530, 10 to 675, 4 to 640, 7 to 507, and 2 to 568 mg P kg(-1), respectively. Degree of soil P saturation (DPS) was estimated by indices based on P sorption index (PSI) and STP (DPSSTP) and P, Fe, and Al extracted by ammonium oxalate (DPSox) or Mehlich-3 (DPSM3). Soil was packed to 1.1 g cm(-3) bulk density in triplicate boxes set at 4% slope. Surface runoff was collected during 75 min of 6.5 cm h(-1) rain. Runoff bioavailable P (BAP) and dissolved reactive P (DRP) increased linearly with increased P rate, STP, DPSox, and DPSM3 but curvilinearly with DPSSTP. Correlations between DRP or BAP and soil tests or saturation indices across soils were greatest (r > or = 0.95) for FeP, OP, and WP and poorest for BP and TPS (r = 0.83-0.88). Excluding the calcareous soil (Calciaquoll) significantly improved correlations only for BP. Differences in relationships between runoff P and the soil tests were small or nonexistent among the noncalcareous soils. Routine soil P tests can estimate relationships between runoff P concentration and P application or soil P, although estimates would be improved by separate calibrations for calcareous and noncalcareous soils.     

Residual soil nitrate after potato harvest

Nitrogen loss by leaching is a major problem, particularly with crops requiring large amounts of N fertilizer. We evaluated the effect of N fertilization and irrigation on residual soil nitrate following potato (Solanum tuberosum L.) harvests in the upper St-John River valley of New Brunswick, Canada. Soil nitrate contents were measured to a 0.90-m depth in three treatments of N fertilization (0, 100, and 250 kg N ha(-1)) at two on-farm sites in 1995, and in four treatments of N fertilization (0, 50, 100, and 250 kg N ha(-1)) at four sites for each of two years (1996 and 1997) with and without supplemental irrigation. Residual soil NO3-N content increased from 33 kg NO3-N ha(-1) in the unfertilized check plots to 160 kg NO3-N ha(-1) when 250 kg N ha(-1) was applied. Across N treatments, residual soil NO3-N contents ranged from 30 to 105 kg NO3-N ha(-1) with irrigation and from 30 to 202 kg NO3-N ha(-1) without irrigation. Residual soil NO3-N content within the surface 0.30 m was related (R2 = 0.94) to the NO3-N content to a 0.90-m depth. Estimates of residual soil NO3-N content at the economically optimum nitrogen fertilizer application (Nop) ranged from 46 to 99 kg NO3-N ha(-1) under irrigated conditions and from 62 to 260 kg NO3-N ha(-1) under nonirrigated conditions, and were lower than the soil NO3-N content measured with 250 kg N ha(-1). We conclude that residual soil NO3-N after harvest can be maintained at a reasonable level (<70 kg NO3-N ha(-1)) when N fertilization is based on the economically optimum N application.     

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.     

Chemical and physical properties of dry flue gas desulfurization products

Beneficial and environmentally safe recycling of flue gas desulfurization (FGD) products requires detailed knowledge of their chemical and physical properties. We analyzed 59 dry FGD samples collected from 13 locations representing four major FGD scrubbing technologies. The chemistry of all samples was dominated by Ca, S, Al, Fe, and Si and strong preferential partitioning into the acid insoluble residue (i.e., coal ash residue) was observed for Al, Ba, Be, Cr, Fe, Li, K, Pb, Si, and V. Sulfur, Ca, and Mg occurred primarily in water- or acid-soluble forms associated with the sorbents or scrubber reaction products. Deionized water leachates (American Society for Testing and Materials [ASTM] method) and dilute acetic acid leachates (toxicity characteristic leaching procedure [TCLP] method) had mean pH values of >11.2 and high mean concentrations of S primarily as SO(2-)4 and Ca. Concentrations of Ag, As, Ba, Cd, Cr, Hg, Pb, and Se (except for ASTM Se in two samples) were below drinking water standards in both ASTM and TCLP leachates. Total toxicity equivalents (TEQ) of dioxins, for two FGD products used for mine reclamation, were 0.48 and 0.53 ng kg(-1). This was similar to the background level of the mine spoil (0.57 ng kg(-1)). The FGD materials were mostly uniform in particle size. Specific surface area (m2 g(-1)) was related to particle size and varied from 1.3 for bed ash to 9.5 for spray dryer material. Many of the chemical and physical properties of these FGD samples were associated with the quality of the coal rather than the combustion and SO2 scrubbing processes used.