Adsorption of RDX to Soil with Low Organic Carbon: Laboratory Results,Field Observations,Remedial Implications

The purpose of this article is to review both laboratory and field observations of RDX adsorption to soils and to use those results to estimate the effects of a planned remedial action. Adsorption isotherms for RDX are generally observed to be linear and reversible. Statistical tests were performed to determine the relationship between K_d and various soil characteristics. A linear relationship between Kd and soil organic carbon was observed, as expected, but regression of K_d to organic carbon content indicated a non-zero intercept, suggesting that other sorbents may also be significant at low OC (e.g., > 0.5 %). No other soil properties were significantly related to Kd so the mechanism of adsorption at low organic carbon was not determined. These results were used to interpret observations of RDX in the vadose zone at Milan Army Ammunition Plant (MAAP), TN. MAAP exhibits widespread soil contamination by RDX. Depth to groundwater ranges from 40 to 80?ft. Unsaturated soils are fine grained near the surface, and sandy near the water table. RDX is concentrated in the upper 2?ft, where concentrations in some places exceed 1 %. Subsurface concentrations are generally less than 50?mg/kg. The distribution of RDX in soil, soil moisture and groundwater, and soil physical testing data were interpreted using simple models. The distribution of RDX is consistent with the following conceptual model: ??Water containing RDX was dis charged to the land surface (prior to 1983); ??Crystalline RDX remains in surface soil (remedial activities are ongo ing); ??Infiltrating rainwater leaches RDX from surface soils; ??This leachate carries RDX through the deeper vadose zone, resulting in significant soil contamination through out the full thickness of the vadose zone; these soils can generate leachate and adversely affect ground- water quality for many years to come. Field results were consistent with the adsorption studies. Simple models consistent with the field and laboratory observations indicate that deeper soils that are not planned to be remediated may continue to leach unacceptable concentrations to groundwater for approximately 180 years. The Army intends to evaluate whether it will be most cost-effective to address this continuing source by treating soils or groundwater.     

Biodegradation of RDX in Unsaturated Soil

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a military explosive that is a common soil and groundwater contaminant at facilities that manufacture, handle, and dispose of munitions. One such facility is the U.S. Department of Energy Pantex Plant, the focus of this research in which the feasibility of in situ bioremediation of contaminated soil in the vadose zone was assessed. A batch technique using ¹⁴C-RDX was developed to investigate the degradation of RDX under aerobic, microaerobic, and anaerobic conditions. In addition, the effect of nutrients (organic carbon and phosphorus) on biodegradation rates was studied. The extent of mineralization was quantified by monitoring the production of ¹⁴CO₂, and RDX biodegradation rates were estimated for each environmental condition. The results showed that RDX degraders were indigenous to the contaminated soil and degraded RDX to a significant extent under anaerobic conditions. Little biotransformation was observed under aerobic conditions. The addition of a biodegradable organic carbon source significantly increased the RDX biodegradation rate. Under appropriate environmental conditions, significant mineralization of RDX also was observed. The half-lives for the degradation of RDX under anaerobic conditions were approximately 60 days and decreased to approximately 40 days with nutrient addition. In contrast, the half-life for aerobic degradation was on the order of 1000 days, with an upper 95% confidence interval approaching infinity.     

A Study of Vadose Zone Transport Model VLEACH

Application of vadose zone transport models has been hampered by lack of model validation. Difficulties to validate vadose zone models using field data not only come from model assumptions that are uncertain to the subsurface transport processes but also from the uncertainties associated with soil contaminants’ release time and quantity, soil sampling, sample transport, and analytical procedures. This article first conducts a test of a popularly used vadose zone transport VLEACH by comparing model results with a set of laboratory soil column infiltration and volatilization study data. The comparison shows a close agreement between the VLEACH model results and the laboratory data. Second, the sorption coefficient K_d calculated in VLEACH is compared with field data. The comparison indicates that VLEACH may overestimate the mass leached from soil to groundwater. The article also discusses the selection of the model simulation timestep, the vertical dimension increment, the Courant criterion, and the lower boundary condition using the sensitivity analysis method based on a case study of soil remediation for trichloroethylene. The procedures presented in this paper are important to practical model application and modification. This level of work should be routinely conducted for any new or modified version of vadose zone models.     

