Effective elution of RDX and TNT from particles of Comp B in surface soil

During live fire training exercises, large amounts of explosives are consumed. Low order detonations of high explosive payloads result in the patchy dispersal of particles of high explosive formulations over large areas of firing range soils. Dissolution of explosives from explosive formulation particles into soil pore water is a controlling factor for transport, fate, and effects of explosive compounds. We developed an empirical method to evaluate soils based on functionally defined effective dissolution rates. An automated Accelerated Solvent Extractor was used to determine the effective elution rates under controlled conditions of RDX and TNT from soil columns containing particles of Comp B. Contrived soils containing selected soil geosorbants and reactive surfaces were used to quantitatively determine the importance of these materials. Natural soils from training ranges of various soil types were also evaluated. The effects of geosorbants on effective elution rates were compound- and sorbent-specific. TNT elution was less than that of RDX and was greatly slowed by humic acid. Iron and iron-bearing clays reduced the effective elution rates of both RDX and TNT. This empirical method is a useful tool for directly generating data on the potential for explosives to leach from firing range soils, to identify general bulk soil characteristics that can be used to predict the potential, and to identify means to engineer soil treatments to mitigate potential transport.     

Physicochemical characterization and mercury speciation of particle-size soil fractions from an abandoned mining area in Mieres, Asturias (Spain)

Soils from old cinnabar mining areas usually exhibit high Hg contents, whose mobility depends on soil parameters and environmental conditions. This paper presents the study of the Hg speciation in soil samples from an abandoned Hg mine and metallurgical plant in Mieres (Asturias, Spain), in relation to their mineralogical and chemical composition and their particle-size distribution. A characterization of samples was made by X-Ray Diffraction Spectrometry, Scanning Electron Microscopy and Atomic Absorption and Emission Spectroscopy analyses. A sequential extraction method was applied to establish Hg mobility in the samples and their grain-size subsamples. The highest Hg mobility was found in well-developed soils, as a consequence of the adsorption processes by iron and manganese oxides, whereas in those more contaminated soils, a higher proportion of Hg was leached in the non-mobile fraction. A higher Hg mobility was found in the finest grain-size subsamples, probably due to the accumulation of clay minerals and oxides in these ranges.     

Chlorpyrifos degradation in Turkish soil

Degradation of chlorpyrifos was evaluated in laboratory studies. Surface (0-15 cm) and subsurface (40-60 cm) clay loam soils from a pesticide-untreated field were incubated in biometer flasks for 97 days at 25 degrees C. The treatment was 2 micrograms g-1 [2,6-pyridinyl-14C] chlorpyrifos, with 74 kBq radioactivity per 100 g soil flask. Evolved 14CO2 was monitored in KOH traps throughout the experiment. Periodically, soil subsamples were also methanol-extracted [ambient shaking, then supercritical fluid extraction (SFE)], then analyzed by thin-layer chromatography. Total 14C and unextractable soil-bound 14C residues were determined by combustion. From the surface and subsurface soils, 41 and 43% of the applied radiocarbon was evolved as 14CO2 during 3 months incubation. The time required for 50% loss of the parent insecticide in surface and subsurface soils was about 10 days. By 97 days, chlorpyrifos residues and their relative concentration (in surface/subsurface) as % of applied 14C were: 14CO2 (40.6/42.6), chlorpyrifos (13.1/12.4), soil-bound residues (11.7/11.4), and 3,5,6-trichloropyridinol (TCP) (3.8/4.8). Chlorpyrifos was largely extracted by simple shaking with methanol, whereas TCP was mainly removed only by SFE. The short persistence of chlorpyrifos probably relates to the high soil pH (7.9-8.1).     

Generalized models for prediction of pentachlorophenol dissipation dynamics in soils

Dissipation of pentachlorophenol (PCP) in soil was investigated and the chemical relationships with soil properties were addressed. The results indicate that the dissipation of extractable PCP residues can be described using first-order kinetics equations, with a half-dissipation time (T(1/2)) ranging from 6.5 to 173.3d. The sharply different patterns of PCP dissipation in different soils were closely related to soil properties. Correlations of stepwise regression equations obtained were significant at 0.01 probability level between soil parameters and extractable PCP residues (R(2)=0.974**) as well as T(1/2) values (R(2)=0.882**). Using pH together with organic carbon content (OC) and soil particle size distribution, the dissipation dynamics of PCP in soil could be accurately predicted.     

