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.     

Use of potassium formate in road winter deicing can reduce groundwater deterioration

We present here an aquifer scale study on the fate of potassium formate, an alternative, weakly corrosive deicing agent in soil and subsurfaces. Potassium formate was used to deice a stretch of a highway in Finland. The fate of the formate was examined by monitoring the groundwater chemistry in the underlying aquifer of which a conceptual model was constructed. In addition, we determined aerobic and anaerobic biodegradation rates of formate at low temperatures (-2 to +6 degrees C) in soil microcosms. Our results show that the formate did not enter the saturated zone through the thin vadose zone; thus, no undesirable changes in the groundwater chemistry were observed. Furthermore, the conceptual model explained the distribution of chloride in the aquifer used in deicing for the past 30 years. We recorded mineralization potential up to 97% and up to 17% within 24 h under aerobic and anaerobic conditions, respectively, in the soil and subsurface samples obtained from the site. This demonstrates that biodegradation in the topsoil layers was responsible for the removal of the formate. We conclude that the use of potassium formate can potentially help diminish the negative impacts of road winter deicing on groundwater without jeopardizing traffic safety.     

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.     

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.     

Direct volatilization of naphthalene to the atmosphere at a phytoremediation site

Phytoremediation systems are known to reduce groundwater contamination by at least three major mechanisms: plant uptake, phytovolatilization, and enhanced rhizosphere bioremediation. The potential for such systems to enhance a fourth remediation pathway--direct surface volatilization of contaminants through the subsurface and into the atmosphere-has not yet been investigated in the field. A vertical flux chamber was used to measure direct surface volatilization of naphthalene over nine months at a creosote-contaminated site in Oneida, Tennessee, where a phytoremediation system of poplar trees was installed in 1997. A maximum flux of 23 microg m(-2) h(-1) was measured in August 2004, and naphthalene removal by the direct volatilization pathway is estimated to be 50 g yr(-1) at this site. Results suggest that direct volatilization fluxes are most strongly affected by the groundwater level (thickness of the saturated zone), soil moisture, and changes in atmospheric pressure. At this site, transpiration and canopy interception resulting from the phytoremediation system significantly reduce the saturated thickness, increasing the vertical concentration gradient of naphthalene in the groundwater and thus increasing the upward diffusive flux of naphthalene through the subsurface. The presence of the trees, therefore, promotes direct volatilization into the atmosphere. This research represents the first known measurement of naphthalene attenuation by the direct volatilization pathway.     

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.     

Effect of saline waste solution infiltration rates on uranium retention and spatial distribution in Hanford sediments

The accidental overfilling of waste liquid from tank BX-102 at the Hanford Site in 1951 put about 10 t of U(VI) into the vadose zone. In order to understand the dominant geochemical reactions and transport processes that occurred during the initial infiltration and to help understand current spatial distribution, we simulated the waste liquid spilling event in laboratory sediment columns using synthesized metal waste solution. We found that, as the plume propagated through sediments, pH decreased greatly (as much as 4 units) at the moving plume front. Infiltration flow rates strongly affect U behavior. Slower flow rates resulted in higher sediment-associated U concentrations, and higher flow rates (> or =5 cm/day) permitted practically unretarded U transport. Therefore, given the very high Ksat of most of Hanford formation, the low permeability zones within the sediment could have been most important in retaining high concentrations of U during initial release into the vadose zone. Massive amount of colloids, including U-colloids, formed at the plume fronts. Total U concentrations (aqueous and colloid) within plume fronts exceeded the source concentration by up to 5-fold. Uranium colloid formation and accumulation at the neutralized plume front could be one mechanism responsible for highly heterogeneous U distribution observed in the contaminated Hanford vadose zone.     

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.     

Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nanoscale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, nonaqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (VOCs) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.     

Use of compound-specific stable carbon isotope analyses to demonstrate anaerobic biodegradation of MTBE in groundwater at a gasoline release site

