Transport of methane and noble gases during gas push-pull tests in dry porous media

A field method called the gas push-pull test (GPPT) was previously developed and tested for the in situ quantification of aerobic methane (CH4) oxidation by soil microorganisms. The GPPT consists of an injection followed by extraction of reactant and tracer gases into and out of the soil. Quantification of microbial activities from GPPTs requires insight in the transport of reactant and tracer gases under diverse field conditions. We investigated how the transport of differenttracer gases (He, Ne, and Ar) compares to that of the reactant gas CH4 during GPPTs conducted in a well-defined, dry porous media that mimicked an open system. Transport of gaseous components during GPPT is mainly driven by advection resulting from injection and extraction and diffusion driven by concentration gradients. Regardless of the advective component (selected injection/ extraction, flow rates 0.2-0.8 L min(-1)), diffusion was the dominant transport mechanism for gaseous components. This resulted in dissimilar transport of CH4 and the tracers He and Ne. Numerical simulations of GPPTs showed that similar transport of these components is only achieved at very high injection/extraction rates that, in practice, are not feasible since they would imply extremely short duration times of GPPTs to allow for consumption of a measurable amount of reactant(s) by soil microorganisms. However, Ar transport was similar to that of CH4. Hence, Ar may be a good tracer provided that it is injected at high concentrations (e.g., >25% [v/v]) to overcome its background concentration in soil air. Using moderate injection/ extraction rates (e.g., 0.6 L min(-1)) with injected volumes of 10-30 L will result in GPPT durations of 1-3 h, which would suffice to attain a measurable consumption of reactant(s) in soils having relatively high (e.g., first-order rate constants >0.3 h(-1)) microbial activities.     

Diffusive partitioning tracer test for nonaqueous phase liquid (NAPL) detection in the vadose zone

This paper proposes the theory and practical application of a new partitioning tracer test for nonaqueous phase liquid (NAPL) detection in the vadose zone, which is based on diffusion. A mixture of chlorofluorocarbons as gaseous tracers is injected into the vadose zone to form a point source at the injection point. While the tracers diffuse away, small volumes of gas are withdrawn from the injection point. The quantitative determination of the NAPL saturation is based on a comparison of the concentration decline of tracers with different air-NAPL partitioning coefficients. The test has been evaluated in laboratory sand columns contaminated with dodecane. NAPL in saturations of 0.8-4% of the total porosity have been quantified in a wide range of different water contents. Actual and measured NAPL saturations calculated as an average from four different tracer pairs agreed within +/-30%. The new method was successfully used for repeated NAPL quantification in a large-scale field lysimeter contaminated with artificial kerosene. This rapid and inexpensive test is potentially of value for site investigations especially in combination with soil gas measurements, because it requires similar equipment. Possible applications are source delineation and repeated NAPL quantification in situ during a remediation.     

Review: Technical and policy challenges in deep vadose zone remediation of metals and radionuclides

Contamination in deep vadose zone environments is isolated from exposure so direct contact is not a factor in its risk to human health and the environment. Instead, movement of contamination to the groundwater creates the potential for exposure and risk to receptors. Limiting flux from contaminated vadose zone is key for protection of groundwater resources, thus the deep vadose zone is not necessarily considered a resource requiring restoration. Contaminant discharge to the groundwater must be maintained low enough by natural attenuation (e.g., adsorption processes or radioactive decay) or through remedial actions (e.g., contaminant mass reduction or mobility reduction) to meet the groundwater concentration goals. This paper reviews the major processes for deep vadose zone metal and radionuclide remediation that form the practical constraints on remedial actions. Remediation of metal and radionuclide contamination in the deep vadose zone is complicated by heterogeneous contaminant distribution and the saturation-dependent preferential flow in heterogeneous sediments. Thus, efforts to remove contaminants have generally been unsuccessful although partial removal may reduce downward flux. Contaminant mobility may be reduced through abiotic and biotic reactions or through physical encapsulation. Hydraulic controls may limit aqueous transport. Delivering amendments to the contaminated zone and verifying performance are challenges for remediation.     

