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At least 271 records · Page 15Linked to original sources

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California↗

Molecular markers and their use in environmental organic geochemistry

Molecular markers are organic substances that carry information about sources of organic matter or contamination. The source/marker relation can be used to indicate the presence of a given source material (qualitative), or, under appropriate conditions, to estimate the amount of a source material (quantitative source apportionment) in the environment. Assemblages of markers can also be used as process probes. In this instance, systematic differences and/or similarities in the physical-chemical properties of markers are coupled with compositional changes in marker composition to infer the operation of natural processes. This paper provides an overview of what molecular markers are, what types of markers are present in the environment, the requirements for the use of markers, and some common applications. To illustrate how molecular markers can answer specific environmental questions, three case studies are presented. The first case study examines the impact of municipal waste on a large urban harbor (Boston Harbor). Linear alkylbenzenes (unreacted residues of linear alkylbenzenesulfonate surfactants) and coprostanol (a fecal indicator) provide information on the sources and likely transport pathways of municipal wastes in a complex hydrologic system. The marker data are also used to estimate the proportion of sewage-derived poly chlorinated biphenyls (PCBs) in polluted harbor sediments. The second case study concerns a portion of the continental shelf off southern California (Palos Verdes) where discharge of municipal wastewaters has led to extensive contamination of sediments and biota. Long-chain alkylbenzenes (surfactant residues), PCBs and the pesticide, DDT (dichlorodiphenyltrichloroethane), are used to develop sedimentation rate estimates for several time periods by molecular stratigraphy. These results, when combined with other information, allow conclusions to be drawn about the most likely transport pathway of sediments at the study site and to predict the fate of historically deposited contaminants. Finally, an investigation of a crude-oil spill in Bemidji, MN illustrates how monoaromatic hydrocarbons can be exploited as process probes, providing insights into the relative importance of different attenuation processes in a contaminated aquifer. The results show that natural attenuation of the monoaromatic hydrocarbons is occurring at this site and is dominated, not by physical and/or chemical processes, but by biodegradation.

Book chapter↗

The next generation of products and methodologies to establish biocrusts in degraded ecosystems

Biological soil crusts (biocrusts) – thin, coherent soil surface layers aggregated and inhabited by communities of tiny photoautotrophic and heterotrophic organisms – support ecosystem functioning in drylands and influence the Earth system. Biocrust loss due to disturbance, global change and land use leads to altered hydrological function, susceptibility to erosion and diminished biogeochemical cycling, with consequences extending to regional and global environmental quality and ecosystem service provisioning. To restore degraded drylands, specific techniques could inform how to 1. produce biocrust biota ex situ for use as an inoculum in degraded environments and then 2. encourage the establishment of the inoculum in high-stress environments. To re-establish lost biocrusts, a promising pathway could be the integration of adding biocrust biota (inoculation), ensuring that it stays where applied (retention) and softening environmental stresses and limitations (amelioration) at approximately the same time. Several techniques, most of them developed in only the past few years, demonstrate this integration: biocrust sods, cloths, pellets, capsules and slurries. Biocrust sods are fabric-reinforced patches of biocrust growing on soil, produced in farms and transported to and deployed intact in field sites. Biocrust cloths are fabrics and sheets with biocrust biota grown directly on their surface in greenhouse-based fog chambers that can be attached to soil in the field. Biocrust pellets are small, protective pieces of a binder material (often clay) infused with biocrust inoculum. Biocrust capsules are biodegradable gel capsules filled with biocrust inoculum, often with protective substances. Both pellets and capsules are broadcast over degraded soils. Biocrust slurries are semi-liquid suspensions of biocrust inoculum and other solids that are sprayed or spread in degraded sites. Emerging techniques like these have the potential to restore highly functional drylands and their ecosystem services. Potential applications include ecological restoration of dryland areas disturbed by fire, overgrazing, agriculture, mining and other factors or environmental engineering in other contexts such as cultural heritage sites, croplands or human infrastructure. The next-generation techniques for biocrust restoration described here are tools that could be applied to solve small- to medium-scaled challenges now and with increased production efficiency and informed, strategic use of the products, large-scaled challenges in the future.

Drylands↗

Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques

The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.

