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At least 721 records · Page 40Linked to original sources
USGS1997

Binding of pyrene to aquatic and commercial humic substances: The role of molecular weight and aromaticity

The binding of pyrene to a number of humic substances isolated from various aquatic sources and a commercial humic acid was measured using the solubility enhancement method. The humic materials used in this study were characterized by various spectroscopic and liquid chromatography methods. A strong correlation was observed between the pyrene binding coefficient, K(doc), and the molecular weights, molar absorptivities at 280 nm, and aromaticity of the aquatic humic substances. Binding of pyrene to the commercial humic acid, however, was significantly stronger and did not obey the relationships observed between K(doc) and the chemical properties of the aquatic humic substrates. These results suggest that the molecular weight and the aromatic content of the humic substrates exert influences on the binding of nonpolar and planar aromatic molecules and that the physicochemical properties of both humic materials and organic solutes are important in controlling the speciation of nonpolar organic contaminants in natural waters.

Environmental Science & Technology↗
USGS1996

Physiological considerations in applying laboratory-determined buoyant densities to predictions of bacterial and protozoan transport in groundwater: Results of in-situ and laboratory tests

Buoyant densities were determined for groundwater bacteria and microflagellates (protozoa) from a sandy aquifer (Cape Cod, MA) using two methods: (1) density-gradient centrifugation (DGC) and (2) Stoke's law approximations using sedimentation rates observed during natural-gradient injection and recovery tests. The dwarf (average cell size, 0.3 μm), unattached bacteria inhabiting a pristine zone just beneath the water table and a majority (∼80%) of the morphologically diverse community of free-living bacteria inhabiting a 5-km-long plume of organically-contaminated groundwater had DGC-determined buoyant densities <1.019 g/cm 3 before culturing. In the aquifer, sinking rates for the uncultured 2-μm size class of contaminant plume bacteria were comparable to that of the bromide tracer (1.9 × 10 - 3 M), also suggesting a low buoyant density. Culturing groundwater bacteria resulted in larger (0.8−1.3 μm), less neutrally-buoyant (1.043−1.081 g/cm 3 ) cells with potential sedimentation rates up to 64-fold higher than those predicted for the uncultured populations. Although sedimentation generally could be neglected in predicting subsurface transport for the community of free-living groundwater bacteria, it appeared to be important for the cultured isolates, at least until they readapt to aquifer conditions. Culturing-induced alterations in size of the contaminant-plume microflagellates (2−3 μm) were ameliorated by using a lower nutrient, acidic (pH 5) porous growth medium. Buoyant densities of the cultured microflagellates were low, i.e., 1.024−1.034 g/cm 3 (using the DGC assay) and 1.017−1.039 g/cm 3 (estimated from in-situ sedimentation rates), sug gesting good potential for subsurface transport under favorable conditions.

Environmental Science & Technology↗
USGS1997

Anaerobic degradation of benzene in diverse anoxic environments

Benzene has often been observed to be resistant to microbial degradation under anoxic conditions. A number of recent studies, however, have demonstrated that anaerobic benzene utilization can occur. This study extends the previous reports of anaerobic benzene degradation to sediments that varied with respect to contamination input, predominant redox condition, and salinity. In spite of differences in methodology, microbial degradation of benzene was noted in slurries constructed with sediments from various geographical locations and range from aquifer sands to fine-grained estuarine muds, under methanogenic, sulfate-reducing, and iron-reducing conditions. In aquifer sediments under methanogenic conditions, benzene loss was concomitant with methane production, and microbial utilization of [ 14 C]benzene yielded 14 CO 2 and 14 CH 4 . In slurries with estuarine and aquifer sediments under sulfate-reducing conditions, the loss of sulfate in amounts consistent with the stoichiometric degradation of benzene or the conversion of [ 14 C]benzene to 14 CO 2 indicates that benzene was mineralized. Benzene loss also occurred in the presence of Fe(III) in sediments from freshwater environments. Microbial benzene utilization, however, was not observed under denitrifying conditions. These results indicate that the potential for the anaerobic degradation of benzene, which was once thought to be resistant to non-oxygenase attack, exists in a variety of aquatic sediments from widely distributed locations.