Content and distribution of forms of organic N in soil and particle size fractions after long-term fertilization

Most of the N in surface soils occurs in organic forms, and when mineralized it plays a key role in soil fertility and plant nutrition. Our objective was to study the effect of long-term applications of organic manure on the content and distribution of forms of organic N in bulk soil and soil particle size fractions to characterize the inherent soil nitrogen fertility. Five treatments were as follows: (1) CK (no fertilizer and no manure added), (2) mineral fertilizer only, (3) straw + NPK, (4) green manure + NPK and (5) pig manure + NPK. Soil particle size fractions (0-2, 2-10, 10-50 and 50-100 microm) were isolated without chemical pretreatment by ultrasonic dispersion in water followed by sedimentation. The content of total N and forms of organic N in the bulk soil increased after long-term fertilization, and the effect varied with fertilizer type. The plot treated with only mineral fertilizer gave the highest NH3-N and the lowest amino sugar-N content in all treatments. The highest content of amino sugar-N and amino acid-N was found in the treatment of pig manure + NPK. The content (g kg(-1) fraction) of hydrolysable N within size fractions was in the order 0-2 > 2-10 > 50-100 > 10-50 microm, but the contribution of different size fraction to hydrolysable N decreased in the sequence 10-50 > 0-2 > 2-10 > 50-100 microm. Most of the applied mineral fertilizer N that remained in soils was distributed in the particle size fraction < 2 microm while most of the remaining N from manure applied with NPK was transferred into amino sugar-N in each size fraction, and amino acid-N in the size fractions > 2 microm during the process of humification.     

UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.     

A case study of contaminants on military ranges: Camp Edwards, Massachusetts, USA

An extensive investigation at the Camp Edwards, Massachusetts Military Reservation (MMR) demonstrates that assessment of groundwater and soil contamination at military ranges can be limited primarily to explosive-related compounds such as RDX, HMX, perchlorate, TNT and their transformation products. A modified analytical method is recommended to expand the list of explosives and to improve the detection limits. Analyses of metals, VOCs, SVOCs, and TICs are unnecessary. Soil samples may require the analyses of PAHs and PCNs for burn areas. Camp Edwards, as one of the few military ranges that have been exhaustively investigated for contaminants, is an ideal point of departure for evaluating other ranges. The permeable site soils promote leaching of contaminants and inhibit biotic and abiotic transformations. Moreover, the site has experienced an unusual extent of activities in its more than ninety years of active use. The recommendations in this report are based on data obtained for more than 200 analytes from more than 15,000 environmental samples.     

Immobilization of lead in shooting range soils by means of cement, quicklime, and phosphate amendments

BACKGROUND, AIM, AND SCOPE: Lead (Pb) contamination at shooting range sites is increasingly under environmental concern. Controlling Pb leachability from shooting range soil media is an important step to minimize Pb exposure to the surrounding environment. This study investigated stabilization of Pb in shooting range soils treated with cement, quicklime, and phosphate. MATERIALS AND METHODS: Two soils were used and collected from two shooting ranges, referred to as SR1 and SR2. The treatment additives were applied to the soils at rates from 2.5% to 10% (w/w). The effectiveness of each treatment was evaluated by Pb (w/w). The effectiveness of each treatment was evaluated by Pb leachability, measured by the Toxicity Characteristic Leaching Procedure (TCLP). The possible mechanisms for Pb immobilization were elucidated using X-ray powder diffraction (XRPD). RESULTS: Cement and quicklime treatments were effective in immobilizing Pb in SR1 soil, with reduction of Pb concentration in TCLP leachate (TCLP-Pb) to be below the U.S. EPA non-hazardous regulatory limit of 5 mg L(-1) at application rates of > or =5% and 28-d incubation. By contrast, cement and quicklime amendments were less effective for Pb stabilization in SR2 soil because the TCLP-Pb levels in the treated soil were still higher than the limit of 5 mg L(-1) at all application rates, although they were significantly reduced in comparison with the untreated soil. Phosphate application was most effective in reducing Pb leach ing in both soils. Even at an application rate as low as 5% and 1-d incubation, phosphate could reduce TCLP-Pb to be below the limit of 5 mg L(-1) in both soils. DISCUSSION: Immobilization of Pb in the SR1 soil amended with cement and quicklime was attributed to the formation of pozzolanic minerals (e.g., calcium silicate hydrate C-S-H and ettringite) that could encapsulate soil Pb. The pozzolanic reaction was limited in the SR2 soil upon the application of cement and quicklime. Reduction of the TCLP-Pb might result from complexation of Pb on the surface of the formed calcite. Phosphate-induced Pb immobilization was mainly attributed to formation of less soluble PbHPO4. CONCLUSIONS: The results indicate that effectiveness of cementitious treatments (cement and quicklime) in immobilizing Pb varies in two soils, being effective in SR1 soil but less in SR2 soil. For one given soil, no difference was observed of the effeciveness between cement and quicklime treatments, whereas phosphate amendment emerges as a most effective treatment means for stabilizing Pb in both two soils, and it also shows a faster immobilization process and little effect on the soil acid buffering capacity. Recommendations and Perspectives. Overall, our study reveals that immobilizing Pb can be one of the best management practices for Pb contamination at shooting range sites. Phosphate amendment is most effective in immobilizing Pb in any kind of the soil ranges to minimize negative Pb impacts on the shooting range sites.     