Environmental Science and Technology↗

Evidence of coupled carbon and iron cycling at a hydrocarbon-contaminated site from time lapse magnetic susceptibility

Conventional characterization and monitoring of hydrocarbon (HC) pollution is often expensive and time-consuming. Magnetic susceptibility (MS) has been proposed as an inexpensive, long-term monitoring proxy of the degradation of HC. We acquired repeated down hole MS logging data in boreholes at a HC-contaminated field research site in Bemidji, MN, USA. The MS data were analyzed in conjunction with redox conditions and iron availability within the source zone to better assess whether MS can serve as a proxy for monitoring HC contamination in unconsolidated sediments. The MS response at the site diminished during the sampling period, which was found to coincide with depletion of solid phase iron in the source zone. Previous geochemical observations and modeling at the site suggest that the most likely cause of the decrease in MS is the transformation of magnetite to siderite, coupled with the exhaustion of ferrihydrite. Although the temporal MS response at this site gives valuable field-scale evidence for changing conditions of iron cycling and stability of iron minerals it does not provide a simple proxy for long-term monitoring of biodegradation of hydrocarbons in the smear zone.

Minnesota↗

Estimation of the potential for atrazine transport in a silt loam soil

The transport potential of the herbicide atrazine (2-chloro-4-ethyl-6-isopropyl- s -triazine) through a 1-meter-thick root zone of corn ( Zea mays L.) in a silty-loam soil in Kansas was estimated for a 22-year period (1972-93) using the one-dimensional water-flow and solute-transport model LEACHM. Results demonstrate that, for this soil, atrazine transport is directly related to the amount and timing of rain that follows spring applications of atrazine. Two other critical transport factors were important in wet years — [1] variability in atrazine application rate, and [2] atrazine degradation rates below the root zone. Results demonstrate that the coincidence of heavy rain soon after atrazine application can cause herbicide to move below the rooting zone into depths at which biodegradation rates are assumed to be low but are often unknown. Atrazine that reaches below the rooting zone and persists in the underlying soil can subsequently be transported into ground water as soil water drains, typically after the growing season. A frequency analysis of atrazine concentrations in subsurface drainage, combined with field data, demonstrates the relative importance of critical transport factors and confirms a need for definitive estimates of atrazine-degradation rates below the root zone. The analysis indicates that periodic leaching of atrazine can be expected for this soil when rainfall that exceeds 20 cm/mo coincides with atrazine presence in soil.

ACS Symposium Series↗

Transport and degradation of semivolatile hydrocarbons in a petroleum-contaminated aquifer, Bemidji, Minnesota

Polycyclic aromatic hydrocarbons (PAH) were used as probes to identify the processes controlling the transport and fate of aqueous semivolatile hydrocarbons (SVHCs) in a petroleum-contaminated aquifer near Bemidji, Minnesota. PAH and other SVHCs were isolated from ground water by field solid-phase extraction and analyzed using gas chromatography/mass spectrometry. Close to the oil body, aqueous aliphatic hydrocarbon compositions are substantially different from the parent oil, suggesting microbial alteration prior to or during dissolution. Aqueous PAH concentrations are elevated above oil-water equilibrium concentrations directly beneath the oil and decrease dramatically at distances ranging from the 25 to 65 m downgradient from the leading edge of the oil body. Variations in downgradient distributions of naphthalene, fluorene and phenanthrene, coupled with their biodegradation, partitioning and volatility characteristics, suggest that the PAH are useful probes for distinguishing between the biogeochemical processes affecting SVHC transport and persistence in ground water.

Minnesota↗

Chitin: 'Forgotten' source of nitrogen: From modern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios

Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of δ 15 N values in chitin. δ 15 N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the δ 15 N value of chitin is indicated by the observation of increasing δ 15 N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence δ 15 N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk δ 15 N values. Hydrous pyrolysis of immature source rocks at 330°C in contact with 15 N-enriched NH 4 Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may partly result from reaction with ammonium-containing pore waters.

ACS Symposium Series↗

Transport of sludge-derived organic pollutants to deep-sea sediments at deep water dump site 106

Linear alkylbenzenes (LABs), coprostanol and epi-coprostanol, were detected in sediment trap and bottom sediment samples at the Deep Water Dump Site 106 located 185 km off the coast of New Jersey, in water depths from 2400 to 2900 m. These findings clearly indicate that organic pollutants derived from dumped sludge are transported through the water column and have accumulated on the deep-sea floor. No significant difference in LABs isomeric composition was observed among sludge and samples, indicating little environmental biodegradation of these compounds. LABs and coprostanol have penetrated down to a depth of 6 cm in sediment, indicating the mixing of these compounds by biological and physical processes. Also, in artificially resuspended surface sediments, high concentrations of LABs and coprostanols were detected, implying that sewage-derived organic pollutants initially deposited on the deep-sea floor can be further dispersed by resuspension and transport processes. Small but significant amounts of coprostanol were detected in the sediment from a control site at which no LABs were detected. The coprostanol is probably derived from feces of marine mammals and sea birds and/or from microbial or geochemical transformations of cholesterol. Polcyclic aromatic hydrocarbons (PAHs) in sediment trap samples from the dump site were largely from the sewage sludge and had a mixed petroleum and pyrogenic composition. In contrast, PAHs in sediments in the dump site were mainly pyrogenic; contributed either from sewage sludge or from atmospheric transport to the overlying waters. & 1994 American Chemical Society.

