Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.     

Microbially mediated redox processes in natural analogues for radioactive waste

Natural analogues allow scientists to investigate biogeochemical processes relevant to radioactive waste disposal that occur on time scales longer than those that may be studied by time-limited laboratory experiments. The Palmottu U-Th deposit in Finland and the Bangombé natural nuclear reactor in Gabon involve the study of natural uranium, and are both considered natural analogues for subsurface radioactive waste disposal. The microbial population naturally present in groundwater may affect the redox conditions, and hence, the radionuclide solubility and migration. Therefore, groundwater samples from the two sites were investigated for microbial populations. The total numbers of cells ranged from 10(4) to 10(6) cells ml(-1). Iron-reducing bacteria (IRB) were the largest culturable microbial population in the Palmottu groundwater and were present at up to 1.3 x 10(5) cells ml(-1). Sulfate-reducing bacteria (SRB) and acetogens could also be cultured from the Palmottu groundwater. The numbers of IRB and SRB were largest in groundwater with the lowest uranium concentrations. Removal of dissolved U(VI) from solution was concomitant with the growth of IRB enrichment cultures and the reduction of iron. The redox buffer in the Palmottu groundwater consists of iron and uranium species, both of which are affected by IRB. IRB and aerobic heterotrophs were cultured from the Bangombé groundwater, where redox potentials are buffered by iron and organic carbon species. Microbial populations similar to those found at Palmottu and Bangombé are found throughout the Fennoscandian Shield, a potential host rock for subsurface radioactive waste disposal. These results confirm that microorganisms can be expected to play a role in stabilizing radioactive waste disposed of in the subsurface by lowering redox potential and immobilizing radionuclides.     

Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.     

Use of Stable Isotopes to Identify Sources of Mercury in Sediments: A Review and Uncertainty Analysis

Mass-dependent and mass-independent mercury isotope fractionation potentially generates unique source signatures that can be used to apportion contributions to sediment contamination. This article reviews findings from previous investigations that have used mercury isotopes to identify sources. It also discusses a mass balance mercury isotope fractionation model that simulates changes in isotopic source signatures in aquatic systems caused by natural biogeochemical cycling. According to the model, the extent of source signature alteration depends on chemical speciation, with more labile forms exhibiting greater isotopic fractionation. Apportionment is tractable when differences between δ²⁰²Hg of sources are larger than potential changes in isotopic signatures following the release of mercury into the environment.     

Co-contamination of arsenic and fluoride in the groundwater of unconsolidated aquifers under reducing environments

The co-contamination of arsenic (As) and fluoride (F⁻) in shallow aquifers is frequently observed worldwide, and the correlations between those contaminants are different according to the redox conditions. This study geochemically explores the reasons for the co-contamination and for the redox-dependent correlations by investigating the groundwater of an alluvial aquifer in Korea. Geochemical signatures of the groundwater in the study area show that the As concentrations are enriched by the reductive dissolution of Fe-(hydr)oxides, and the correlations between As and F⁻ concentrations are poor comparatively to those observed in the oxidizing aquifers. However, F⁻ concentrations are strongly dependent on pH. Desorption/adsorption experiments using raw soils and citrate-bicarbonate-dithionite treated soils indicated that Fe-(hydr)oxides are the important As and F⁻ hosts causing the co-contamination phenomenon. The weaker correlation between F⁻ and As in reducing aquifers is likely to be associated with sulfate reduction, which removes As from groundwater without changing the F⁻ concentration.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.     

Characterisation of microbial activity in the framework of natural attenuation without groundwater monitoring wells?: a new Direct-Push probe