Bioavailable DDT residues in sediments: laboratory assessment of ageing effects using semi-permeable membrane devices

We describe the reduction in bioavailability of DDT in contaminated soil after it was incubated as sediment for 365 d. Bioavailability was assessed using semi-permeable membranes. Contaminated soils from three cattle dip sites, one spiked paired uncontaminated site, and one spiked OECD standard soil were studied. Sandy soil with residues of 1880 mg/kg summation operator DDT incurred since 1962, initially had 4.6% of summation operator DDT available, reducing to 0.6% following 365 d. Clay soil (1108 mg summation operator DDT/kg) had 4.1% initially available, reducing to 0.3% after 365 d. Freshly spiked soils had a greater amount of DDT initially available (10.9%), but this reduced to 1.5% by the end of the incubation. Of the DDT congeners, both o,p'-DDD and p,p'-DDD were most bioavailable in the soils, but also had the most significant decrease following incubation.     

High uptake of 2,4,6-trinitrotoluene by vetiver grass--potential for phytoremediation?

2,4,6-Trinitrotoluene (TNT) is a potent mutagen, and a Group C human carcinogen that has been widely used to produce munitions and explosives. Vast areas that have been previously used as ranges, munition burning, and open detonation sites are heavily contaminated with TNT. Conventional remediation activities in such sites are expensive and damaging to the ecosystem. Phytoremediation offers a cost-effective, environment-friendly solution, utilizing plants to extract TNT from contaminated soil. We investigated the potential use of vetiver grass (Vetiveria zizanioides) to effectively remove TNT from contaminated solutions. Vetiver grass plants were grown in hydroponic systems containing 40 mg TNTL(-1) for 8d. Aqueous concentrations of TNT reached the method detection limit ( approximately 1 microg L(-1)) within the 8-d period, demonstrating high affinity of vetiver for TNT, without any visible toxic effects. Results from this preliminary hydroponic study are encouraging, but in need of verification using TNT-contaminated soils.     

Dissipation of chlorpyrifos in two soil environments of semi-arid India

The dissipation of chlorpyrifos (20 EC) at environment-friendly doses in the sandy loam and loamy sand soils of two semi-arid fields and the presence of pesticide residues in the harvested groundnut seeds, were monitored. The movement of chlorpyrifos through soil and its binding in the loamy sand soil was studied using 14C chlorpyrifos. Chlorpyrifos was moderately stable in both loamy sand and sandy loam soils, with half-life of 12.3 and 16.4 days, respectively. With 20 EC treatments the dissipation was slower for standing crop than seed treatment, indicative of the high degradation rates in the bioactive rhizosphere. In soil, 3,5,6-trichloro-2-pyridinol (TCP) was the principal breakdown product. Presence of 3,5,6-trichloro-2-methoxypyridine (TMP), the secondary metabolite, detected in the rhizospheric samples during this study, has not been reported earlier in field soils. The rapid dissipation of the insecticide from the soil post-application might have resulted from low sorption due to the alkalinity of the soil and its low organic matter content, fast topsoil dissipation possibly by volatilization and photochemical degradation, aided by the low water solubility, limited vertical mobility due to confinement of residues to the upper 15 cm soil layers and microbial mineralization and nucleophilic hydrolysis. Contrary to the reports of relatively greater mobility of its metabolites in temperate soils, TMP and TCP remained confined to the top 15 cm soil. The formation of bound residues (half-life 13.4 days) in the loamy sand soil was little and not "irreversible." A decline in bound residues could be correlated to decreasing TCP concentration. Higher pod yields were obtained from pesticide treated soils in comparison to controls. Post-harvest no pesticide residues were detected in the soils and groundnut seeds.     