Calculation of soil cleanup criteria for volatile organic compounds as controlled by the soil‐to‐groundwater pathway: Comparison of four unsaturated soil zone leaching models

Four computer models that predict leaching of chemicals in the unsaturated soil zone were used to calculate example soil cleanup criteria for volatile organic compounds, using a hypothetical environmental scenario. The criteria were calculated so that allowable groundwater concentrations for the chemicals were not exceeded. The models used were the Pesticide Root Zone Model (PRZM) and the Seasonal Soil Compartment Model (SESOIL) from the U.S. Environmental Protection Agency, the Sanitary Landfill Model (SLM1) from Oregon State University, and the Integrated Moisture and Aqueous Contaminant Transport model (IMPACT) under development for the State of New Jersey. The hypothetical scenario assumed a water table depth of 10 ft, a contaminated zone from 0 to 4 ft, and sandy loam soil properties. Transport times to groundwater were similar for all four models. The calculated soil criteria for many chemicals using the four models agreed to within an order of magnitude. In a few instances, SLM1 and PRZM predicted much lower cleanup criteria than the other two models because volatilization losses were not modeled. Calculated criteria were often quite low when degradation was assumed to be zero. When estimated degradation rates were employed, criteria were sometimes considerably higher.     

VIRTUS, a model of virus transport in unsaturated soils.

As a result of the recently proposed mandatory groundwater disinfection requirements to inactivate viruses in potable water supplies, there has been increasing interest in virus fate and transport in the subsurface. Several models have been developed to predict the fate of viruses in groundwater, but few include transport in the unsaturated zone and all require a constant virus inactivation rate. These are serious limitations in the models, as it has been well documented that considerable virus removal occurs in the unsaturated zone and that the inactivation rate of viruses is dependent on environmental conditions. The purpose of this research was to develop a predictive model of virus fate and transport in unsaturated soils that allows the virus inactivation rate to vary on the basis of changes in soil temperature. The model was developed on the basis of the law of mass conservation of a contaminant in porous media and couples the flows of water, viruses, and heat through the soil. Model predictions were compared with measured data of virus transport in laboratory column studies and, with the exception of one point, were within the 95% confidence limits of the measured concentrations. The model should be a useful tool for anyone wishing to estimate the number of viruses entering groundwater after traveling through the soil from a contamination source. In addition, model simulations were performed to identify parameters that have a large effect on the results. This information can be used to help design experiments so that important variables are measured accurately.     

The role of microbial populations in the containment of aromatic hydrocarbons in the subsurface

A survey of soil gases associated with gasoline stations on theSwan Coastal Plain of Western Australia has shown that 20% leak detectable amountsof petroleum. The fates of volatile hydrocarbons in the vadose zone at one contaminatedsite, and dissolved hydrocarbons in groundwater at another site were followed in anumber of studies which are herein reviewed. Geochemical evidence from a plume ofhydrocarbon-contaminated groundwater has shown that sulfate reduction rapidly developedas the terminal electron accepting process. Toluene degradation but not benzene degradationwas linked to sulfate reduction. The sulfate-reducing bacteria isolated from the plumerepresented a new species, Desulfosporosinus meridiei. Strains of the speciesdo not mineralise ¹⁴C-toluene in pure culture. The addition of large numbersof cells and sulfate to microcosms did stimulate toluene mineralisation but not benzenemineralisation. Attempts to follow populations of sulfate-reducing bacteria byphospholipid signatures, or Desulfosporosinus meridiei by FISH in the plume were unsuccessful, but fluorescently-labeled polyclonal antibodies were successfully used.In the vadose zone at a different site, volatile hydrocarbons were consumed in thetop 0.5 m of the soil profile. The fastest measured rate of mineralisation of ¹⁴C-benzenein soils collected from the most active zone (6.5 mg kg^-1 day^-1) could accountfor the majority of the flux of hydrocarbon vapour towards the surface. The studiesconcluded that intrinsic remediation by subsurface microbial populations in groundwateron the Swan Coastal Plain can control transport of aromatic hydrocarbon contamination,except for the transport of benzene in groundwater. In the vadose zone, intrinsicremediation by the microbial populations in the soil profile can contain the transportof aromatic hydrocarbons, provided the physical transport of gases, inparticular oxygen from the atmosphere, is not impeded by structures.     