At many contaminated field sites in Europe, monitored natural attenuation is a feasible site remediation option. Natural attenuation includes several processes but only the microbial degradation leads to real contaminant removal and very few methods are accepted by the authorities providing real evidence of microbial contaminant degradation activity. One of those methods is the recently developed in situ microcosm approach (BACTRAP®). These in situ microcosms consist of perforated stainless steel cages or PTFE tubes filled with an activated carbon matrix that is amended with ¹³C-labelled contaminants; the microcosms are then exposed within groundwater monitoring wells. Based on this approach, natural attenuation was accepted by authorities as a site remediation option for the BTEX-polluted site Zeitz in Germany. Currently, the in situ microcosms are restricted to the use inside groundwater monitoring wells at the level of the aquifer. The (classical) system therefore is only applicable on field sites with a network of monitoring wells, and only microbial activity inside the monitoring wells at the level of the aquifer can be assessed. In order to overcome these limitations, a new Direct-Push BACTRAP probe was developed on the basis of the Geoprobe® equipment. With respect to the mechanical boundary conditions of the DP technique, these new probes were constructed in a rugged and segmented manner and are adaptable to various sampling concepts. With this new probe, the approach can be extended to field sites without existing monitoring wells, and microbial activity was demonstrated to be measureable even under very dry conditions inside the vadose zone above the aquifer. In a field test, classical and Direct-Push BACTRAPs were applied in the BTEX-contaminated aquifer at the ModelPROBE reference site Zeitz (Germany). Both types of BACTRAPs were incubated in the centre and at the fringe of the BTEX plume. Analysis of phospholipid fatty acid (PLFA) patterns showed that the bacterial communities on DP-BACTRAPs were more similar to the soil than those found on classical BACTRAPs. During microbial degradation of the ¹³C-labelled substrate on the carrier material of the microcosms, the label was only slightly incorporated into bacterial biomass, as determined by PLFA analysis. This provides clear indication for decreased in situ natural attenuation potential in comparison to earlier sampling campaigns, which is presumably caused by a large-scale source remediation measure in the meantime. In conclusion, Direct-Push-based BACTRAPs offer a promising way to monitor natural attenuation or remediation success at field sites which are currently inaccessible by the technique due to the lack of monitoring wells or due to a main contamination present within the vadose zone.     

Degradation of the herbicide dichlobenil and its metabolite BAM in soils and subsurface sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in surface water and groundwater. To evaluate the potential for natural attenuation of this BAM pollution in groundwater, we studied the degradation of BAM and dichlobenil in 16 samples of clayey till, unconsolidated sand and limestone, including sediments from both oxidized and reduced conditions. The degradation of dichlobenil occurred primarily in the upper few meters below surface, although dichlobenil was strongly sorbed to these sediments. However, the degradation of dichlobenil to BAM could not be correlated to either sorption, water chemistry, composition of soils or sediments. Degradation of dichlobenil to BAM was limited (<2% degraded) in the deeper unsaturated zones, and no degradation was observed in aquifer sediments. This illustrates, that dichlobenil transported to aquifers does not contribute to the BAM-contamination in aquifers. A small, but significant degradation of BAM was observed in the upper part of the unsaturated zones in sandy sediments, but no degradation was observed in the clayey till sediment or in the deeper unsaturated zones. The insignificant degradation of BAM in aquifer systems shows that BAM pollution detected in aquifers will appear for a long time; and consequently the potential for natural attenuation of BAM in aquifer systems is limited.     

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 mumol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH4 and CO2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.     

Biogeochemical characterisation of a coal tar distillate plume

The distillation of acidified coal tars for up to 50 years has given rise to a phenol plume approximately 500 m long, 50 m deep and containing up to 15 g l(-1) dissolved organic carbon (DOC) in the Triassic Sandstones aquifer. A conceptual biogeochemical model based on chemical and microbiological analysis of groundwater samples has been developed as a preliminary to more detailed studies of the controls on natural attenuation. While the development of redox zones and the production of methane and carbon dioxide provide evidence of natural attenuation, it appears that degradation is slow. The existence of sulphate in the plume indicates that this electron acceptor has not been depleted and that consequently methanogenesis is probably limited. Based on a simple estimate of sulphate input concentration, a half-life of about 15 years has been estimated for sulphate reduction. Geochemical modelling predicts that increased alkalinity within the plume has not led to carbonate precipitation, and thus within the limits of accuracy of the measurement, alkalinity may reflect the degree of biodegradation. This implies a loss of around 18% of the DOC over a 30-year period. Despite limited degradation, microbial studies show that there are diverse microbial communities in the aquifer with the potential for both anaerobic and aerobic biodegradation. Microbial activity was found to be greatest at the leading edge of the plume where DOC concentrations are 60 mg l(-1) or less, but activity could still be observed in more contaminated samples even though cells could not be cultured. The study suggests that degradation may be limited by the high phenol concentrations within the core of the plume, but that once diluted by dispersion, natural attenuation may proceed. More detailed studies to confirm these initial findings are identified and form the basis of associated papers.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