Scavenging of BHCs and DDTs from soil by thermal desorption and solvent washing

Intensive remediation of abandoned former organochlorine pesticides (OCPs) manufacturing areas is necessary because the central and surrounding soils contaminated by OCPs are harmful to crop production and food safety. Organochlorine and its residues are persistent in environments and difficult to remove from contaminated soils due to their low solubility and higher sorption to the soils. We performed a comprehensive study on the remediation of OCPs-contaminated soils using thermal desorption technique and solvent washing approaches. The tested soil was thermally treated at 225, 325, 400, and 500 °C for 10, 20, 30, 45, 60, and 90 min, respectively. In addition, we tested soil washing with several organic solvents including n-alcohols and surfactants. The optimal ratio of soil/solvent was tested, and the recycling of used ethanol was investigated. Finally, activities of polyphenol oxidase (PPO), urease (URE), alkaline phosphatase, acid phosphatase (ACP), and invertase (INV) were assayed in the treated soils. The tested soil was thermally treated at 500 °C for 30 min, and the concentration of contaminants in soil was decreased from 3,115.77 to 0.33 mg kg^?1. The thermal desorption in soil was governed by the first-order kinetics model. For the chemical washing experiment, ethanol showed a higher efficiency than any other solvent. Using a 1:20 ratio of soil/solvent, the maximum removal of OCPs was achieved within 15 min. Under this condition, approximately 87 % of OCPs was removed from the soils. More than 90 % of ethanol in the spent wash fluid could be recovered. Activities of some enzymes in soils were increased after ethanol treatment. But ALP, ACP, and INV activities were decreased and PPO and URE showed slightly higher activities following remediation by thermal treatment. Both heating temperature and time were the key factors for thermal desorption of OCPs. The n-alcohol solvent showed higher removal of OCPs from soils than surfactants. The highly efficient removal of OCPs from soil was achieved using ethanol. More than 90 % of ethanol could be recovered and be reused following distillation. This study provides a cost-effective and highly efficient way to remediate the OCPs-contaminated soils.     

Metal distributions in soil receiving urban pavement runoff and snowmelt.

Wet and dry deposition of anthropogenic metals and particulates generated from urban and traffic activities can result in contamination of urban-land-use soils. These particulate residuals encompass a wide size gradation, from 1 to greater than 10 000 microm. This study hypothesized that such contamination of surficial soils can be analyzed and explained as a function of the soil/residual granulometry. This study analyzed the gradation-based physical characteristics for 10 urban transportation land-use sites with soil/residual complexes (SRCs) located throughout metropolitan Cincinnati, Ohio, and an urban residential reference site. Particle density (rho(s)) of SRCs ranged from 2.8 to 2.1 g/cm3, with the lower particle density associated with particles less than 100 microm. For each site, specific surface area generally increased with decreasing particle size, while the predominance of total surface area was associated with the coarser size fractions, except for the clayey glacial till reference site not influenced by traffic. Cumulative analysis for lead, copper, cadmium, and zinc associated with SRCs indicated that more than 50% of the metal mass was associated with particles greater than 250 microm, with more than 80% associated with particles greater than 106 microm. Study results are similar to rainfall-runoff and snowmelt distributions. Results provide guidance when considering potential fate and control of metals transported by urban drainage and are distributed across the SRC size gradation.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of (14)C labeled isoproturon have been determined in two Moroccan soils by beta -counting-liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.     

