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At least 433 records · Page 24Linked to original sources
USGS1996

Anaerobic hydrocarbon degradation in petroleum-contaminated harbor sediments under sulfate-reducing and artificially imposed iron-reducing conditions

The potential use of iron(III) oxide to stimulate in-situ hydrocarbon degradation in anaerobic petroleum-contaminated harbor sediments was investigated. Previous studies have indicated that Fe(III)-reducing bacteria (FeRB) can oxidize some electron donors more effectively than sulfate- reducing bacteria (SRB). In contrast to previous results in freshwater sediments, the addition of Fe(III) to marine sediments from San Diego Bay, CA did not switch the terminal electron-accepting process (TEAP) from sulfate reduction to Fe-(III) reduction. Addition of Fe(III) also did not stimulate anaerobic hydrocarbon oxidation. Exposure of the sediment to air [to reoxidize Fe(II) to Fe(III)] followed by anaerobic incubation of the sediments, resulted in Fe-(III) reduction as the TEAP, but contaminant degradation was not stimulated and in some instances was inhibited. The difference in the ability of FeRB to compete with the SRB in the different sediment treatments was related to relative population sizes. Although the addition of Fe(III) did not stimulate hydrocarbon degradation, the results presented here as well as other recent studies demonstrate that there may be significant anaerobic hydrocarbon degradation under sulfate-reducing conditions in harbor sediments.

Environmental Science & Technology↗
USGS1997

Chemical factors influencing colloid-facilitated transport of contaminants in porous media

The effects of colloids on the transport of two strongly sorbing solutes a hydrophobic organic compound, phenanthrene, and a metal ion, Ni 2+ were studied in sand-packed laboratory columns under different pH and ionic strength conditions. Two types of column experiments were performed as follows: (i) sorption/mobilization experiments where the contaminant was first sorbed in the column under conditions where no colloids were released and mobilized under conditions where colloids were released as a result of ionic strength reduction in the influent; and (ii) transport experiments where the contaminant, dissolved or sorbed on colloids, was injected into columns packed with a strongly sorbing porous medium. In the first type of experiment, contaminant mobilization was significant only when all releasable colloids were flushed from the column. In all other cases, although high colloid particle concentrations were encountered, there was no marked effect on total contaminant concentrations. In the second type of experiment, colloid deposition efficiencies were shown to control the enhancement of transport. The deposition efficiency was a function of the pH (for a high organic content sand) and of the contaminant concentration (for a charged species such as Ni 2+ ).

Environmental Science & Technology↗
USGS1997

Effect of tributary inflows on the distribution of trace metals in fine- grained bed sediments and benthic insects of the Clark Fork River, Montana

The effect of tributary inflows on metal concentrations in <63-μm sediments and benthic insects was examined on two scales (380 km and <2 km) in a river impacted by mining. A dilution−mixing model effectively described large-scale dispersion of Cd, Cu, and Pb in the sediments of the river. Input of metal from contaminated flood plains may introduce additional contamination in the middle reaches of the river. Intensive sampling around the confluences of two tributaries showed that there were significant, localized decreases in some metal concentrations immediately downstream of the inflows. Sediment metal concentrations 1 km below the inflows returned to values within the range predicted by the dilution−mixing model. Metal concentrations in benthic insects exhibited spatial patterns similar to those of the sediments, indicating that biological exposures to metals are at least partially dependent on the physical processes controlling the dispersion of sediment-bound metals. Tributary inflows introduce variability in metal contamination on different spatial scales that must be considered when assessing ecological risks in contaminated rivers. In addition to large-scale dilution of contaminants, smaller areas of reduced metal exposure occur near tributary inflows. These may shelter metal-sensitive taxa from severe metal contamination in the mainstem.

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

Response of aluminum solubility to elevated nitrification in soil of a red spruce stand in eastern Maine

Elevated concentrations of soluble Al can impair tree growth and be toxic to aquatic biota, but effects of acidic deposition on Al solubility in forest soils are only partially understood because of complex interactions with H+ and organic matter. We therefore evaluated Al solubility in two red spruce stands in eastern Maine, one of which received dry (NH4)2SO4 at a rate of 1800 equiv ha-1 yr-1 during 19891995. Samples of soil (Spodosol Oa and Bh horizons) and soil solution were collected on five dates from 1992 to 1995. The treatment elevated nitrification, causing an increase in acid input that led to inorganic Al concentrations of greater than 60 ??mol L-1 in both the Oa and Bh horizons. Solubility of Al was also lower in the Bh horizon of the treated stand than in the reference stand, a response related to higher DOC concentrations in the treated stand. Concentrations of CuCl2 and pyrophosphate-extractable Al were higher in the Oa horizon of the treated watershed than the reference stand, a result of accelerated weathering of mineral particles caused by lower solution pH in the treated stand (3.47) than in the reference stand (3.69). Dissolved Al concentrations in these soils are the result of complex mechanisms through which mineral matter, organic matter, and pH interact to control Al solubility; mechanisms that are not incorporated in current Al solubility models.