Currently it is unclear if natural attenuation is an appropriate remedial approach for groundwater impacted by methyl tertiary butyl ether (MTBE). Site-characterization data at most gasoline release sites are adequate to evaluate attenuation in MTBE concentrations over time or distance. But, demonstrating natural biodegradation of MTBE requires laboratory microcosm studies, which could be expensive and time-consuming. Recently, compound-specific carbon isotope ratio analyses (13C/12C expressed in delta13C notation) have been used to demonstrate aerobic biodegradation of MTBE in laboratory incubations. This study explored the potential of this approach to distinguish MTBE biodegradation from other abiotic processes in an anaerobic groundwater plume that showed extensive decrease in MTBE concentrations. To our knowledge, this is the first study to use delta13C of MTBE data in groundwater and laboratory microcosms to demonstrate anaerobic biodegradation of MTBE. The delta13C of MTBE in monitoring wells increased by up to 31 per thousand (-25.5 per thousand to +5.5 per thousand) along with a 40-fold decrease in MTBE concentrations. Anaerobic incubations in laboratory microcosms indicated up to 20-fold reduction in MTBE concentrations with a corresponding increase in delta13C of MTBE of up to 33.4 per thousand (-28.7 per thousand to +4.7 per thousand) in live microcosms. Little enrichment was observed in autoclaved controls. These results demonstrate that anaerobic biodegradation was the dominant natural attenuation mechanism for MTBE at this site. The estimated isotopic enrichment factors (epsilon(field) = -8.10 per thousand and epsilon(lab) = -9.16 per thousand) were considerably larger than the range (-1.4 per thousand to -2.4 per thousand) previously reported for aerobic biodegradation of MTBE in laboratory incubations. These observations strongly suggest that delta13C of MTBE could be potentially useful as an "indicator" of in-situ MTBE biodegradation.     

Relative importance of gas-phase diffusive and advective tichloroethene (TCE) fluxes in the unsaturated zone under natural conditions

It was hypothesized that atmospheric pressure changes can induce gas flow in the unsaturated zone to such an extent that the advective flux of organic vapors in unsaturated-zone soil gas can be significant relative to the gas-phase diffusion flux of these organic vapors. To test this hypothesis, a series of field measurements and computer simulations were conducted to simulate and compare diffusion and advection fluxes at a trichloroethene-contaminated field site at Picatinny Arsenal in north-central New Jersey. Moisture content temperature, and soil-gas pressure were measured at multiple depths (including at land surface) and times for three distinct sampling events in August 1996, October 1996, and August 1998. Gas pressures in the unsaturated zone changed significantly over time and followed changes measured in the atmosphere. Gas permeability of the unsaturated zone was estimated using data from a variety of sources, including laboratory gas permeability measurements made on intact soil cores from the site, a field air pump test, and calibration of a gas-flow model to the transient, one-dimensional gas pressure data. The final gas-flow model reproduced small pressure gradients as observed in the field during the three distinct sampling events. The velocities calculated from the gas-flow model were used in transient, one-dimensional transport simulations to quantify advective and diffusive fluxes of TCE vapor from the subsurface to the atmosphere as a function of time for each sampling event. Effective diffusion coefficients used for these simulations were determined from independent laboratory measurements made on intact soil cores collected from the field site. For two of the three sampling events (August 1996 and August 1998), the TCE gas-phase diffusion flux at land surface was significantly greater than the advection flux over the entire sampling period. For the second sampling event (October 1996), the advection flux was frequently larger than the diffusion flux. When averaged over the second sampling event, the advection and diffusion fluxes were comparable in magnitude. Sensitivity analyses indicate that diffusion fluxes increase significantly with increases in air-filled porosity near land surface, whereas advection fluxes do not. For October 1996, the comparable advection and diffusion fluxes were caused by high moisture content near land surface and a subsequent reduction in the diffusion flux relative to the advection flux. These results indicate that under certain environmental conditions, the organic vapor advection flux from the unsaturated zone to the atmosphere may be equal to or greater than the diffusion flux.     

Push-pull tests to quantify in situ degradation rates at a phytoremediation site

Nine push-pull tests (PPTs) were performed to determine in-situ aerobic respiration rates at a creosote-contaminated site and to assess the contribution of hybrid poplar trees to the remediation of polynuclear aromatic hydrocarbons (PAH) in groundwater. PPTs were conducted by injecting a solution containing dissolved oxygen and naphthalene (reactive tracers) with bromide (nonreactive tracer) into wells constructed in a shallow unconfined aquifer. The objective of this study was to determine seasonal variation and spatial differences (contaminated versus uncontaminated areas and treed versus untreed areas) in the rate of consumption of dissolved oxygen. First-order aerobic respiration rates varied from 0.0 (control well) to 1.25 hr(-1), which occurred at a planted area in early summer (June). Rates measured in winter at treed areas were greater by a factor of 3-5 when compared to winter rates determined at nontreed areas of the site. Rates at treed regions were found to increase by over 4 times in summer relative to winter at the same location.     

Measurement of Air and VOC Vapor Fluxes during Gas-Driven Soil Remediation: Bench-Scale Experiments

In this laboratory study, an experimental method was developed for the quantitative analyses of gas fluxes in soil during advective air flow. One-dimensional column and two- and three-dimensional flow chamber models were used in this study. For the air flux measurement, n-octane vapor was used as a tracer, and it was introduced in the air flow entering the physical models. The tracer (n-octane) in the gas effluent from the models was captured for a finite period of time using a pack of activated carbon, which then was analyzed for the mass of n-octane. The air flux was calculated based on the mass of n-octane captured by the activated carbon and the inflow concentration. The measured air fluxes are in good agreement with the actual values for one- and two-dimensional model experiments. Using both the two- and three-dimensional models, the distribution of the air flux at the soil surface was measured. The distribution of the air flux was found to be affected by the depth of the saturated zone. The flux and flux distribution of a volatile contaminant (perchloroethene) was also measured by using the two-dimensional model. Quantitative information of both air and contaminant flux may be very beneficial for analyzing the performance of gas-driven subsurface remediation processes including soil vapor extraction and air sparging.     