Volatilization and biodegradation of naphthalene in the vadose zone impacted by phytoremediation

The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated for naphthalene remediation at a creosote-contaminated site where a poplar tree-based phytoremediation system has been installed. Concurrent field and laboratory experiments were conducted to study the transport and biodegradation of naphthalene in the vadose zone. Soil gas sampling showed that more than 90% of the naphthalene vapors were biodegraded aerobically within 5-10 cm above the water table during the summer months. Peak naphthalene soil gas concentrations were observed in the late summer, corresponding with peak naphthalene aqueous concentrations and the minimum saturated zone thickness. An analytical solution was developed for vapor transport where the diffusion coefficient and first-order biodegradation rate vary vertically in two discrete zones. First-order aerobic biodegradation rates in laboratory columns using unsaturated site soil ranged from 5 to 28 days(-1) with a mean rate of 11 days(-1). The observed naphthalene mass flux at the source (3.3-22 microg cm(-2) d(-1)) was enhanced by aerobic biodegradation and was greater than the mean observed flux in the abiotic control column and the maximum theoretical mass flux by factors of 7 and 28, respectively.     

Biofiltration for mitigation of methane emission from animal husbandry

Removal of methane from exhaust air of animal houses and manure storage has a large potential for the reduction of greenhouse gas emissions from animal husbandry. The aim of this study was to design a biofilter for methane removal at a full-scale livestock production facility. Air from the headspace of a covered 6 m3 liquid manure storage (air flow: 0.75-8.5 m3 m(-3) h(-1); CH4: 500-5500 mg m(-3)) was treated in an experimental biofilter (160 L). The filterbed, a mixture of compost and perlite in a 40:60 (v/v) ratio, was inoculated with activated sludge that had shown a good methane oxidation rate as compared to pure cultures in preceding laboratory tests. Methane removal up to 85% could be achieved in the experimental biofilter. The methane removal (g m(-3) h(-1)) appeared to be proportional to the concentration (g m(-3)) with k = 2.5 h(-1). Relatively low methane concentrations and high air flows, as reported for the exhaust air of animal houses, would require very large biofilter sizes. Extrapolation of the results showed that treatment of air from a 1000 m3 liquid manure storage with a methane concentration of 22 g m(-3) would require a 20 m3 biofilter for a desired emission reduction of 50%. The costs for such a biofilter are USD 26 per t of CO2 equiv reduction.     

Capacity for biodegradation of CFCs and HCFCs in a methane oxidative counter-gradient laboratory system simulating landfill soil covers

The attenuation of methane and four chlorofluorocarbons was investigated in a dynamic methane and oxygen counter-gradient system simulating a landfill soil cover. Soil was sampled at Skellingsted Landfill, Denmark. The soil columns showed a high capacity of methane oxidation with oxidation rates of 210 g m(-2) d(-1) corresponding to a removal efficiency of 81%. CFC-11 and to a lesser extent also CFC-12 were degraded in the active soil columns. The average removal efficiency was 90% and 30% for CFC-11 and CFC-12, respectively. Soil gas concentration profiles indicated that the removal was due to anaerobic degradation, which was verified in anaerobic batch experiments where CFC-11 was rapidly degraded. HCFC-21 and HCFC-22 were also degraded in active soil columns (61% and 41%, respectively), but compared to the CFCs, the degradation was located in the upper oxic part of the column with overlapping gradients of methane and oxygen. High oxidation rates of methane and HCFCs were obtained in soil microcosms incubated with methane. When increasing the column inlet flow, the oxidation zone was moved upward in the column, and the removal efficiency of methane and HCFCs decreased. The removal of CFCs was, however, less affected since the anaerobic zone expanded with increasing inlet flow rates. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play a very important role in reducing the emission of not only methane but also trace components into the atmosphere.     