Environmental Science & Technology↗

Bioreactors for removing methyl bromide following contained fumigations

Use of methyl bromide (MeBr) as a quarantine, commodity, or structural fumigant is under scrutiny because its release to the atmosphere contributes to the depletion of stratospheric ozone. A closed-system bioreactor consisting of 0.5 L of a growing culture of a previously described bacterium, strain IMB-1, removed MeBr (>110 μmol L -1 ) from recirculating air. Strain IMB-1 grew slowly to high cell densities in the bioreactor using MeBr as its sole carbon and energy source. Bacterial oxidation of MeBr produced CO 2 and hydrobromic acid (HBr), which required continuous neutralization with NaOH for the system to operate effectively. Strain IMB-1 was capable of sustained oxidation of large amounts of MeBr (170 mmol in 46 d). In an open-system bioreactor (10-L fermenter), strain IMB-1 oxidized a continuous supply of MeBr (220 μmol L -1 in air). Growth was continuous, and 0.5 mol of MeBr was removed from the air supply in 14 d. The specific rate of MeBr oxidation was 7 × 10 -16 mol cell -1 h -1 . Bioreactors such as these can therefore be used to remove large quantities of contaminant MeBr, which opens the possibility of biodegradation as a practical means for its disposal.

Environmental Science & Technology↗

Biotransformation of tributyltin to tin in freshwater river-bed sediments contaminated by an organotin release

The largest documented release of organotin compounds to a freshwater river system in the United States occurred in early 2000 in central South Carolina. The release consisted of an unknown volume of various organotin compounds such tetrabutyltin (TTBT), tributyltin (TBT), tetraoctyltin (TTOT), and trioctyl tin (TOT) and resulted in a massive fish kill and the permanent closures of a municipal wastewater treatment plant and a local city's only drinking-water intake. Initial sampling events in 2000 and 2001 indicated that concentrations of the ecologically toxic TTBT and TBT were each greater than 10 000 ??g/kg in surface-water bed sediments in depositional areas, such as lakes and beaver ponds downstream of the release. Bed-sediment samples collected between 2001 and 2003, however, revealed a substantial decrease in bed-sediment organotin concentrations and an increase in concentrations of degradation intermediate compounds. For example, in bed sediments of a representative beaver pond located about 1.6 km downstream of the release, total organotin concentrations [the sum of TTBT, TBT, and the TBT degradation intermediates dibutyltin (DBT) and monobutyltin (MBT)] decreased from 38 670 to 298 ??g/kg. In Crystal Lake, a large lake about 0.4 km downstream from the beaver pond, total organotin concentrations decreased from 28 300 to less than 5 ??g/kg during the same time period. Moreover, bed-sediment inorganic tin concentrations increased from pre-release levels of less than 800 to 32 700 ??g/kg during this time. These field data suggest that the released organotin compounds, such as TBT, are being transformed into inorganic tin by bed-sediment microbial processes. Microcosms were created in the laboratory that contained bed sediment from the two sites and were amended with tributyltin (as tributyltin chloride) under an ambient air headspace and sacrificially analyzed periodically for TBT, the biodegradation intermediates DBT and MBT, and tin. TBT concentrations decreased faster [half-life (t1/2) = 28 d] in the organic-rich sediments (21.5%) that characterized the beaver pond as compared to the slower (t1/2 = 78 d) degradation rate in the sandy, organic-poor, sediments (0.43%) of Crystal Lake. Moreover, the concentration of inorganic tin increased in microcosms containing bed sediments from both locations. These field and laboratory results suggest that biotransformation of the released organotins, in particular the ecologically detrimental TBT, does occur in this fresh surface-water system impacted with high concentrations of neat organotin compounds.