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.     

An evaluation of compound-specific isotope analyses for assessing the biodegradation of MTBE at Port Hueneme, CA

The use of compound-specific isotope analysis (CSIA) as a diagnostic tool for MTBE biodegradation in aquifers was tested at the Port Hueneme, CA site. There, a 1500-m long dissolved MTBE plume and associated engineered aerobic flow-through biobarrier have been well-studied, leading to delineation of regions of known significant and limited bioattenuation. This allowed comparison of field-scale CSIA results with a priori knowledge of aerobic MTBE biodegradation, leading to conclusions concerning the utility of CSIA as a diagnostic tool for other aerobic biodegradation sites. Groundwater samples were collected and analyzed for both 13C and 2H (D) in MTBE through the bioactive treatment zone and within the larger MTBE plume. For reference, the 13C enrichment factor for MTBE biodegradation in laboratory-scale microcosms using site groundwater and sediments was also quantified. Aerobic microcosms showed a 13C enrichment of 5.5 to 6.4 +/- 0.2 per thousand over a two-order of magnitude concentration decrease, with an average isotope enrichment factor (epsilon(c)) of -1.4 per thousand, in agreement with other aerobic microcosm studies. Less 13C enrichment (about 25%) was observed for similar MTBE concentration reductions in groundwater samples collected within the aerobic biotreatment zone, and this enrichment was comparable to the scatter in delta13C values within the source zone. Increasing enrichment with decreasing MTBE concentration seen in microcosm data was not evident in either the 13C or D field data. The discrepancy between field and laboratory data may reflect small-scale (<1 m) spatial heterogeneity in MTBE biodegradation activity and the mixing of water from adjacent strata during groundwater sampling; for example, relatively nonattenuated MTBE-impacted water from one stratum could be mixed with highly attenuated/low-MTBE concentration from another, and this could produce a sample with both reduced MTBE concentration and low enrichment. Overall, the results suggest that 13C data alone may produce inconclusive results at sites where MTBE undergoes aerobic biodegradation, and that even with two-dimensional CSIA (13C and D), an increase in the confidence of data interpretation may only be possible with data sets larger than those typically collected in practice.     

Linking soil O2, CO2, and CH4 concentrations in a Wetland soil: implications for CO2 and CH4 fluxes

Oxygen (O(2)) availability and diffusivity in wetlands are controlling factors for the production and consumption of both carbon dioxide (CO(2)) and methane (CH(4)) in the subsoil and thereby potential emission of these greenhouse gases to the atmosphere. To examine the linkage between high-resolution spatiotemporal trends in O(2) availability and CH(4)/CO(2) dynamics in situ, we compare high-resolution subsurface O(2) concentrations, weekly measurements of subsurface CH(4)/CO(2) concentrations and near continuous flux measurements of CO(2) and CH(4). Detailed 2-D distributions of O(2) concentrations and depth-profiles of CO(2) and CH(4) were measured in the laboratory during flooding of soil columns using a combination of planar O(2) optodes and membrane inlet mass spectrometry. Microsensors were used to assess apparent diffusivity under both field and laboratory conditions. Gas concentration profiles were analyzed with a diffusion-reaction model for quantifying production/consumption profiles of O(2), CO(2), and CH(4). In drained conditions, O(2) consumption exceeded CO(2) production, indicating CO(2) dissolution in the remaining water-filled pockets. CH(4) emissions were negligible when the oxic zone was >40 cm and CH(4) was presumably consumed below the depth of detectable O(2). In flooded conditions, O(2) was transported by other mechanisms than simple diffusion in the aqueous phase. This work demonstrates the importance of changes in near-surface apparent diffusivity, microscale O(2) dynamics, as well as gas transport via aerenchymous plants tissue on soil gas dynamics and greenhouse gas emissions following marked changes in water level.     