Environmental Science & Technology↗
USGS1997

From the 1988 drought to the 1993 flood: Transport of halogenated organic compounds with the Mississippi river suspended sediment at Thebes, Illinois

Suspended sediment was isolated from water samples collected from the Mississippi River at Thebes, IL, eight times over a 5-year period from May 1988 through September 1993 in order to evaluate the transport of lipophilic halogenated organic compounds associated with the suspended sediment. Two hydrologic extremes were included-the 1988 drought and the 1993 flood. Halogenated organic compounds included polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachloroanisole, DCPA (dacthal), trifluralin, aldrin, dieldrin, and chlordane components. Sediment transport of most of these organic compounds was substantially higher during the 1993 flood then at other sampling times. The extreme transports during the flood were due to unusually high concentrations of some contaminants on the suspended sediment, low to average concentrations of suspended sediment being transported, and unusually high water discharges.

Illinois↗
USGS1997

Lack of correlation between organic acid concentrations and predominant electron-accepting processes in a contaminated aquifer

Long-term (1992-1995) monitoring data from a petroleum hydrocarbon- contaminated aquifer were used to examine the hypothesis that concentrations of low molecular weight (LMW) aliphatic organic acids reflect terminal electron-accepting processes. During the period of study, concentrations of dissolved hydrogen (H2) indicated that methanogenic, sulfate-reducing, and iron(III)-reducing conditions predominated at the site. However, there was no correlation between LMW organic acid concentrations and concentrations of dissolved H2. These results indicate that organic acid concentrations are not a reliable indicator of local redox conditions at this site.

Environmental Science & Technology↗
USGS1997

Transport and recovery of bacteriophage PRD1 in a sand and gravel aquifer: Effect of sewage-derived organic matter

To test the effects of sewage-derived organic matter on virus attachment, 32P-labeled bacteriophage PRD1, linear alkylbenzene sulfonates (LAS), and tracers were injected into sewage-contaminated (suboxic, elevated organic matter) and uncontaminated (oxic, low organic matter) zones of an iron oxide-coated quartz sand and gravel aquifer on Cape Cod, MA. In the uncontaminated zone, 83% of the PRD1 were attenuated over the first meter of transport by attachment to aquifer grains. In the contaminated zone, 42% of the PRD1 were attenuated over the first meter of transport. Sewage-derived organic matter contributed to the difference in PRD1 attenuation by blocking attachment sites in the contaminated zone. At greater distances down gradient (to a total transport distance of 3.6 m), a near-constant amount of PRD1 continued to break through, suggesting that aquifer grain heterogeneities allowed a small amount of reversible attachment. Injection of an LAS mixture (25 mg L-1), a common sewage constituent, remobilized 87% of the attached PRD1 in the contaminated zone, but only 2.2% in the uncontaminated zone. LAS adsorption promoted virus recovery in the contaminated zone by altering the PRD1-surface interactions; however, the amount of LAS adsorbed was not sufficient to promote release of the attached PRD1 in the uncontaminated zone.

Environmental Science & Technology↗
USGS1997

Matrix-enhanced degradation of p,p'-DDT during gas chromatographic analysis: A consideration

Analysis of p,p &lsquo;-DDT in environmental samples requires monitoring the GC-derived breakdown of this insecticide, which produces p,p &lsquo;-DDD and/or p,p &lsquo;-DDE, both also primary environmental degradation products. A performance evaluation standard (PES) containing p,p &lsquo;-DDT but not p,p &lsquo;-DDD or p,p &lsquo;-DDE can be injected at regular intervals throughout an analytical sequence to monitor GC degradation. Some U.S. EPA methods limit GC breakdown of DDT in the PES to &le;20%. GC/MS analysis of large-volume natural water samples fortified with deuterium- and 13 C-labeled p,p &lsquo;-DDT exhibited up to 65% DDT breakdown by the GC inlet. These matrix-enhanced GC degradation amounts substantially exceeded the <20% breakdown levels indicated by bracketing injections of the PES containing unlabeled and labeled DDT. Substantial matrix-enhanced GC degradation was not observed during analysis of a limited number of fractionated bed-sediment extracts containing labeled DDT. Use of isotopically labeled DDT seems to provide an effective tool for monitoring sample-specific DDT breakdown during GC/MS analysis. However, analyte co-elutions render impractical their use in GC/ECD analysis. The oc currence of matrix-enhanced GC degradation might have important implications on data quality and the resultant interpretations of the environmental degradation of DDT and other thermolabile contaminants.