The organic geochemistry of a sanitary landfill leachate plume

Leachate from the North Bay municipal landfill has contaminated an unconfined, sandy aquifer throughout the 700 m flow system from the site to a discharge zone at a creek. The major organic contaminants identified are aromatic hydrocarbons, especially substituted benzenes. The high groundwater velocity of about 75 m yr⁻¹ and the low organic sorption properties of the sand have permitted non-transformed contaminants to spread throughout the total flow system. There is considerable temporal and spatial variability in groundwater chemistry.Most of the aqueous organic carbon has a nominal molecular weight of <2000 and the general decrease in the mass of this fraction relative to Cl indicates it is being mineralized significantly during transport. IR spectra indicate a general trend of increased aromaticity and decreased OH content of organic matter along the flow system. The aqueous organic matter has a significant apparent complexing capacity and so it is somewhat surprising that toxic metal concentrations in leachate-impacted groundwaters are low. In the leachate plume, this complexing capacity is taken up by major cations and H⁺ and to a far lesser extent by toxic metals such as Pb, Cd or Zn.Dispersion is clearly responsible for considerable decrease in contaminant concentration along the flow system. Biotransformation under strictly anaerobic conditions has probably caused 1,1,1-trichloroethane and trichloroethylene to be restricted to the immediate vicinity of the landfill. A simple method of comparing the concentrations of pairs of organics at points along the flow system provides relative transformation rates for pairs of organics even with variable inputs from the landfill and dispersive dilution. Relative to ethylbenzene, o-xylene is rapidly lost from this system. O-xylene may be less persistent than m- or p-xylene; a result unexpected from previous studies of these dimethylbenzenes. In the initial, strictly anarobic segment of the flow system 1,2,4-trimethylbenzene and 1,4-dichlorobenzene are equally persistent, but in the final, less anaerobic segment, the former appears to be degraded more rapidly than the latter.Contaminant distributions in aquifers reflect the results of a number of processes integrated in a complex manner and so are difficult to interpret in terms of specific processes. However, they do provide evidence for what processes are most significant in real groundwater systems and they will also provide critical tests of how well laboratory-derived information relates to real groundwater contamination situations.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.     

Uptake and mobility of uranium in black oaks: implications for biomonitoring depleted uranium-contaminated groundwater

In a preliminary study, the uptake and the mobility of uranium (U) by black oak trees (Quercus velutina) were assessed by measuring the isotopic composition of tree rings in two mature oak trees in a heavy metal contaminated bog in Concord, MA. The bog is adjacent to a nuclear industrial facility that has been processing depleted uranium (DU) since 1959. Over the past 40 years, DU has been leaking from an onsite holding basin and cooling pond down gradient to the bog where the oaks are located. Because DU has no source outside the nuclear industry, contamination from the industrial facility is readily discernable from uptake of natural U by measuring isotopic compositions. Isotope ratio analysis confirms the occurrence of DU in bark, sapwood and heartwood tree rings dating back to 1937, pre-dating the introduction of DU at the site by at least 20 years. Isotope dilution analysis indicates high concentrations of U (>3 ppb) in sapwood that drop rapidly to relatively constant concentrations (0.3-0.4 ppb) in heartwood. These data indicate that once incorporated into tree cells, U is mobile, possibly by diffusion through the tree wood. Concentrations of U in sapwood are approximately equal to average U concentrations in groundwater onsite over the past 10 years, suggesting that oak trees can be used as present-day bioindicators of U-contaminated groundwater. We suggest that regional sampling of oak bark and sapwood is a reasonable, inexpensive alternative to drilling wells to monitor shallow groundwater U contamination.     

Partitioning microbial respiration between jet fuel and native organic matter in an organic-rich long time-contaminated aquifer

The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.     