Fluorescence imaging of tracer distributions in soil profiles

To evaluate and parametrize transport models for the vadose (partially water-unsaturated) zone, information about the spatial distributions of solutes is needed. We describe a technique for the simultaneous imaging of several fluorescent tracers in structured field soils. With this technique, we obtain information on local mixing under field conditions. Local dispersion is a decisive process that discriminates different flow regimes. The imaging device consists of a high-power xenon lamp and a sensitive charge coupled device (CCD) camera. The three fluorescent dyes Brilliant sulfaflavine (BF), Sulforhodamine B (SB), and Oxazine 170 (OX) were chosen as solute tracers for their spectroscopic properties and different sorption coefficients. We conducted a field experiment using these tracers and took images of their distribution in a vertical soil profile. The fluorescence images (1242 by 1152 pixels) were corrected for nonuniform lighting, changing surface roughness, and varying optical properties of the soil profile. The resulting two-dimensional relative concentration distributions were similar for BF and SB. The reason might be the fast transport regime, which prevents the establishment of sorption equilibria. According to its higher sorption coefficient, OX was more strongly retarded. In this paper, we show that the fluorescence imaging technique is a powerful tool for the in-situ investigation of transport processes of fluorescent solute tracers in soil profiles. Due to the high spatial resolution of the tracer concentration maps and the ability to detect the flow field characteristics of differently reactive tracers simultaneously under field conditions, this technique provides valuable experimental data for the test and development of theoretical models for heterogeneous solute transport in soils.     

Transport of methane and noble gases during gas push-pull tests in variably saturated porous media

The gas push-pull test (GPPT) is a single-well gas-tracer method to quantify in situ rates of CH4 oxidation in soils. To improve the design and interpretation of GPPT field experiments, gas component transport during GPPTs was examined in abiotic porous media over a range of water saturations (0.0 < or = Sw < or = 0.61). A series of GPPTs using He, Ne, and Ar as tracers for CH4 were performed at two injection/extraction gas flow rates (approximately 200 and approximately 700 mL min(-1)) in a laboratory tank. Extraction phase breakthrough curves and mass recovery curves of the gaseous components became more similar at higher Sw as water in the pore space restricted diffusive gas-phase transport. Diffusional fractionation of the stable carbon isotopes of CH4 during the extraction period of GPPTs also decreased with increasing Sw (particularly when Sw > 0.42). Gas-component transport during GPPTs was numerically simulated using estimated hydraulic parameters for the porous media and no fitting of data for the GPPTs. Numerical simulations accurately predicted the relative decline of the gaseous components in the breakthrough curves, but slightly overestimated recoveries at low Sw (< or = 0.35) and underestimated recoveries at high Sw (> or = 0.49). Comparison of numerical simulations considering and not considering air-water partitioning indicated that removal of gaseous components through dissolution in pore water was not significant during GPPTs, even at Sw = 0.61. These data indicate that Ar is a good tracer for CH4 physical transport over the full range of Sw studied, whereas, at Sw > 0.61, any of the tracers could be used. Greater mass recovery at higher Sw raises the possibility to reduce gas flow rates, thereby extending GPPT times in environments such as tundra soils where low activity due to low temperatures may require longer test times to establish a quantifiable difference between reactant and tracer breakthrough curves.     

Biofiltration and inhibitory interactions of gaseous benzene, toluene, xylene, and methyl tert-butyl ether

This study evaluated the individual and combined removal capacities of benzene, toluene, and xylene (B, T, and X) in the presence and absence of methyl tert-butyl ether (MTBE) in a polyurethane biofilter inoculated with a BTX-degrading microbial consortium, and further examined their interactive effects in various mixtures. In addition, Polymerase chain reaction-denaturing gradient gel electrophoresis and phylogenetic analysis of 16S rRNA gene sequences were used to compare the microbial community structures found in biofilters exposed to the various gases and gas mixtures. The maximum individual elimination capacities (MECs) of B, T, and X were 200, 238, and 400 g m(-3) h(-1), respectively. There was no significant elimination of MTBE alone. Addition of MTBE decreased the MECs of B,T, and X to 75, 100, and 300 g m(-3) h(-1), respectively, indicating that benzene was most strongly inhibited by MTBE. When the three gases were mixed (B + T + X), the removal capacities of individual B, T, and X were 50, 90, and 200 g m(-3) h(-1), respectively. These capacities decreased to 40, 50, and 100 g m(-3) h(-1) when MTBE was added to the mix. The MEC of the three-gas mixture (B + T + X) was 340 g m(-3) h(-1), and that of the four-gas mixture was 200 g m(-3) h(-1). Although MTBE alone was not degraded by the biofilter, it could be co-metabolically degraded in the presence of toluene, benzene, or xylene with the MECs of 34, 23, and 14 g m(-3) h(-1), respectively. The microbial community structure analysis revealed that two large groups could be distinguished based on the presence or absence of MTBE, and many of the dominant bacteria in the consortia were closely related to bacteria isolated from aromatic hydrocarbon-contaminated sites and/ or oil wastewaters. These findings provide important new insights into biofiltration and may be used to improve the rational design of biofilters for remediation of petroleum gas-contaminated airstreams according to composition types of mixed gases.     