Environmental Science & Technology↗
USGS1997

Analysis of environmental data with censored observations

The potential threats to humans and to terrestrial and aquatic ecosystems from environmental contamination could depend on the sum of the concentrations of different chemicals. However, direct summation of environmental data is not generally feasible because it is common for some chemical concentrations to be recorded as being below the analytical reporting limit. This creates special problems in the analysis of the data. A new model selection procedure, named forward censored regression, is introduced for selecting an appropriate model for environmental data with censored observations. The procedure is demonstrated using concentrations of atrazine (2-chloro-4-ethylamino-6-isopropylamino- s -triazine), deethylatrazine (DEA, 2-amino-4-chloro-6-isopropylamino- s -triazine), and deisopropylatrazine (DIA, 2-amino-4-chloro-6-ethylamino- s -triazine) in groundwater in the midwestern United States by using the data derived from a previous study conducted by the U.S. Geological Survey. More than 80% of the observations for each compound for this study were left censored at 0.05 &mu;g/L. The values for censored observations of atrazine, DEA, and DIA are imputed with the selected models. The summation of atrazine residue (atrazine + DEA + DIA) can then be calculated using the combination of observed and imputed values to generate a pseudo-complete data set. The all-subsets regression procedure is applied to the pseudo-complete data to select the final model for atrazine residue. The methodology presented can be used to analyze similar cases of environmental contamination involving censored data.

Environmental Science & Technology↗
USGS1997

Bacterial oxidation of methyl bromide in Mono Lake, California

The oxidation of methyl bromide (MeBr) in the water column of Mono Lake, CA, was studied by measuring the formation of H14CO3 from [14C]MeBr. Potential oxidation was detected throughout the water column, with highest rates occurring in the epilimnion (5-12 m depth). The oxidation of MeBr was eliminated by filter-sterilization, thereby demonstrating the involvement of bacteria. Vertical profiles of MeBr activity differed from those obtained for nitrification and methane oxidation, indicating that MeBr oxidation is not simply a co-oxidation process by either nitrifiers or methanotrophs. Furthermore, specific inhibitors of methane oxidation and/or nitrification (e.g., methyl fluoride, acetylene, allyl sulfide) had no effect upon the rate of MeBr oxidation in live samples. Of a variety of potential electron donors added to Mono Lake water, only trimethylamine resulted in the stimulation of MeBr oxidation. Cumulatively, these results suggest that the oxidation of MeBr in Mono Lake waters is attributable to trimethylamine-degrading methylotrophs. Neither methyl chloride nor methanol inhibited the oxidation of [14C]MeBr in live samples, indicating that these bacteria directly oxidized MeBr rather than the products of MeBr nucleophilic substitution reactions.

