Neutralization potential determination of siderite (FeCO3) using selected oxidants

Siderite (FeCO3) is commonly found in coal overburden and, when present, can cause interference in the determination of neutralization potential (NP). Under acidic testing conditions, FeCO3 reacts to neutralize acid, which contributes to the NP. However, continued weathering of FeCO3 (oxidation of Fe2+ and hydrolysis of Fe3+) produces a neutral to slightly acidic solution. The effects of hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and O2 on the laboratory measurement of NP of siderite samples taken from overburden were examined. All oxidation treatments lowered the NP values of the siderite samples as compared with the standard USEPA method. However, oxidation with H2O2 produced variable results depending on the amount of H2O2 added. Neutralization potential values obtained after oxidation treatments were highly correlated with Mn concentration. Reaction products (i.e., 2-line ferrihydrite) of siderite samples with H2O2 and KMnO4 were not representative of natural siderite weathering. Oxidation with O2 produced the lowest NP values for siderite samples. The reaction products produced by oxidation with O2 most closely represent those intermediate products formed when siderite is exposed to atmospheric weathering conditions. Oxidation with O2 also proved to be the most reproducible method for accurately assessing NP when siderite is present in overburden samples.     

Influence of soil pH and application rate on the oxidation of calcium sulfite derived from flue gas desulfurization

Calcium sulfite hemihydrate (CaSO(3).0.5H2O), a common byproduct of coal-fired utilities, is fairly insoluble and can decompose to release toxic SO2 under highly acidic soil conditions; however, it can also oxidize to form gypsum. The objective of this study was to examine the effects of application rate and soil pH on the oxidation of calcium sulfite under laboratory conditions. Oxidation rates measured by release of SO4-S to solution decreased with increasing application rate. Leachate SO4-S from soils amended with 1.0 to 3.0 g kg-1 CaSO3 increased over a 21 to 28 d period before reaching a plateau. At 4 g kg-1, maximum SO4-S release was delayed until Week 7. Oxidation and release of SO4-S from soil amended with 3.0 g kg-1 calcium sulfite increased markedly with decreasing soil pH. After only 3 d incubation, the concentrations of SO4-S in aqueous leachates were 77, 122, 170, 220, and 229 mg L-1 for initial soil pH values of 7.8, 6.5, 5.5, 5.1, and 4.0, respectively. At an initial soil pH value of 4.0, oxidation/dissolution did not increase much after 3 d. At higher pH values, oxidation was maximized after 21 d. These results suggest that autumn surface applications of calcium sulfite in no-till systems should permit ample time for oxidation/dissolution reactions to occur without introducing biocidal effects related to oxygen scavenging. Soil and annual crops can thus benefit from additions of soluble Ca and SO4 if calcium sulfite is applied in advance of spring planting.     

Environmental factors influencing attenuation of methane and hydrochlorofluorocarbons in landfill cover soils

The influence of different environmental factors on methane oxidation and degradation of hydrochlorofluorocarbons (HCFCs) was investigated in microcosms containing soil sampled at Skellingsted Landfill, Denmark. The soil showed a high capacity for methane oxidation resulting in a maximum oxidation rate of 104 microg CH4 g(-1) h(-1) and a low affinity of methane with a half-saturation constant of 2.0% v/v. The hydrochlorofluorocarbons HCFC-21 (dichlorofluoromethane) and HCFC-22 (chlorodifluoromethane) were rapidly oxidized and the oxidation occurred in parallel with the oxidation of methane. The maximal HCFC oxidation rates were 0.95 and 0.68 microg g(-1) h(-1) for HCFC-21 and HCFC-22, respectively. Increasing concentrations of HCFCs resulted in decreased methane oxidation rates. However, compared with typical concentrations in landfill gas, relatively high HCFC concentrations were needed to obtain a significant inhibition of methane oxidation. In general, the environmental factors studied influenced the degradation of HCFCs in almost the same way as they influenced methane oxidation. Temperature had a strong influence on the methanotrophic activity giving high Q10 values of 3.4 to 4.1 over the temperature range of 2 to 25 degrees C. Temperature optimum was around 30 degrees C; however, oxidation occurred at temperatures as low as 2 degrees C. A moisture content of 25% w/w yielded the maximum oxidation rate as it allowed good gas transport together with sufficient microbial activity. The optimum pH was around neutrality (pH = 6.5-7.5) showing that the methanotrophs were optimally adapted to the in situ pH, which was 6.9. Copper showed no inhibitory effect when added in relatively high concentrations (up to 60 mg kg(-1)), most likely due to sorption of copper ions to soil particles. At higher copper concentrations the oxidation rates decreased. The oxidation rates for methane, HCFC-21, and HCFC-22 were unaltered in ammonium-amended soil up to 14 mg kg(-1). Higher ammonium concentrations inhibited the oxidation process. The most important parameters controlling oxidation in landfill cover soil were found to be temperature, soil moisture, and methane and oxygen supply.     