Expression in grasses of multiple transgenes for degradation of munitions compounds on live‐fire training ranges

The deposition of toxic munitions compounds, such as hexahydro‐1, 3, 5‐trinitro‐1, 3, 5‐triazine (RDX), on soils around targets in live‐fire training ranges is an important source of groundwater contamination. Plants take up RDX but do not significantly degrade it. Reported here is the transformation of two perennial grass species, switchgrass (Panicum virgatum) and creeping bentgrass (Agrostis stolonifera), with the genes for degradation of RDX. These species possess a number of agronomic traits making them well equipped for the uptake and removal of RDX from root zone leachates. Transformation vectors were constructed with xplA and xplB, which confer the ability to degrade RDX, and nfsI, which encodes a nitroreductase for the detoxification of the co‐contaminating explosive 2, 4, 6‐trinitrotoluene (TNT). The vectors were transformed into the grass species using Agrobacterium tumefaciens infection. All transformed grass lines showing high transgene expression levels removed significantly more RDX from hydroponic solutions and retained significantly less RDX in their leaf tissues than wild‐type plants. Soil columns planted with the best‐performing switchgrass line were able to prevent leaching of RDX through a 0.5‐m root zone. These plants represent a promising plant biotechnology to sustainably remove RDX from training range soil, thus preventing contamination of groundwater.     

Fate and Transport of 2,4,6-Trinitrotoluene in Loams at a Former Explosives Factory

Natural attenuation processes affecting 2,4,6-trinitrotoluene (TNT) were determined within loams for two study areas at the former Explosives Factory Maribyrnong, Australia. TNT fate and transport was investigated through spectrophotometric/High Performance Liquid Chromatography (HPLC) analyses of soil and groundwater, adsorption and microcosm testwork. A five tonne crystalline TNT source zone delineated within near surface soils at the base of a TNT process waste lagoon was found to be supplying aqueous TNT loading (7 ppm) to subsurface soils and groundwater. The resultant plume was localized within the loam aquitard due to a combination of natural attenuation processes and hydrogeological constraints, including low hydraulic conductivity and upward hydraulic gradients. Freundlich described sorptive partitioning was the main TNT sink (K_F = 29 mL/g), while transformation rates were moderate (1.01 × 10^-4 h^-1) under the aerobic conditions. Increasing 2-amino-4,6-dinitrotoluene predominance over 4-amino-2,6-dinitrotoluene was discovered with depth (in situ) and time (microcosms). Simplified dissolution rate calculations indicate that without mitigation of the TNT source, contaminant persistence within the vadose zone may approach 2000 years, while ATRANS20 simulations demonstrate that the TNT plume propagates very slowly along the flow path within the aquitard.     