One-year measurements of chloroethenes in tree cores and groundwater at the SAP Mimoň Site, Northern Bohemia

Chlorinated ethenes (CE) are among the most frequent contaminants of soil and groundwater in the Czech Republic. Because conventional methods of subsurface contamination investigation are costly and technically complicated, attention is directed on alternative and innovative field sampling methods. One promising method is sampling of tree cores (plugs of woody tissue extracted from a host tree). Volatile organic compounds can enter into the trunks and other tissues of trees through their root systems. An analysis of the tree core can thus serve as an indicator of the subsurface contamination. Four areas of interest were chosen at the experimental site with CE groundwater contamination and observed fluctuations in groundwater concentrations. CE concentrations in groundwater and tree cores were observed for a 1-year period. The aim was to determine how the CE concentrations in obtained tree core samples correlate with the level of contamination of groundwater. Other factors which can affect the transfer of contaminants from groundwater to wood were also monitored and evaluated (e.g., tree species and age, level of groundwater table, river flow in the nearby Plou?nice River, seasonal effects, and the effect of the remediation technology operation). Factors that may affect the concentration of CE in wood were identified. The groundwater table level, tree species, and the intensity of transpiration appeared to be the main factors within the framework of the experiment. Obtained values documented that the results of tree core analyses can be used to indicate the presence of CE in the subsurface. The results may also be helpful to identify the best sampling period for tree coring and to learn about the time it takes until tree core concentrations react to changes in groundwater conditions. Interval sampling of tree cores revealed possible preservation of the contaminant in the wood of trees.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Improving the knowledge of pesticide and nitrate transfer processes using age-dating tools (CFC, SF6, H) in a volcanic island (Martinique, French West Indies)

Numerous successful examples of CFC and SF₆ groundwater dating applications were recently published. However the proposed CFC/SF₆ method needs various hydrodynamic parameters that are not always available. In order to predict groundwater-quality trends in areas where the hydrogeological context is poorly known, a dating method using tritium, CFC and SF₆ was successfully implemented in Martinique. Hydrogeological understanding is limited in this volcanic island where groundwater contamination by pesticides and nitrate has been recently proven in various areas. A negative correlation was observed between nitrate concentrations and groundwater ages while pesticide contamination showed a more complex schema. Consequently the presence of old groundwater clearly explained the absence or low pesticide and nitrate concentrations in some areas. However a possible degradation of the water quality is to be feared in the future. In view of the relatively long transfer times and the complexity of the remobilization processes of solutes, the expected effects of any modifications in the use of fertilizers, or of changes in pesticide-use legislation, would take a long time to become apparent.     

Microbial degradation of methyl tert-butyl ether and tert-butyl alcohol in the subsurface

The fate of fuel oxygenates such as methyl tert-butyl ether (MTBE) in the subsurface is governed by their degradability under various redox conditions. The key intermediate in degradation of MTBE and ethyl tert-butyl ether (ETBE) is tert-butyl alcohol (TBA) which was often found as accumulating intermediate or dead-end product in lab studies using microcosms or isolated cell suspensions. This review discusses in detail the thermodynamics of the degradation processes utilizing various terminal electron acceptors, and the aerobic degradation pathways of MTBE and TBA. It summarizes the present knowledge on MTBE and TBA degradation gained from either microcosm or pure culture studies and emphasizes the potential of compound-specific isotope analysis (CSIA) for identification and quantification of degradation processes of slowly biodegradable pollutants such as MTBE and TBA. Microcosm studies demonstrated that MTBE and TBA may be biodegradable under oxic and nearly all anoxic conditions, although results of various studies are often contradictory, which suggests that site-specific conditions are important parameters. So far, TBA degradation has not been shown under methanogenic conditions and it is currently widely accepted that TBA is a recalcitrant dead-end product of MTBE under these conditions. Reliable in situ degradation rates for MTBE and TBA under various geochemical conditions are not yet available. Furthermore, degradation pathways under anoxic conditions have not yet been elucidated. All pure cultures capable of MTBE or TBA degradation isolated so far use oxygen as terminal electron acceptor. In general, compared with hydrocarbons present in gasoline, fuel oxygenates biodegrade much slower, if at all. The presence of MTBE and related compounds in groundwater therefore frequently limits the use of in situ biodegradation as remediation option at gasoline-contaminated sites. Though degradation of MTBE and TBA in field studies has been reported under oxic conditions, there is hardly any evidence of substantial degradation in the absence of oxygen. The increasing availability of field data from CSIA will foster our understanding and may even allow the quantification of degradation of these recalcitrant compounds. Such information will help to elucidate the crucial factors of site-specific biogeochemical conditions that govern the capability of intrinsic oxygenate degradation.