Revegetation of high zinc and lead tailings with municipal biosolids and lime: greenhouse study

Acidic (pH 4.1) and high Cd, Pb, and Zn mine tailings (mean +/- SD: 17 +/- 0.4, 3800 +/- 100, and 3500 +/- 100 mg kg(-1), respectively) from an alluvial tailings deposit in Leadville, Colorado were amended with municipal biosolids (BS) (224 Mg ha(-1)) and different types of lime (calcium carbonate equivalent of 224 Mg ha(-1) CaCO3) in a greenhouse column study to test the ability of the amendments to neutralize surface and subsoil acidity and restore plant growth. The types of lime included coarse, agricultural, and fine-textured lime (CL, AL, and FL), sugar beet lime (SBL), and lime kiln dust (LK). The FL was also added alone. All treatments increased bulk pH in the amended horizon in comparison to the control, with the most significant increases observed in the FL, SBL+BS, and LK+BS treatments (7.33, 7.34, and 7.63, respectively). All treatments, excluding the FL, increased the pH in the horizon directly below the amended layer, with the most significant increases observed in the SBL+BS and LK+BS treatments (6.01 and 5.41, respectively). Significant decreases in 0.01 M Ca(NO3)2-extractable Zn and Cd were observed in the subsoil for all treatments that included BS, with the largest decrease in the SBL+BS treatment (344 and 3.9 versus 4 and 0.1 mg kg(-1) Zn and Cd, respectively). Plant growth of annual rye (Lolium multiflorum L.) was vigorous in all treatments that included BS with plant Zn, Cd, and Pb concentrations reduced over the control.     

Methane oxidation in an intensively cropped tropical rice field soil under long-term application of organic and mineral fertilizers

Methane (CH4) oxidation is the only known biological sink process for mitigating atmospheric and terrestrial emissions of CH4, a major greenhouse gas. Methane oxidation in an alluvial soil planted to rice (Oryza sativa L.) under long-term application of organic (compost with a C/N ratio of 21.71), and mineral fertilizers was measured in a field-cum-laboratory incubation study. Oxidation rates were quantified in terms of decrease in the concentration of CH4 in the headspace of incubation vessels and expressed as half-life (t(1)2) values. Methane oxidation rates significantly differed among the treatments and growth stages of the rice crop. Methane oxidation rates were high at the maximum tillering and maturity stages, whereas they were low at grain-filling stage. Methane oxidation was low (t(1)2) = 15.76 d) when provided with low concentration of CH4. On the contrary, high concentration of CH4 resulted in faster oxidation (t(1)2) = 6.67 d), suggesting the predominance of "low affinity oxidation" in rice fields. Methane oxidation was stimulated following the application of mineral fertilizers or compost implicating nutrient limitation as one of the factors affecting the process. Combined application of compost and mineral fertilizer, however, inhibited CH4 oxidation probably due to N immobilization by the added compost. The positive effect of mineral fertilizer on CH4 oxidation rate was evident only at high CH4 concentration (t(1)2 = 4.80 d), while at low CH4 concentration their was considerable suppression (t(1) = 17.60 d). Further research may reveal that long-term application of fertilizers, organic or inorganic, may not inhibit CH4 oxidation.     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