Plants as Bio-Indicators of Subsurface Conditions: Impact of Groundwater Level on BTEX Concentrations in Trees

Numerous studies have demonstrated trees’ ability to extract and translocate moderately hydrophobic contaminants, and sampling trees for compounds such as BTEX can help delineate plumes in the field. However, when BTEX is detected in the groundwater, detection in nearby trees is not as reliable an indicator of subsurface contamination as other compounds such as chlorinated solvents. Aerobic rhizospheric and bulk soil degradation is a potential explanation for the observed variability of BTEX in trees as compared to groundwater concentrations. The goal of this study was to determine the effect of groundwater level on BTEX concentrations in tree tissue. The central hypothesis was increased vadose zone thickness promotes biodegradation of BTEX leading to lower BTEX concentrations in overlying trees. Storage methods for tree core samples were also investigated as a possible reason for tree cores revealing lower than expected BTEX levels in some sampling efforts. The water level hypothesis was supported in a greenhouse study, where water table level was found to significantly affect tree BTEX concentrations, indicating that the influx of oxygen coupled with the presence of the tree facilitates aerobic biodegradation of BTEX in the vadose zone.     

Plants as Bio-Indicators of Subsurface Conditions: Impact of Groundwater Level on Btex Concentrations in Trees

Numerous studies have demonstrated trees’ ability to extract and translocate moderately hydrophobic contaminants, and sampling trees for compounds such as BTEX can help delineate plumes in the field. However, when BTEX is detected in the groundwater, detection in nearby trees is not as reliable an indicator of subsurface contamination as other compounds such as chlorinated solvents. Aerobic rhizospheric and bulk soil degradation is a potential explanation for the observed variability of BTEX in trees as compared to groundwater concentrations. The goal of this study was to determine the effect of groundwater level on BTEX concentrations in tree tissue. The central hypothesis was increased vadose zone thickness promotes biodegradation of BTEX leading to lower BTEX concentrations in overlying trees. Storage methods for tree core samples were also investigated as a possible reason for tree cores revealing lower than expected BTEX levels in some sampling efforts. The water level hypothesis was supported in a greenhouse study, where water table level was found to significantly affect tree BTEX concentrations, indicating that the influx of oxygen coupled with the presence of the tree facilitates aerobic biodegradation of BTEX in the vadose zone.     

VIRTUS, a model of virus transport in unsaturated soils.

As a result of the recently proposed mandatory groundwater disinfection requirements to inactivate viruses in potable water supplies, there has been increasing interest in virus fate and transport in the subsurface. Several models have been developed to predict the fate of viruses in groundwater, but few include transport in the unsaturated zone and all require a constant virus inactivation rate. These are serious limitations in the models, as it has been well documented that considerable virus removal occurs in the unsaturated zone and that the inactivation rate of viruses is dependent on environmental conditions. The purpose of this research was to develop a predictive model of virus fate and transport in unsaturated soils that allows the virus inactivation rate to vary on the basis of changes in soil temperature. The model was developed on the basis of the law of mass conservation of a contaminant in porous media and couples the flows of water, viruses, and heat through the soil. Model predictions were compared with measured data of virus transport in laboratory column studies and, with the exception of one point, were within the 95% confidence limits of the measured concentrations. The model should be a useful tool for anyone wishing to estimate the number of viruses entering groundwater after traveling through the soil from a contamination source. In addition, model simulations were performed to identify parameters that have a large effect on the results. This information can be used to help design experiments so that important variables are measured accurately.     

干旱区包气带土壤水分运移能量关系及驱动力研究评述

包气带土壤能量和水分平衡及其驱动因子是维系地下水-土壤-植物-大气连续体(GSPAC)系统中水分运移发生的关键因素。在降水稀少、水资源短缺的干旱地区,开展包气带土壤水分形态、运移过程与能量的耦合规律研究对揭示区域水资源形成和转化机理具有极其重要的现实意义。文章总结了土壤水分运移理论研究进展,探讨了水分参与水文循环过程及干旱环境下土壤水分可能表现形态及其降雨入渗、再分布、渗漏、蒸发、毛管水上升等过程驱动机制,评述了包气带土壤水分与能量过程在不同空间尺度上生态水分效应。在一个非饱和土壤系统中,水分运移受包气带结构,土壤物理特征,植物根系和土壤生化环境的综合控制,物质和能量平衡改变是驱动水分循环的源动力,而土壤环境变化是导致水分运移形态的发生变化根本原因。因此,在气候变化背景下,研究干旱区土壤与大气界面以及包气带与饱和带界面水、汽、热耦合转化形式与能量驱动过程,能够提升我们对包气带土壤水分运移规律机理的深入理解,丰富对区域气候和水文变化认知。为干旱区生态植被恢复建设和水资源精细化管理提供理论向导。     