Environmental Science & Technology↗
USGS1997

Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

Environmental Science & Technology↗
USGS1997

Risk of nitrate in groundwaters of the United States - A national perspective

Nitrate contamination of groundwater occurs in predictable patterns, based on findings of the U.S. Geological Survey's (USGS) National Water Quality Assessment (NAWQA) Program. The NAWQA Program was begun in 1991 to describe the quality of the Nation's water resources, using nationally consistent methods. Variables affecting nitrate concentration in groundwater were grouped as 'input' factors (population density end the amount of nitrogen contributed by fertilizer, manure, and atmospheric sources) and 'aquifer vulnerability' factors (soil drainage characteristic and the ratio of woodland acres to cropland acres in agricultural areas) and compiled in a national map that shows patterns of risk for nitrate contamination of groundwater. Areas with high nitrogen input, well-drained soils, and low woodland to cropland ratio have the highest potential for contamination of shallow groundwater by nitrate. Groundwater nitrate data collected through 1992 from wells less than 100 ft deep generally verified the risk patterns shown on the national map. Median nitrate concentration was 0.2 mg/L in wells representing the low-risk group, and the maximum contaminant level (MCL) was exceeded in 3% of the wells. In contrast, median nitrate concentration was 4.8 mg/L in wells representing the high-risk group, and the MCL was exceeded in 25% of the wells.Nitrate contamination of groundwater occurs in predictable patterns, based on findings of the U.S. Geological Survey's (USGS) National Water Quality Assessment (NAWQA) Program. The NAWQA Program was begun in 1991 to describe the quality of the Nation's water resources, using nationally consistent methods. Variables affecting nitrate concentration in groundwater were grouped as `input' factors (population density and the amount of nitrogen contributed by fertilizer, manure, and atmospheric sources) and `aquifer vulnerability' factors (soil drainage characteristic and the ratio of woodland acres to cropland acres in agricultural areas) and compiled in a national map that shows patterns of risk for nitrate contamination of groundwater. Areas with high nitrogen input, well-drained soils, and low woodland to cropland ratio have the highest potential for contamination of shallow groundwater by nitrate. Groundwater nitrate data collected through 1992 from wells less than 100 ft deep generally verified the risk patterns shown on the national map. Median nitrate concentration was 0.2 mg/L in wells representing the low-risk group, and the maximum contaminant level (MCL) was exceeded in 3% of the wells. In contrast, median nitrate concentration was 4.8 mg/L in wells representing the high-risk group, and the MCL was exceeded in 25% of the wells.

Environmental Science & Technology↗
USGS1997

Herbicides and their metabolites in rainfall: Origin, transport, and deposition patterns across the midwestern and northeastern United States, 1990-1991

Herbicides were detected in rainfall throughout the midwestern and northeastern United States during late spring and summer of 1990 and 1991. Herbicide concentrations exhibited distinct geographic and seasonal patterns. The highest concentrations occurred in midwestern cornbelt states following herbicide application to cropland. Volume-weighted concentrations of 0.2−0.4 μg/L for atrazine and alachlor were typical in this area during mid-April through mid-July, and weighted concentrations as large as 0.6−0.9 μg/L occurred at several sites. Concentrations of 1−3 μg/L were measured in a few individual samples. Atrazine was detected most often followed by alachlor, deethylatrazine, metolachlor, cyanazine, and deisopropylatrazine. The high ratio (∼0.5) of deethylatrazine to atrazine in rainfall suggests atmospheric degradation of atrazine. Mass deposition of herbicides was greatest in areas where herbicide use was high and decreased with distance from the cornbelt. Estimated deposition rates for both atrazine and alachlor ranged from more than 240 μg m - 2 yr - 1 for some areas in the midwestern states to less than 10 μg m - 2 yr - 1 for the New England states. The estimated annual deposition of atrazine on the Great Lakes ranged from about 12 to 63 μg m - 2 yr - 1 . The total amounts of atrazine and alachlor deposited annually in rainfall in the study area represent about 0.6% of the atrazine and 0.4% of the alachlor applied annually to crops in the study area.

Environmental Science & Technology↗
USGS1997

Enhancement and inhibition of microbial activity in hydrocarbon- contaminated arctic soils: Implications for nutrient-amended bioremediation

Bioremediation is being used or proposed as a treatment option at many hydrocarbon-contaminated sites. One such site is a former bulk-fuel storage facility near Barrow, AK, where contamination persists after approximately 380 m3 of JP-5 was spilled in 1970. The soil at the site is primarily coarse sand with low organic carbon (<1%) end low moisture (1-3%) contents. We examined the effects of nutrient additions on microorganisms in contaminated soil from this site in laboratory microcosms and in mesocosms incubated for 6 weeks in the field. Nitrogen was the major limiting nutrient in this system, but microbial populations and activity were maximally enhanced by additions of both nitrogen and phosphorus. When nutrients were added to soil in the field at three levels of N:P (100:45, 200:90, and 300:135 mg/kg soil), the greatest stimulation in microbial activity occurred at the lowest, rather than the highest, level of nutrient addition. The total soil-water potentials ranged from -2 to -15 bar with increasing levels of fertilizer. Semivolatile hydrocarbon concentrations declined significantly only in the soils treated at the low fertilizer level. These results indicate that an understanding of nutrient effects at a specific site is essential for successful bioremediation.Bioremediation is being used or proposed as a treatment option at many hydrocarbon-contaminated sites. One such site is a former bulk-fuel storage facility near Barrow, AK, where contamination persists after approximately 380 m3 of JP-5 was spilled in 1970. The soil at the site is primarily coarse sand with low organic carbon (<1%) and low moisture (1-3%) contents. We examined the effects of nutrient additions on microorganisms in contaminated soil from this site in laboratory microcosms and in mesocosms incubated for 6 weeks in the field. Nitrogen was the major limiting nutrient in this system, but microbial populations and activity were maximally enhanced by additions of both nitrogen and phosphorus. When nutrients were added to soil in the field at three levels of N:P (100:45, 200:90, and 300:135 mg/kg soil), the greatest stimulation in microbial activity occurred at the lowest, rather than the highest, level of nutrient addition. The total soil-water potentials ranged from -2 to -15 bar with increasing levels of fertilizer. Semi-volatile hydrocarbon concentrations declined significantly only in the soils treated at the low fertilizer level. These results indicate that an understanding of nutrient effects at a specific site is essential for successful bioremediation.