Novel passive co-treatment of acid mine drainage and municipal wastewater

A laboratory-scale, four-stage continuous-flow reactor system was constructed to test the viability of high-strength acid mine drainage (AMD) and municipal wastewater (MWW) passive co-treatment. Synthetic AMD of pH 2.6 and acidity of 1870 mg L(-1) as CaCO3 equivalent containing a mean 46, 0.25, 2.0, 290, 55, 1.2, and 390 mg L(-1) of Al, As, Cd, Fe, Mn, Pb, and Zn, respectively, was added at a 1:2 ratio with raw MWW from the City of Norman, OK, to the system which had a total residence time of 6.6 d. During the 135-d experiment, dissolved Al, As, Cd, Fe, Mn, Pb, and Zn concentrations were consistently decreased by 99.8, 87.8, 97.7, 99.8, 13.9, 87.9, and 73.4%, respectively, pH increased to 6.79, and net acidic influent was converted to net alkaline effluent. At a wasting rate of 0.69% of total influent flow, the system produced sludge with total Al, As, Cd, Cr, Cu, Fe, Pb, and Zn concentrations at least an order of magnitude greater than the influent mix, which presents a metal reclamation opportunity. Results indicate that AMD and MWW passive co-treatment is a viable approach to use wastes as resources to improve water quality with minimal use of fossil fuels and refined materials.     

Cottongrass effects on trace elements in submersed mine tailings

Phytostabilization may limit the leakage of metals and As from submersed mine tailings, thus treatment of acid mine drainage with lime could be reduced. Tall cottongrass (Eriophorum angustifolium Honckeny) and white cottongrass (E. scheuchzeri Hoppe) were planted in pots with unlimed (pH 5.0) and limed (pH 10.9) tailings (containing sulfides) amended with sewage sludge (SS) or a bioashsewage sludge mixture (ASM). Effects of the amendments on plant growth and plant element uptake were studied. Also, effects of plant growth on elements (Cd, Cu, Pb, Zn, and As), pH, electrical conductivity (EC), and concentrations of SO4(2-), in the drainage water as well as dissolved oxygen in tailings, were measured. Both plant species grew better and the shoot element concentrations of white cottongrass were lower in SS than in ASM. Metal concentrations were lowest in drainage water from limed tailings, and plant establishment had little effect on metal release, except for an increase in Zn levels, even though SO4(2-) levels were increased. In unlimed tailings, plant growth increased SO4(2-) levels slightly; however, pH was increased and metal concentrations were low. Thus, metals were stabilized by plant uptake and high pH. Amendments or plants did not affect As levels in the drainage water from unlimed tailings. Thus, to reduce the use of lime for stabilizing metals, phytostabilization with tall cottongrass and white cottongrass on tailings is a sound possibility.     

高铁酸钾氧化去除弱碱性地下水中低浓度石油类污染物实验研究

研究一般地下水弱碱性水溶液中,高铁酸钾对低浓度石油烃类污染物的氧化去除率.采用0#柴油模拟石油类污染物试验水样,氧化反应在200mL烧杯中模拟完全混合状态完成.实验分析浓度分别为5.02mg/L、2.05mg/L、1.01mg/L和0.52mg/L4个水样石油类污染物氧化去除率.实验研究显示,石油类污染浓度与高铁酸钾浓...     