Environmental Science & Technology↗
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

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

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

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

Kinetics of DCE and VC mineralization under methanogenic and Fe(III)- reducing conditions

The kinetics of anaerobic mineralization of DCE and VC under methanogenic and Fe(III)-reducing conditions as a function of dissolved contaminant concentration were evaluated. Microorganisms indigenous to creek bed sedi ments, where groundwater contaminated with chlorinated ethenes continuously discharges, demonstrated significant mineralization of DCE and VC under methanogenic and Fe(III)-reducing conditions. Over 37 days, the recovery of [1,2- 14 C]VC radioactivity as 14 CO 2 ranged from 5% to 44% and from 8% to 100% under methanogenic and Fe(III)-reducing conditions, respectively. The recovery of [1,2- 14 C]DCE radioactivity as 14 CO 2 ranged from 4% to 14% and did not vary significantly between methanogenic and Fe(III)-reducing conditions. VC mineralization was described by Michaelis−Menten kinetics. Under methanogenic condi tions, V max was 0.19 ± 0.01 μmol L -1 d -1 and the half-saturation constant, k m , was 7.6 ± 1.7 μM. Under Fe(III)-reducing conditions, V max was 0.76 ± 0.07 μmol L -1 d -1 and k m was 1.3 ± 0.5 μM. In contrast, DCE mineralization could be described by first-order kinetics. The first-order degradation rate constant for DCE mineralization was 0.6 ± 0.2% d -1 under methanogenic and Fe(III)-reducing conditions. The results indicate that the kinetics of chlorinated ethene mineralization can vary significantly with the specific contaminant and the predominant redox conditions under which mineralization occurs.

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

Organic carbon and nitrogen content associated with colloids and suspended particulates from the Mississippi River and some of its tributaries

Suspended material samples were collected at 16 sites along the Mississippi River and some of its tributaries during July-August 1991, October-November 1991, and April-May 1992, and separated into colloid and particulate fractions to determine the organic carbon content of these two fractions of suspended material. Sample collection involved centrifugation to isolate the suspended particulate fraction and ultrafiltration to isolate the colloid fraction. For the first time, particulate and colloid concentrations and organic carbon and nitrogen content were investigated along the entire reach of the Mississippi River from above Minneapolis, Minnesota, to below New Orleans, Louisiana. Organic carbon content of the colloid (15.2 percent) was much higher than organic carbon content of the particulate material (4.8 percent). Carbon/nitrogen ratios of colloid and particulate phases were more similar to ratios for microorganisms than to ratios for soils, humic materials, or plants.Suspended material samples were collected at 16 sites along the Mississippi River and some of its tributaries during July-August 1991, October-November 1991, and April-May 1992, and separated into colloid and particulate fractions to determine the organic carbon content of these two fractions of suspended material. Sample collection involved centrifugation to isolate the suspended particulate fraction and ultrafiltration to isolate the colloid fraction. For the first time, particulate and colloid concentrations and organic carbon and nitrogen content were investigated along the entire reach of the Mississippi River from above Minneapolis, Minnesota, to below New Orleans, Louisiana. Organic carbon content of the colloid (15.2 percent) was much higher than organic carbon content of the particulate material (4.8 percent). Carbon/nitrogen ratios of colloid and particulate phases were more similar to ratios for microorganisms than to ratios for soils, humic materials, or plants.

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

Contribution of hydroxylated atrazine degradation products to the total atrazine load in midwestern streams

The contribution of hydroxylated atrazine degradation products (HADPs) to the total atrazine load (i.e., atrazine plus stable metabolites) in streams needs to be determined in order to fully assess the impact of atrazine contamination on stream ecosystems and human health. The objectives of this study were (1) to determine the contribution of HADPs to the total atrazine load in streams of nine midwestern states and (2) to discuss the mechanisms controlling the concentrations of HADPs in streams. Stream samples were collected from 95 streams in northern Missouri at preplant and postplant of 1994 and 1995, and an additional 46 streams were sampled in eight midwestern states at postplant of 1995. Samples were analyzed for atrazine, deethylatrazine (DEA), deisopropylatrazine (DIA), and three HADPs. Overall, HADP prevalence (i.e., frequency of detection) ranged from 87 to 100% for hydroxyatrazine (HA), 0 to 58% for deethylhydroxyatrazine (DEHA), and 0% for deisopropylhydroxyatrazine (DIHA) with method detection limits of 0.04−0.10 μg L -1 . Atrazine metabolites accounted for nearly 60% of the atrazine load in northern Missouri streams at preplant, with HA the predominant metabolite present. Data presented in this study and a continuous monitoring study are used to support the hypothesis that a combination of desorption from stream sediments and dissolved-phase transport control HADP concentrations in streams.

Environmental Science & Technology↗
USGS1998

Evaluation of microtiter-plate enzyme-linked immunosorbent assay for the analysis of triazine and chloroacetanilide herbicides in rainfall

Triazine and chloroacetanilide concentrations in rainfall samples collected from a 23-state region of the United States were analyzed with microtiter-plate enzyme-linked immunosorbent assay (ELISA). Thirty-six percent of rainfall samples (2072 out of 5691) were confirmed using gas chro matography/mass spectrometry (GC/MS) to evaluate the operating performance of ELISA as a screening test. Comparison of ELISA to GC/MS results showed that the two ELISA methods accurately reported GC/MS results ( m = 1), but with more variability evident with the triazine than with the chloroacetanilide ELISA. Bayes's rule, a standardized method to report the results of screening tests, indicated that the two ELISA methods yielded comparable predictive values (80%), but the triazine ELISA yielded a false-positive rate of 11.8% and the chloroacetanilide ELISA yielded a false-negative rate of 23.1%. The false-positive rate for the triazine ELISA may arise from cross reactivity with an unknown triazine or metabolite. The false-negative rate of the chloroacetanilide ELISA probably resulted from a combination of low sensitivity at the reporting limit of 0.15 μg/L and a distribution characterized by 75% of the samples at or below the reporting limit of 0.15 μg/L.

Environmental Science & Technology↗