Distribution of atmospheric SF6 near a large urban area as recorded in the vadose zone

Local emissions of SF6 are of interest for studying their impact on the use of SF6 as a groundwater-dating tool near source regions as well as for investigating the spatial distributions of (inert) gaseous compounds spreading from urban or industrial centers. A precondition for the use of SF6 in such studies is the capability to document the temporal and spatial evolution of SF6 in and around source regions with sufficient resolution. Here we present a time series of SF6 measurements in soil air at a site (Sparkill, NY) about 25 km north of New York City carried out between May 2000 and January 2002. The data show that, below about 2 m depth, the vadose zone integrates atmospheric SF6 mixing ratios over time scales greater than 1 month. SF6 mixing ratios in soil air at these depths match averaged high-resolution atmospheric measurements performed at Lamont-Doherty Earth Observatory in Palisades, NY, located about 3 km south of Sparkill. To a first-order approximation, a simple one-dimensional diffusion model reproduces the measured SF6 profiles in the vadose zone, suggesting that the soil indeed acts as a low-pass filter for inert atmospheric gases. These findings indicate that measurements of soil air can be used to determine the spatial pattern of SF6 excess relative to the remote atmosphere for a given region. A transect of soil profiles from Manhattan to the tip of Long Island indicates that emissions from sites close to New York City lead to significant SF6 excesses (ca. 25% or more) above the clean air mixing ratios over distances of the order of 80 km.     

Comparative oxidation and net emissions of methane and selected non-methane organic compounds in landfill cover soils

The surface emissions of methane (CH4) and non-methane organic compounds (NMOCs) were determined at two different areas at a French landfill: a permanently covered and fully vegetated area (40 cm coarse sand + 80 cm of loam) and a temporarily covered area (40 cm of coarse sand). The 37 NMOCs quantified in the landfill gas samples included alkanes (C1-C10), alkenes (C1-C4), halogenated hydrocarbons (including (H)CFCs), and aromatic hydrocarbons. Both positive and negative CH4 fluxes ranging from -0.01 to 0.008 g m(-2) d(-1) were measured from the permanently covered cell. However, high spatial variation was observed, and a hot spot with a high flux (10 g m(-2) d(-1)) was identified. A higher CH4 emission occurred from the temporarily covered cell (CH4 flux of 49.9 g m(-2) d(-1)) as compared to the permanently covered cell. The NMOC fluxes from the permanently covered zone were all very small with both positive and negative fluxes in the order of 10(-7) to 10(-5) g m(-2) d(-1). Higher and mainly positive NMOC fluxes in the order of 10(-5) to 10(-4) g m(-2) d(-1) were obtained from the temporarily covered zone. The lower emission from the permanently covered and fully vegetated cell was attributable to the thicker soil layer, which functions as microbial habitat for methanotrophic bacteria. The NMOC oxidation capacity was investigated in soil microcosms incubated with CH4. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.06 and 8.56 microg (g of soil)(-1) d(-1). Fully substituted hydrocarbons (tetrachloromethane, perchloroethylene, CFC-11, CFC-12, and CFC-113) were not degraded in the presence of CH4 and O2. Benzene and toluene were rapidly degraded, giving very high maximal oxidation rates (28 and 39 microg (g of soil)(-1) d(-1)). On the basis of the emission measurements and the batch experiments conducted, a general pattern was observed between emissions and biodegradability of various NMOCs. The emissions mainly consisted of compounds that were not degradable or slowly degradable, while an uptake of easily degradable compounds was registered. As an example, perchloroethylene, trichloromethane, CFC-11, and CFC-12 were emitted, while atmospheric consumption of aromatic hydrocarbons and lower chlorinated hydrocarbons such as vinyl chloride, dichloromethane, and chloromethane was observed. This study demonstrates that landfill soil covers show a significant potential for CH4 oxidation and co-oxidation of NMOCs. Under certain conditions, landfills may even function as sinks for CH4 and selected NMOCs, like aromatic hydrocarbons and lower chlorinated compounds.     