Compost and calcium surface treatment effects on subsoil chemistry in acidic minespoil columns

Surface incorporation of a liming agent in combination with compost or biosolids is a proven way to revegetate acidic minespoils, but little is known about the effect of the surface amendments on subsoil chemistry. We conducted a greenhouse column experiment to investigate how different surface amendments affected plant growth and subsoil chemistry in highly acidic minespoil material. Columns were filled with shale minespoil material (pH approximately 2.5), amended with CaCO3, CaSO4 x 2H2O (gypsum), and two rates of compost, and seeded with birdsfoot trefoil (Lotus corniculatus L.) and 'Kentucky 31' tall fescue (Festuca arundinacea Schreb.). We measured leachate and plant growth over a 170-d period with extensive irrigation. Without CaCO3, plants could only grow at the high compost rate (68.8 g kg(-1)), even though the soil pH in those treatments was below 3.5, indicating the capability of natural organic matter to detoxify Al(3+) by forming Al-organic matter complexes. Compost had no effect on the subsoil. When CaCO3 or gypsum was added to the surface, extractable Ca increased in the subsoil, but there was no relevant increase in subsoil pH. Even in the first 5 cm of subsoil material, extractable Al did not decrease very much, possibly because a jurbanite-like solid phase controlled subsoil Al(3+) activities. During the reclamation of highly acidic minespoil material one should therefore not expect significant effects of the surface treatment on the untreated subsoil. A sufficient root zone would have to be achieved by incorporating the liming agent down to the desired rooting depth.     

Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation

This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.     

Nitrous oxide and ammonia fluxes in a soybean field irrigated with swine effluent

In the United States, swine (Sus scrofa) operations produce more than 14 Tg of manure each year. About 30% of this manure is stored in anaerobic lagoons before application to land. While land application of manure supplies nutrients for crop production, it may lead to gaseous emissions of ammonia (NH3) and nitrous oxide (N2O). Our objectives were to quantify gaseous fluxes of NH3 and N2O from effluent applications under field conditions. Three applications of swine effluent were applied to soybean [Glycine max (L.) Merr. 'Brim'] and gaseous fluxes were determined from gas concentration profiles and the flux-gradient gas transport technique. About 12% of ammonium (NH4-N) in the effluent was lost through drift or secondary volatilization of NH3 during irrigation. An additional 23% was volatilized within 48 h of application. Under conditions of low windspeed and with the wind blowing from the lagoon to the field, atmospheric concentrations of NH3 increased and the crop absorbed NH3 at the rate of 1.2 kg NH3 ha(-1) d(-1), which was 22 to 33% of the NH3 emitted from the lagoon during these periods. Nitrous oxide emissions were low before effluent applications (0.016 g N2O-N ha(-1) d(-1)) and increased to 25 to 38 g N2O-N ha(-1) d(-1) after irrigation. Total N2O emissions during the measurement period were 4.1 kg N2O-N ha(-1), which was about 1.5% of total N applied. The large losses of NH3 and N2O illustrate the difficulty of basing effluent irrigation schedules on N concentrations and that NH3 emissions can significantly contribute to N enrichment of the environment.     

Field dissipation of acetochlor in two New Zealand soils at two application rates

The persistence of pesticides in soils has both economic and environmental significance and is often used as a key parameter in pesticide risk assessment. Persistence of acetochlor [2'-ethyl-6'-methyl-N-(ethoxymethyl)-2-chloroacetylanilide] in two New Zealand field soils was measured over two years and the data were used to identify models that adequately describe acetochlor persistence in the field. Acetochlor was sprayed onto six fallow plots (3 x 9 m each) at each site at the recommended rate (2.5 kg a.i. ha(-1)) and at twice that rate. Acetochlor concentrations were measured in soil cores. Simple first-order kinetics (Model 1) adequately described acetochlor persistence in Hamilton clay loam soil (Humic Hapludull, Illuvial Spadic) at the high application rate, but overestimated it at the low application rate. A quadratic model (Model 2), a first-order double-exponential model (Model 3), a first-order biphasic model (Model 4), or a two-compartment model (Model 5) better described acetochlor persistence at the low application rate. The time for 50% (DT50) and 90% (DT90) of initial acetochlor loss was approximately 9 and 56 d, and 18 and 63 d at low and high application rates, respectively. The more complex Models 2 through 5 also better described the biphasic dissipation of acetochlor in Horotiu sandy loam soil (Typic Orthic Allophanic) than Model 1, with Model 1 significantly underestimating acetochlor concentrations on the day of application at both application rates. The DT50 and DT90 values were 5 and 29 d and 7 and 31 d at low and high application rates, respectively. Overall, application rate significantly affected the DT50 and DT90 values in the Hamilton soil, but not in the Horotiu soil. Faster acetochlor loss in the Horotiu soil possibly resulted from the higher soil organic carbon content that retained more acetochlor near the soil surface where higher temperature and photolysis accelerated the loss.     