Biodegradation of trichloroethylene and toluene by indigenous microbial populations in vadose sediments

The unsaturated subsurface (vadose zone) receives significant amounts of hazardous chemicals, yet little is known about its microbial communities and their capacity to biodegrade pollutants. Trichloroethylene (TCE) biodegradation occurs readily in surface soils; however, the process usually requires enzyme induction by aromatic compounds, methane, or other cosubstrates. The aerobic biodegradation of toluene and TCE by indigenous microbial populations was measured in samples collected from the vadose zone at unpolluted and gasoline-contaminated sites. Incubation at field moisture levels showed little activity on either TCE or toluene, so samples were tested in soil suspensions. No degradation occurred in samples suspended in water or phosphate buffer solution; however, both toluene and TCE were degraded in samples suspended in mineral salts medium. TCE degradation depended on toluene degradation, and little loss occurred under sterile conditions. Studies with specific nutrients showed that addition of ammonium sulfate was essential for degradation, and addition of other mineral nutrients further enhanced the rate. Additional studies with vadose sediments amended with nutrients showed similar trends to those observed in sediment suspensions. Initial rates of biodegradation in suspensions were faster in uncontaminated samples than in gasolinecontaminated samples, but the same percentages of chemicals were degraded. Biodegradation was slower and less extensive in shallower samples than deeper samples from the uncontaminated site. Two toluene-degrading organisms isolated from a gasoline-contaminated sample were identified as Corynebacterium variabilis SVB74 and Acinetobacter radioresistens SVB65. Inoculation with 10⁶ cells of C. variabilis ml^–1 of soil solution did not enhance the rate of degradation above that of the indigenous population. These results indicate that mineral nutrients limited the rate of TCE and toluene degradation by indigenous populations and that no additional benefit was derived from inoculation with a toluene-degrading bacterial strain. Correspondence to: K.M. Scow     

Modeling Dissolution of High Explosive Formulations

A water dissolution model for solid-phase compounds in soil has been developed that is a variation of previous such models. The formulation for this model is presented along with comparison to previous formulations. The model is applied to experiments reported in the literature involving water dissolution of high explosive (HE) compounds and compared with those reported experimental results. This dissolution model is used in the TREECS? contaminant fate modeling system that was developed for predicting surface water and groundwater contaminant concentrations resulting from solid-phase contaminant particles deposited in soil. The dissolution model performed well against measured results for a single component HE (TNT), but input adjustments, primarily for initial particle size and solubility, were required for good agreement for multi-component HE formulations. These adjustments are presented.     

RDX degrading microbial communities and the prediction of microorganisms responsible for RDX bioremediation

The explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has caused significant soil and groundwater contamination. To remediate these sites, there is a need to determine which microorganisms are responsible for in situ biodegradation of RDX to enable the appropriate planning of bioremediation efforts. Here, studies are examined that have reported on the microbial communities linked with RDX biodegradation. Dominant microorganisms across samples are discussed and summarized. This information is then compared to current knowledge on RDX degrading isolates to predict which organisms may be responsible for RDX degradation in soils and groundwater. From the phyla with known RDX degrading isolates, Firmicutes and Proteobacteria (particularly Gammaproteobacteria) were the most dominant organisms in many contaminated site derived samples. Organisms in the phyla Deltaproteobacteria, Alphaproteobacteria and Actinobacteria were dominant in these studies less frequently. Notably, organisms within the class Betaproteobacteria were dominant in many samples and yet this class does not appear to contain any known RDX degraders. This analysis is valuable for the future development of molecular techniques to track the occurrence and abundance of RDX degraders at contaminated sites.     