Isotopic and geochemical assessment of in situ biodegradation of chlorinated hydrocarbons

Currently there is no in situ method to detect and quantify complete mineralization of chlorinated hydrocarbons (CHCs) to CO2. Combined isotopic measurements in conjunction with traditional chemical techniques were used to assess in situ biodegradation of trichloroethylene (TCE) and carbon tetrachloride (CT). Vadose zone CHC, ethene, ethane, methane, O2, and CO2 concentrations were analyzed using gas chromatography over 114 days at the Savannah River Site. delta13C of CHC and delta13C and 14C of vadose zone CO2, sediment organic matter, and groundwater dissolved inorganic carbon (DIC)were measured. Intermediate metabolites of TCE and CT accounted for < or = 10% of total CHCs. Delta13C of cis-1,2-dichloroethylene (DCE) was always heavier than TCE indicating substantial DCE biodegradation. 14C-CO2 values ranged from 84 to 128 percent modern carbon (pMC), suggesting that plant root-respired CO2 was dominant. 14C-CO2 values decreased over time (up to 12 pMC), and contaminated groundwater 14C-DIC (76 pMC) was substantially depleted relative to the control (121 pMC). 14C provided a direct measure of complete CHC mineralization in vadose zone and groundwater in situ and may improve remediation strategies.     

Sequestration and remobilization of radioiodine (129I) by soil organic matter and possible consequences of the remedial action at Savannah River Site

In order to investigate the distributions and speciation of (129)I (and (127)I) in a contaminated F-Area groundwater plume of the Savannah River Site that cannot be explained by simple transport models, soil resuspension experiments simulating surface runoff or stormflow and erosion events were conducted. Results showed that 72-77% of the newly introduced I(-) or IO(3)(-) were irreversibly sequestered into the organic-rich riparian soil, while the rest was transformed by the soil into colloidal and truly dissolved organo-iodine, resulting in (129)I remobilization from the soil greatly exceeding the 1 pCi/L drinking water permit. This contradicts the conventional view that only considers I(-) or IO(3)(-) as the mobile forms. Laboratory iodination experiments indicate that iodine likely covalently binds to aromatic structures of the soil organic matter (SOM). Under very acidic conditions, abiotic iodination of SOM was predominant, whereas under less acidic conditions (pH ≥5), microbial enzymatically assisted iodination of SOM was predominant. The organic-rich soil in the vadose zone of F-Area thus acts primarily as a "sink," but may also behave as a potentially important vector for mobile radioiodine in an on-off carrying mechanism. Generally the riparian zone provides as a natural attenuation zone that greatly reduces radioiodine release.     

Mechanisms affecting the infiltration and distribution of ethanol-blended gasoline in the vadose zone

One- and two-dimensional experiments were conducted to examine differences in the behavior of gasoline and gasohol (10% ethanol by volume) as they infiltrate through the unsaturated zone and spread at the capillary fringe. Ethanol in the spilled gasohol quickly partitions into the residual water in the vadose zone and is retained there as the gasoline continues to infiltrate. Under the conditions tested, over 99% of the ethanol was initially retained in the vadose zone. Depending on the volume of gasoline spilled and the depth to the water table, this causes an increase in the aqueous-phase saturation and relative permeability, thus allowing the ethanol-laden water to drain into the gasoline pool. Under the conditions tested, the presence of ethanol does not have a significant impact on the overall size or shape of the resulting gasoline pool at the capillary fringe. Residual gasoline saturations in the vadose zone were significantly reduced however because of reduced surface and interfacial tensions associated with high ethanol concentrations. The flux of ethanol in the effluent of the column ranged from 1.4 x 10(-4) to 4.5 x 10(-7) g/(cm2 min) with the LNAPL and from 6 x 10(-3) to 3.0 x 10(-4) g/(cm2 min) after water was introduced to simulate rain infiltration. The experimental results presented here illustrate that the dynamic effects of ethanol partitioning into the aqueous phase in the vadose zone create an initial condition that is significantly different than previously understood.     