Environmental Science & Technology↗

Fate of 4-nonylphenol and 17β-estradiol in the Redwood River of Minnesota

The majority of previous research investigating the fate of endocrine-disrupting compounds has focused on single processes generally in controlled laboratory experiments, and limited studies have directly evaluated their fate and transport in rivers. This study evaluated the fate and transport of 4-nonylphenol, 17β-estradiol, and estrone in a 10-km reach of the Redwood River in southwestern Minnesota. The same parcel of water was sampled as it moved downstream, integrating chemical transformation and hydrologic processes. The conservative tracer bromide was used to track the parcel of water being sampled, and the change in mass of the target compounds relative to bromide was determined at two locations downstream from a wastewater treatment plant effluent outfall. In-stream attenuation coefficients ( k stream ) were calculated by assuming first-order kinetics (negative values correspond to attenuation, whereas positive values indicate production). Attenuation of 17β-estradiol ( k stream = −3.2 ± 1.0 day –1 ) was attributed primarily due to sorption and biodegradation by the stream biofilm and bed sediments. Estrone ( k stream = 0.6 ± 0.8 day –1 ) and 4-nonylphenol ( k stream = 1.4 ± 1.9 day –1 ) were produced in the evaluated 10-km reach, likely due to biochemical transformation from parent compounds (17β-estradiol, 4-nonylphenolpolyethoxylates, and 4-nonyphenolpolyethoxycarboxylates). Despite attenuation, these compounds were transported kilometers downstream, and thus additive concentrations from multiple sources and transformation of parent compounds into degradates having estrogenic activity can explain their environmental persistence and widespread observations of biological disruption in surface waters.

Minnesota↗

Susceptibility of synthetic long-chain alkylbenzenes to degradation in reducing marine sediments

Long-chain alkylbenzenes (LCABs) synthesized for production of alkylbenzene sulfonate surfactants have been used as molecular markers of anthropogenic waste for 25 years. Synthetic LCABs comprise two classes, the tetrapropylene-based alkylbenzenes (TABs) and the linear alkylbenzenes (LABs). LABs supplanted TABs in the mid-1960s because of improved biodegradability of their sulfonated analogs. Use of LCABs for molecular stratigraphy depends on their preservation in sediments over decadal time scales. Most laboratory and field studies suggest that LABs degrade rapidly under aerobic conditions but are resistant to degradation when oxygen is absent. However, recent work indicates that LABs may not be as persistent under reducing conditions as previously thought. To assess the potential for degradation of LCABs in reducing sediments, box cores collected in 1992 and 2003 near a submarine wastewater outfall system were analyzed using gas chromatography/mass spectrometry. The TABs were effectively preserved; differences between whole-core inventories were within analytical error. By contrast, whole-core inventories of the LABs decreased by about 50−60% during the same time interval. Based on direct comparison of chemical inventories in coeval core sections, LAB transformation rates are estimated at 0.07 ± 0.01 yr −1 . These results indicate that caution should be exercised when using synthetic LCABs for reconstruction of depositional records.

Environmental Science & Technology↗

Fate of sulfamethoxazole, 4-nonylphenol, and 17β-estradiol in groundwater contaminated by wastewater treatment plant effluent

Organic wastewater contaminants (OWCs) were measured in samples collected from monitoring wells located along a 4.5-km transect of a plume of groundwater contaminated by 60 years of continuous rapid infiltration disposal of wastewater treatment plant effluent. Fifteen percent of the 212 OWCs analyzed were detected, including the antibiotic sulfamethoxazole (SX), the nonionic surfactant degradation product 4-nonylphenol (NP), the solvent tetrachloroethene (PCE), and the disinfectant 1,4-dichlorobenzene (DCB). Comparison of the 2005 sampling results to data collected from the same wells in 1985 indicates that PCE and DCB are transported more rapidly in the aquifer than NP, consistent with predictions based on compound hydrophobicity. Natural gradient in situ tracer experiments were conducted to evaluate the subsurface behavior of SX, NP, and the female sex hormone 17β-estradiol (E2) in two oxic zones in the aquifer: (1) a downgradient transition zone at the interface between the contamination plume and the overlying uncontaminated groundwater and (2) a contaminated zone located beneath the infiltration beds, which have not been loaded for 10 years. In both zones, breakthrough curves for the conservative tracer bromide (Br − ) and SX were nearly coincident, whereas NP and E2 were retarded relative to Br − and showed mass loss. Retardation was greater in the contaminated zone than in the transition zone. Attenuation of NP and E2 in the aquifer was attributed to biotransformation, and oxic laboratory microcosm experiments using sediments from the transition and contaminated zones show that uniform-ring-labeled 14 C 4-normal-NP was biodegraded more rapidly (30−60% recovered as 14 CO 2 in 13 days) than 4- 14 C E2 (20−90% recovered as 14 CO 2 in 54 days). There was little difference in mineralization potential between sites.