The extractability and mineralisation of cypermethrin aged in four UK soils

Cypermethrin is a widely used insecticide that has caused concern due to its toxicity in the aquatic environment. As with all land applied pesticides, the most significant source of water pollution is from the soil, either due to leaching or washoff. The behaviour of cypermethrin in the soil controls the likelihood of future pollution incidents, with two of the most significant processes being the formation of bound residues and microbial degradation. The formation of bound residues and mineralisation was measured in four organically managed soils from the UK. The formation of bound residues was measured using three different extraction solutions, 0.01 M CaCl₂, 0.05 M HPCD and acetonitrile. Biodegradation was assessed by measurement of mineralisation of cypermethrin to CO₂. The formation of bound residues varied according to extraction method, soil type and length of ageing. In two of the four soils studied, acetonitrile extractability decreased from 100% initially to 12-14% following 100 d ageing. The extent of mineralisation increased after 10-21 d ageing, reaching 33% of remaining activity in one soil, however following 100 d ageing the extent of mineralisation was significantly reduced in three out of the four soils. As with the formation of bound residues, mineralisation was impacted by soil type and length of ageing.     

Evaluation of remediation process with plant-derived biosurfactant for recovery of heavy metals from contaminated soils

A washing process was studied to evaluate the efficiency of saponin on remediating heavy metal contaminated soils. Three different types of soils (Andosol: soil A, Cambisol: soil B, Regosol: soil C) were washed with saponin in batch experiments. Utilization of saponin was effective for removal of heavy metals from soils, attaining 90-100% of Cd and 85-98% of Zn extractions. The fractionations of heavy metals removed by saponin were identified using the sequential extraction. Saponin was effective in removing the exchangeable and carbonated fractions of heavy metals from soils. In recovery procedures, the pH of soil leachates was increased to about 10.7, leading to separate heavy metals as hydroxide precipitates and saponin solute. In addition recycle of used saponin is considered to be effective for the subsequent utilization. The limits of Japanese leaching test were met for all of the soil residues after saponin treatment. As a whole, this study shows that saponin can be used as a cleaning agent for remediation of heavy metal contaminated soils.     

Influence of ageing of residues on the availability of herbicides for leaching

Losses by leaching of chlorotoluron, isoproturon and triasulfuron from small intact columns of a structured clay loam and an unstructured sandy loam soil were measured in five separate field experiments. In general, losses of all three herbicides were greater from the clay loam than from the sandy loam soil and the order between herbicides was always triasulfuron > isoproturon > chlorotoluron. Differences between experiments were also consistent for every soil/herbicide combination. There was no relationship between total loss and either total rainfall or cumulative leachate volume. When weighting factors were applied to the rainfall data to make early rainfall more important than later rainfall, there were significant positive relationships between cumulative weighted rainfall and total losses. Also, there were significant negative correlations between total losses and the delay to accumulation of 25 mm rainfall (equivalent to one pore volume of available water) in the different experiments. In laboratory incubations, there was a more rapid decline in aqueous (0.01 M calcium chloride) extractable residues than in total solvent extractable residues indicating increasing sorption with residence time. However, the rate of change in water extractable residues could not completely explain the decrease in leachability with ageing of residues in the field. Short-term sorption studies with aggregates of the two soils indicated slower sorption by those of the clay loam than by those of the sandy loam suggesting that diffusion into and out of aggregates may affect availability for leaching in the more structured soil. Small scale leaching studies with aggregates of the soils also demonstrated reductions in availability for leaching as residence time in soil was increased, which could not be explained by degradation. These results therefore indicate that time-dependent sorption processes are important in controlling pesticide movement in soils, although the data do not give a mechanistic explanation of the changes in leaching with ageing of residues.     

Influence of humic fractions on retention of isoproturon residues in two Moroccan soils

The influence of different fractions of soil organic matter on the retention of the herbicide isoproturon (IPU) has been evaluated. Water and methanol extractable residues of ¹⁴C labeled isoproturon have been determined in two Moroccan soils by β -counting–liquid chromatography. The quantification of bound residues in soil and in different fractions of soil humic substances has been performed using pyrolysis/scintillation-detected gas-chromatography. Microbial mineralization of the herbicide and soil organic matter has been also monitored. Retention of isoproturon residues after 30-days incubation ranged from 22% to 32% (non-extractable fraction). The radioactivity extracted in an aqueous environment was from 20% to 33% of the amount used for the treatment; meanwhile, methanol was able to extract another 48%. Both soils showed quantities of bound residues into the humin fraction higher than humic and fulvic acids. The total amount of residues retained into the organic matter of the soils was about 65 % of non-extractable fraction, and this percentage did not change with incubation time; on the contrary, the sorption rate of the retention reaction is mostly influenced by the clay fraction and organic content of the soil. Only a little part of the herbicide was mineralized during the experimental time.