Oxidation of H2S by iron oxides in unsaturated conditions

Previous studies have demonstrated that gas-phase H2S can immobilize certain redox-sensitive contaminants (e.g., Cr, U, Tc) in vadose zone environments. A key issue for effective and efficient delivery of H2S in these environments is the reactivity of the gas with indigenous iron oxides. To elucidate the factors that control the transport of H2S in the vadose zone, laboratory column experiments were conducted to identify reaction mechanisms and measure rates of H2S oxidation by iron oxide-coated sands using several carrier gas compositions (N2, air, and O2) and flow rates. Most experiments were conducted using ferrihydrite-coated sand. Additional studies were conducted with goethite- and hematite-coated sand and a natural sediment. Selective extractions were conducted at the end of each column experiment to determine the mass balance of the reaction products. XPS was used to confirm the presence of the reaction products. For column experiments in which ferrihydrite-coated sand was the substrate and N2 was the carrier gas, the major H2S oxidation products were FeS and elemental sulfur (mostly S8(0), represented as S(0) for simplicity) at ratios that were consistent with the stoichiometry of the postulated reactions. When air or O2 were used as the carrier gas, S(0) became the dominant reaction product along with FeS2 and smaller amounts of FeS, sulfate, and thiosulfate. A mathematical model of reactive transport was used to test the hypothesis that S(0) forming on the iron oxide surfaces reduces access of H2S to the reactive surface. Several conceptual models were assessed in the context of the postulated reactions with the final model based on a linear surface poisoning model and fitted reaction rates. These results indicate that carrier gas selection is a critical consideration with significant tradeoffs for remediation objectives.     

Recovery of phenanthrene-degrading bacteria after simulated in situ persulfate oxidation in contaminated soil

A continuous-flow column study was conducted to investigate the long-term effects of persulfate oxidation on the abundance and activity of the indigenous microbial community and phenanthrene-degrading bacteria in contaminated soil from a former manufactured gas plant (MGP) site. Approximately six pore volumes of a 20 g/L persulfate solution were introduced into the column, followed by simulated groundwater for 500 days. Soil samples were collected from the surface of the soil bed and along the column length immediately before and after persulfate injection and up to 500 days following injection. Exposure to persulfate led to a 2- to 3-log reduction in total bacterial 16S rRNA genes, severe inhibition of (14)C-acetate mineralization (as a measure of general microbial activity), and a decrease in community diversity. However, relatively rapid recovery of both bacterial gene abundance and activity was observed within 30 days after persulfate exposure. Mineralization of (14)C-phenanthrene was also inhibited but did not recover until 100 days postoxidation. Known phenanthrene-degrading bacterial groups decreased to below detection limits throughout the column, with recovery times from 100 to 500 days after persulfate injection. These findings suggest that coupling biological processes with persulfate oxidation is possible, although recovery of specific contaminant degraders may occur much later than the general microbial community recovers. Furthermore, the use of total bacterial quantity or nonspecific measures of activity as a surrogate for the recovery of contaminant degraders may be inappropriate for evaluating the compatibility of chemical treatment with subsequent bioremediation.     

Soil column evaluation of factors controlling biodegradation of DNT in the vadose zone

High concentrations of 2,4-dinitrotoluene (2,4-DNT) and 2,6-dinitrotoluene (2,6-DNT) are present in vadose zone soils at many facilities where explosives manufacturing has taken place. Both DNT isomers can be biodegraded under aerobic conditions, but rates of intrinsic biodegradation observed in vadose zone soils are not appreciable. Studies presented herein demonstrate that nutrient limitations control the onset of rapid 2,4-DNT biodegradation in such soils. In column studies conducted at field capacity, high levels of 2,4-DNT biodegradation were rapidly stimulated by the addition of a complete mineral medium but not by bicarbonate-buffered distilled deionized water or by phosphate-amended tap water. Biodegradation of 2,6-DNT was not observed under any conditions. Microcosm studies using a DNT-degrading culture from column effluent suggest that, after the onset of 2,4-DNT degradation, nitrite evolution will eventually control the extent of degradation achieved by two mechanisms. First, high levels of nitrite (40 mM) were found to strongly inhibit 2,4-DNT degradation. Second, nitrite production reduces the solution pH, and at pH levels below 6.0, 2,4-DNT degradation slows rapidly. Under conditions evaluated in laboratory-scale studies, 2,4-DNT biodegradation enhanced the rate of contaminant loss from the vadose zone by a factor of 10 when compared to the washout due to leaching.     