Massachusetts↗

Fate of linear alkylbenzene sulfonate in the Mississippi River

The 2 800-km reach of the Mississippi River between Minneapolis, MN, and New Orleans, LA, was examined for the occurrence and fate of linear alkylbenzene sulfonate (LAS), a common anionic surfactant found in municipal sewage effluents. River water and bottom sediment were sampled in the summer and fall of 1991 and in the spring of 1992. LAS was analyzed using solid-phase extraction/derivatization/ gas chromatography/mass spectrometry. LAS was present on all bottom sediments at concentrations ranging from 0.01 to 20 mg/kg and was identified in 21% of the water samples at concentrations ranging from 0.1 to 28.2 μg/L. The results indicate that LAS is a ubiquitous contaminant on Mississippi River bottom sediments and that dissolved LAS is present mainly downstream from the sewage outfalls of major cities. The removal of the higher LAS homologs and external isomers indicates that sorption and biodegradation are the principal processes affecting dissolved LAS. Sorbed LAS appears to degrade slowly.

Environmental Science & Technology↗

Hydrologic and microbiological factors affecting persistence and migration of petroleum hydrocarbons spilled in a continuous-permafrost region

Fuel spills, totaling about 1300 m3, occurred between 1976 and 1978 adjacent to Imikpuk Lake, a drinking water source near Barrow, AK. Substantial contamination of soils and groundwater near the lake persists. We examined the magnitude and direction of groundwater flux and the microbial activity at this site to understand the persistence of contamination and its effect on the lake. We found that groundwater flux is small due to shallow permafrost, which restricts the cross-sectional area available for flow, and to the short annual thaw season (ca. 90 days). The small flux and limited depth also constrain contaminant transport and dispersion, resulting in persistent, shallow contamination. The numbers of hydrocarbon-oxidizing microorganisms and their laboratory mineralization potentials for benzene (at 10 ??C) were higher in samples from contaminated areas than in reference samples. Benzene mineralization potentials in groundwater samples were comparable to more temperate systems (0.1-0.5 mg of benzene mineralized L-1 day-1) and were stimulated by nutrient additions. Field measurements of dissolved oxygen, nitrate, ferrous iron, and sulfide in groundwater provided evidence that biodegradation of petroleum hydrocarbons is occurring in situ. Despite evidence of an active microbial population, microbial processes, like contaminant transport, are likely limited at this site by the short annual thaw season.

Environmental Science & Technology↗

Degradation of 1,1,2,2-tetrachloroethane in a freshwater tidal wetland: Field and laboratory evidence

Degradation reactions controlling the fate of 1,1,2,2-tetrachloroethane (PCA) in a freshwater tidal wetland that is a discharge area for a contaminated aquifer were investigated by a combined field and laboratory study. Samples from nested piezometers and porous-membrane sampling devices (peepers) showed that PCA concentrations decreased and that less chlorinated daughter products formed as the groundwater became increasingly reducing along upward flow paths through the wetland sediments. The cis and trans isomers of 1,2-dichloroethylene (12DCE) and vinyl chloride (VC) were the predominant daughter products detected from degradation of PCA in the field and in microcosms constructed under methanogenic conditions. Significantly lower ratios of cis-12DCE to trans-12DCE were produced by PCA degradation than by degradation of trichloroethylene, a common co-contaminant with PCA. 1,1,2-Trichloroethane (112TCA) and 1,2-dichloroethane (12DCA) occurred simultaneously with 12DCE, indicating simultaneous hydrogenolysis and dichloroelimination of PCA. From an initial PCA concentration of about 1.5 ??mol/L, concentrations of PCA and its daughter products decreased to below detection within a 1.0-m vertical distance in the wetland sediments and within 34 days in the microcosms. The results indicate that natural attenuation of PCA through complete anaerobic biodegradation can occur in wetlands before sensitive surface water receptors are reached.

Environmental Science & Technology↗

Acetogenic microbial degradation of vinyl chloride

Under methanogenic conditions, microbial degradation of [1,2- 14 C]vinyl chloride (VC) resulted in significant (14 ± 3% maximum recovery) but transient recovery of radioactivity as 14 C-acetate. Subsequently, 14 C-acetate was degraded to 14 CH 4 and 14 CO 2 (18 ± 2% and 54 ± 3% final recoveries, respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14 C-acetate recovery remained high (27 ± 1% maximum recovery) throughout the study, no 14 CH 4 was produced, and the final recovery of 14 CO 2 was only 35 ± 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH 4 and CO 2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO 2 reported previously under Fe(III)-reducing, SO 4 -reducing, and humic acids-reducing conditions.

Environmental Science & Technology↗