Environmental Science & Technology↗
USGS1997

Marine bacterial degradation of brominated methanes

Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.

Environmental Science & Technology↗
USGS1997

Groundwater record of halocarbon transport by the Danube River

Groundwater dating studies have supported the concept that aquifers with low coefficients of dispersion may contain coherent records of past conditions in recharge areas. Groundwater records can provide unique information about natural or anthropogenic changes in the atmosphere and hydrosphere where long-term monitoring data are not available. Here we describe a 40-year record of halocarbon contamination in the Danube River that was retrieved from a shallow aquifer in northwest Hungary. The time scale is based on 3H and He isotope dating of groundwaters that were recharged by the Danube River and moved horizontally away from the river in a surficial gravel aquifer with minor dispersion at a maximum rate of at least 500 m/yr. Analyses of dated groundwaters along a flow path indicate that the river loads of selected compounds (including CFC-12, CFC-113, and trichloroethane) were negligible before about 1950, rose rapidly to peak values in the 1960s and 1970s, and then decreased by varying degrees to the present. Peak concentrations are tentatively attributed to point sources in upstream urban-industrial centers; while recent decreases presumably resulted from declining manufacturing rates and(or) improvements in control of urban- industrial runoff and sewage effluent entering the river in upstream areas.

Danube River↗
USGS1998

Occurrence of pesticides in shallow groundwater of the United States: initial results from the National Water-Quality Assessment program

The first phase of intensive data collection for the National Water-Quality Assessment (NAWQA) was completed during 1993&minus;1995 in 20 major hydrologic basins of the United States. Groundwater land-use studies, designed to sample recently recharged groundwater (generally within 10 years) beneath specific land-use and hydrogeologic settings, are a major component of the groundwater quality as sessment for NAWQA. Pesticide results from the 41 land-use studies conducted during 1993&minus;1995 indicate that pesticides were commonly detected in shallow groundwater, having been found at 54.4% of the 1034 sites sampled in agricultural and urban settings across the United States. Pesticide concentrations were generally low, with over 95% of the detections at concentrations less than 1 &mu;g/L. Of the 46 pesticide compounds examined, 39 were detected. The compounds detected most frequently were atrazine (38.2%), deethylatrazine (34.2%), simazine (18.0%), metolachlor (14.6%), and prometon (13.9%). Statistically significant relations were observed between frequencies of detection and the use, mobility, and persistence of these compounds. Pesticides were commonly detected in both agricultural (56.4%; 813 sites) and urban (46.6%; 221 sites) settings. Frequent detections of pesticides in urban areas indicate that, as is the case with agricultural pesticide use in agricultural areas, urban and suburban pesticide use significantly contribute to pesticide occurrence in shallow groundwater. Although pesticides were detected in groundwater sampled in urban areas and all nine of the agricultural land-use categories examined, significant variations in occurrence were observed among these categories. Maximum contaminant levels (MCLs) established by the U.S. Environmental Protection Agency for drinking water were exceeded for only one pesticide (atrazine, 3 &mu;g/L) at a single location. However, MCLs have been established for only 25 of the 46 pesticide compounds examined, do not cover pesticide degradates, and, at present, do not take into account additive or synergistic effects of combinations of pesticide compounds or potential effects on nearby aquatic ecosystems.

Environmental Science & Technology↗