Liming poultry manures to decrease soluble phosphorus and suppress the bacteria population

Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH)2 for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH)2 at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed for microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793,000 to 6500 mL-1. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.     

Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices

After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.     

Poultry litter ash as a potential phosphorus source for agricultural crops

Maryland will impose restrictions on poultry litter application to soils with excessive P by the year 2005. Alternative uses for poultry litter are being considered, including burning as a fuel to generate electricity. The resulting ash contains high levels of total P, but the availability for crop uptake has not been reported. Our objective was to compare the effectiveness of poultry litter ash (PLA) and potassium phosphate (KP) as a P source for wheat (Triticum aestivum L.) in acidic soils, without and with limestone application. Two acidic soils (pH 4.25 and 4.48) were studied, unlimed or limed to pH 6.5 before cropping. The PLA and KP were applied at 0, 39, and 78 kg P ha(-1), after which wheat was grown. Limestone significantly increased wheat yield, but the P sources without limestone did not. The two P sources were not significantly different as P fertilizer. At the 78 kg P ha(-1) rate, wheat shoot-P concentrations were 1.10 and 1.12 g kg(-1) for the PLA treatment compared with 0.90 and 0.89 g kg(-1) for KP in the nonlimed and limed soils, respectively. Trace element concentrations in wheat shoots from the PLA treatment were less than or equal to KP and the control. The low levels of water-soluble P and metals in the soils and the low metal concentrations in wheat suggest that PLA is an effective P fertilizer. Further studies are needed to determine the optimum application rate of PLA as a P fertilizer.     

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline 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.     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.     

Reclamation of acid sulfate soils using lime-stabilized biosolids

Excavation of sulfidic materials during construction has resulted in acid rock drainage (ARD) problems throughout Virginia. The most extensive documented uncontrolled disturbance at a single location is Stafford Regional Airport (SRAP) in Stafford, Virginia. Beginning in 1998, over 150 ha of sulfidic Coastal Plain sediments were disturbed, including steeply sloping cut surfaces and spoils placed into fills. Acid sulfate soils developed, and ARD generated on-site degraded metal and concrete structures and heavily damaged water quality with effects noted over 1 km downstream. The site was not recognized as sulfidic until 2001 when surface soil sampling revealed pH values ranging from 1.9 to 5.3 and peroxide potential acidity (PPA) values ranging from 1 to 42 Mg CaCO(3) per 1000 Mg material. In February 2002 a water quality program was established in and around the site to monitor baseline pH, EC, NO(3)-N, NH(4)-N, PO(4)-P, Fe, Al, Mn, and SO(4)-S, and initial pH values as low as 2.9 were noted in on-site receiving streams. In the spring and fall of 2002, the site was treated with variable rates of lime-stabilized biosolids, straw-mulch, and acid- and salt-tolerant legumes and grasses. By October 2002, the site was fully revegetated (> or = 90% living cover) with the exception of a few highly acidic outcrops and seepage areas. Surface soil sampling in 2003, 2004, and 2006 revealed pH values typically > 6.0. Water quality responded quickly to treatment, although short-term NH(4)(+) release occurred. Despite heavy loadings, no significant surface water P losses were observed.