Identifying the sources of subsurface contamination at the Hanford Site in Washington using high-precision uranium isotopic measurements

In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple-collector ICP source magnetic sector mass spectrometry, high-precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The isotope ratios 236U/238U, 234U/238U, and 238U/235U are used to distinguish contaminant sources. On the basis of the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high-level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a significant source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of approximately 0.7-0.8 m/day showing slight retardation relative to a groundwater flow of approximately 1 m/day.     

Measurement of N2, N2O, NO, and CO2 emissions from soil with the gas-flow-soil-core technique

Here we describe a newly designed system with three stand-alone working incubation vessels for simultaneous measurements of N(2), N(2)O, NO, and CO(2) emissions from soil. Due to the use of a new micro thermal conductivity detector and the redesign of vessels and gas sampling a so-far unmatched sensitivity (0.23 μg N(2)-N h(-1) kg(-1) ds or 8.1 μg N(2)-N m(-2) h(-1)) for detecting N(2) gas emissions and repeatability of experiments could be achieved. We further tested different incubation methods to improve the quantification of N(2) emission via denitrification following the initialization of soil anaerobiosis. The best results with regard to the establishment of a full N balance (i.e., the changes in mineral N content being offset by simultaneous emission of N gases) were obtained when the anaerobic soil incubation at 25 °C was preceded by soil gas exchange under aerobic conditions at a lower incubation temperature. The ratios of N and C gas emission changed very dynamically following the initialization of anaerobiosis. For soil NO(3)(-) contents of 50 mg N kg(-1) dry soil (ds) and dissolved organic carbon (DOC) concentrations of approximately 300 mg C kg(-1) ds, the cumulative emissions of N(2), N(2)O, and NO were 24.3 ± 0.1, 12.6 ± 0.4, and 10.1 ± 0.3 mg N kg(-1) ds, respectively. Thus, N gas emissions accounted (on average) for 46.2% (N(2)), 24.0% (N(2)O), and 19.2% (NO) of the observed changes in soil NO(3)(-). The maximum N(2) emission reached 1200 μg N h(-1) kg(-1) ds, whereas the peak emissions of N(2)O and NO were lower by a factor of 2-3. The overall N(2):N(2)O and NO:N(2)O molar ratios were 1.6-10.0 and 1.6-2.3, respectively. The measurement system provides a reliable tool for studying denitrification in soil because it offers insights into the dynamics and magnitude of gaseous N emissions due to denitrification under various incubation conditions.     

Reduction of crop contamination by soil resuspension within the 30-km zone of the Chernobyl nuclear power plant

A field experiment was conducted within the 30-km zone of the Chernobyl Nuclear Power Plant to analyze whether the application of mulching reduced resuspension of 137Cs contaminated soil in oat (Avena sativa) crops. In 1993, we applied a mulch treatment at a dose of 200 g m(-2), and soil resuspension was measured by estimating soil loadings onto plant surfaces from Ti concentrations in plants. In 1994, two mulch doses were applied, 200 and 50 g m(-2), and we estimated the contribution of soil resuspension by using artificial resuspension collection devices (ARC). In the 1993 experiment between 4.6 and 34.4% of the plant's total 137Cs contamination was attributed to external soil contamination. The mean amount of soil-derived 137Cs attached to vegetation was 124.7 Bq kg(-1)(plant) in control plots and 53.7 Bq kg(-1)(plant) in mulched plots. In the 1994 experiment, covering the soil with a mulch layer decreased the radiocesium content in ARC by about 70%. Results obtained in these experiments suggest that soil resuspension was a significant mechanism for plant contamination and that mulching was effective in reducing that contamination.