Monte Carlo Vadose Zone Model for Soil Remedial Criteria

Many vadose zone models are available for environmental remediation, but few offer the procedures for verifying model predictions with field data and for dealing with uncertainties associated with model input parameters. This article presents a modified model combining a one-dimensional vadose-zone transport model and a simple groundwater mixing model with a function of Monte Carlo simulation (MCS). The modified model is applied to determine soil remedial concentrations for methyl tertiary butyl ether (MTBE). The modified model generates a distribution of MTBE ground-water concentrations at the point of compliance. This distribution can be used to estimate the risk of exceeding groundwater quality standard given soil remedial concentrations. In a case study, soil remedial concentration for MTBE is established to be 5?µg/kg, with a 95% and 10?µg/kg with a 50% probability that groundwater concentration will not exceed the water quality objective of 13?µg/L. Furthermore, this study uses MCS to investigate uncertainties of model input parameter hydraulic conductivity (K). One set of data (K1) is based on the results of hydraulic conductivity laboratory tests, and the other (K2) is based on the results of slug tests conducted in the field. As expected, the laboratory data show smaller K values than the field data. The comparison of the MCS results obtained from the two sets of K data indicates that the MTBE groundwater concentrations calculated based on K1 are generally 160 to 625% greater than those calculated based on K2 at the same percentiles of the MCS distribution. A higher soil remedial concentration of9jig/kg is then calculated based on the MCS results from K2 at 95%ile and 19?µg/kg at 50%ile.     

Bioventing soils contaminated with petroleum hydrocarbons

Summary Bioventing combines the capabilities of soil venting and enhanced bioremediation to cost-effectively remove light and middle distillate hydrocarbons from vadose zone soils and the groundwater table. Soil venting removes the more volatile fuel components from unsaturated soil and promotes aerobic biodegradation by driving large volumes of air into the subsurface. In theory, air is several thousand times more effective than water in penetrating and aerating fuel-saturated and low permeability soil horizons. Aerobic microbial degradation can mitigate both residual and vapor phase hydrocarbon concentrations. Soil venting is being evaluated at a number of U.S. military sites contaminated with middle distillate fuels to determine its potential to stimulate in situ aerobic biodegradation and to develop techniques to promote in situ vapor phase degradation. In situ respirometric evaluations and field pilot studies at sites with varying soil conditions indicate that bioventing is a cost-effective method to treat soils contaminated with jet fuels and diesel.     

Involvement of cytochrome c CymA in the anaerobic metabolism of RDX by Shewanella oneidensis MR-1

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a cyclic nitramine explosive commonly used for military applications that is responsible for severe soil and groundwater contamination. In this study, Shewanella oneidensis MR-1 was shown to efficiently degrade RDX anaerobically (3.5?μmol·h(-1)·(g protein)(-1)) via two initial routes: (1) sequential N-NO(2) reductions to the corresponding nitroso (N-NO) derivatives (94% of initial RDX degradation) and (2) denitration followed by ring cleavage. To identify genes involved in the anaerobic metabolism of RDX, a library of ~2500 mutants of MR-1 was constructed by random transposon mutagenesis and screened for mutants with a reduced ability to degrade RDX compared with the wild type. An RDX-defective mutant (C9) was isolated that had the transposon inserted in the c-type cytochrome gene cymA. C9 transformed RDX at ~10% of the wild-type rate, with degradation occurring mostly via early ring cleavage caused by initial denitration leading to the formation of methylenedinitramine, 4-nitro-2,4-diazabutanal, formaldehyde, nitrous oxide, and ammonia. Genetic complementation of mutant C9 restored the wild-type phenotype, providing evidence that electron transport components have a role in the anaerobic reduction of RDX by MR-1.     