Laboratory and field verification of a method to estimate the extent of petroleum biodegradation in soil

We describe a new and rapid quantitative approach to assess the extent of aerobic biodegradation of volatile and semivolatile hydrocarbons in crude oil, using Shushufindi oil from Ecuador as an example. Volatile hydrocarbon biodegradation was both rapid and complete-100% of the benzene, toluene, xylenes (BTEX) and 98% of the gasoline-range organics (GRO) were biodegraded in less than 2 days. Severe biodegradation of the semivolatile hydrocarbons occurred in the inoculated samples with 67% and 87% loss of the diesel-range hydrocarbons (DRO) in 3 and 20 weeks, respectively. One-hundred percent of the naphthalene, fluorene, and phenanthrene, and 46% of the chrysene in the oil were biodegraded within 3 weeks. Percent depletion estimates based on C(30) 17α,21β(H)-hopane (hopane) underestimated the diesel-range organics (DRO) and USEPA 16 priority pollutant PAH losses in the most severely biodegraded samples. The C(28) 20S-triaromatic steroid (TAS) was found to yield more accurate depletion estimates, and a new hopane stability ratio (HSR = hopane/(hopane + TAS)) was developed to monitor hopane degradation in field samples. Oil degradation within field soil samples impacted with Shushufindi crude oil was 83% and 98% for DRO and PAH, respectively. The gas chromatograms and percent depletion estimates indicated that similar levels of petroleum degradation occurred in both the field and laboratory samples, but hopane degradation was substantially less in the field samples. We conclude that cometabolism of hopane may be a factor during rapid biodegradation of petroleum in the laboratory and may not occur to a great extent during biodegradation in the field. We recommend that the hopane stability ratio be monitored in future field studies. If hopane degradation is observed, then the TAS percent depletion estimate should be computed to correct for any bias that may result in petroleum depletion estimates based on hopane.     

Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/Lto a depth of 1.5 m, and MTBE concentrations decreased to <1 microg/L prior to discharge. MTBE mass flux calculations indicate that 96% of MTBE mass loss occurs in the relatively small oxic zone prior to discharge. Samples of a natural microbial biofilm present in the oxic zone beneath the ditch completely degraded [U-14C]MTBE to [14C]CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE- and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.     

Particle-phase dry deposition and air-soil gas-exchange of polybrominated diphenyl ethers (PBDEs) in Izmir, Turkey

The particle-phase dry deposition and soil-air gas-exchange of polybrominated diphenyl ethers (PBDEs) were measured in Izmir, Turkey. Relative contributions of different deposition mechanisms (dry particle, dry gas, and wet deposition) were also determined. BDE-209 was the dominating congener in all types of samples (air, deposition, and soil). Average dry deposition fluxes of total PBDEs (sigma7PBDE) for suburban and urban sites were 67.6 and 128.8 ng m(-2) day(-1), respectively. Particulate dry deposition velocities ranged from 11.5 (BDE-28) to 3.9 cm s(-1) (BDE-209) for suburban sites and 7.8 (BDE-28) to 2.8 cm s(-1) (BDE-154) for urban sites with an overall average of 5.8 +/- 3.7 cm s(-1). The highest sigma7PBDE concentration (2.84 x 10(6) ng kg(-1) dry wt) was found around an electronic factory among the 13 soil samples collected from different sites. The concentration in a bag filter dust from a steel plant was also high (2.05 x 10(5) ng kg(-1)), indicating that these industries are significant PBDE sources. Calculated net soil-air gas exchange flux of sigma7PBDE ranged from 11.8 (urban) to 23.4 (industrial) ng m(-2) day(-1) in summer, while in winter it ranged from 3.2 (urban) to 11.6 (suburban) ng m(-2) day(-1). All congeners were deposited at all three sites in winter and summer. It was estimated that the wet deposition also contributes significantly to the total PBDE deposition to soil. Dry particle, wet, and gas deposition contribute 60, 32, and 8%, respectively, to annual PBDE flux to the suburban soil.     

Bacterial chemotaxis along vapor-phase gradients of naphthalene

The role of bacterial growth and translocation for the bioremediation of organic contaminants in the vadose zone is poorly understood. Whereas air-filled pores restrict the mobility of bacteria, diffusion of volatile organic compounds in air is more efficient than in water. Past research, however, has focused on chemotactic swimming of bacteria along gradients of water-dissolved chemicals. In this study we tested if and to what extent Pseudomonas putida PpG7 (NAH7) chemotactically reacts to vapor-phase gradients forming above their swimming medium by the volatilization from a spot source of solid naphthalene. The development of an aqueous naphthalene gradient by air-water partitioning was largely suppressed by means of activated carbon in the agar. Surprisingly, strain PpG7 was repelled by vapor-phase naphthalene although the steady state gaseous concentrations were 50-100 times lower than the aqueous concentrations that result in positive chemotaxis of the same strain. It is thus assumed that the efficient gas-phase diffusion resulting in a steady, and possibly toxic, naphthalene flux to the cells controlled the chemotactic reaction rather than the concentration to which the cells were exposed. To our knowledge this is the first demonstration of apparent chemotactic behavior of bacteria in response to vapor-phase effector gradients.