Denitrification in the vadose zone and in surficial groundwater of a sandy entisol with citrus production

A portion of nitrate (NO ₃ ⁻ ), a final breakdown product of nitrogen (N) fertilizers, applied to soils and/or that produced upon decomposition of organic residues in soils may leach into groundwater. Nitrate levels in water excess of 10 mg L⁻¹ (NO₃–N) are undesirable as per drinking water quality standards. Nitrate concentrations in surficial groundwater can vary substantially within an area of citrus grove which receives uniform N rate and irrigation management practice. Therefore, differences in localized conditions which can contribute to variations in gaseous loss of NO ₃ ⁻ in the vadose zone and in the surficial aquifer can affect differential concentrations of NO₃–N in the groundwater at different points of sampling. The denitrification capacity and potential in a shallow vadose zone soil and in surficial groundwater were studied in two large blocks of a citrus grove of ‘Valencia’ orange trees (Citrus sinensis (L.) Obs.) on Rough lemon rootstock ( Citrus jambhiri (L.)) under a uniform N rate and irrigation program. The NO₃–N concentration in the surficial groundwater sampled from four monitoring wells (MW) within each block varied from 5.5- to 6.6-fold. Soil samples were collected from 0 to 30, 30 to 90, or 90 to 150 cm depths, and from the soil/groundwater interface (SGWI). Groundwater samples from the monitoring wells (MW) were collected prior to purging (stagnant water) and after purging five well volumes. Without the addition of either C or N, the denitrification capacity ranged from 0.5 to 1.53, and from 0.0 to 2.25 mg N₂O–N kg⁻¹ soil at the surface soil and at the soil/groundwater interface, respectively. The denitrification potential increased by 100-fold with the addition of 200 mg kg⁻¹ each of N and C. The denitrification potential in the groundwater also followed a pattern similar to that for the soil samples. Denitrification potential in the soil or in the groundwater was greatest near the monitor well with shallow depth of vadose zone (MW3). Cumulative N₂O–N emission (denitrification capacity) from the SGWI soil samples and from stagnant water samples strongly correlated to microbial most probable number (MPN) counts (r² = 0.84 – 0.89), and dissolved organic C (DOC) (r² = 0.96 – 0.97). Denitrification capacity of the SGWI samples moderately correlated to water-filled pore space (WFPS) (r² = 0.52). However, extractable NO₃-N content of the SGWI soil samples poorly (negative) correlated to denitrification capacity (r² = 0.35). However, addition C, N or both to the soil or water samples resulted in significant increase in cumulative N₂O emission. This study demonstrated that variation in denitrification capacity, as a result of differences in denitrifier population, and the amount of readily available carbon source significantly (at 95% probability level) influenced the variation in NO₃–N concentrations in the surficial groundwater samples collected from different monitoring wells within an area with uniform N management. This revised version was published online in June 2006 with corrections to the Cover Date.     

In Situ Biodegradation of High Explosives in Soils: Field Demonstration

The first field pilot-scale demonstration of a technology for in situ remediation of vadose zone soils contaminated with high explosives (HEs) has been performed at the Department of Energy's Pantex Plant. The HEs of concern at the demonstration site were hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and the 2,4,6-trinitrotoluene (TNT) metabolite 1,3,5-trinitrobenzene (TNB). Concentrations ranged from 70 ppm, above the (prior to 1999) risk reduction clean-up criteria of 2.6 and 0.51 ppm, respectively. The shallow (<10?m depth) soils at the site could not be excavated due to the presence of buried utilities. Based on previous laboratory studies, it was found that the contaminated soils had indigenous microbial populations that could be stimulated to degrade the RDX and TNB anaerobically. A 5-spot well pattern with injection at the central well and extraction at the four outer wells (each 4.6?m from the injection well) was used to flood the target vadose zone soils with nitrogen gas with the intent of stimulating the activity of the HE degraders. The system was monitored periodically for gas composition as well as HE concentrations and microbial activity in retrievable soil samples. After 295 days of in situ treatment, the average target HE concentrations were approximately one-third lower than the initial site averages. Operation of the pilot-scale treatment system continues.