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At least 775 records · Page 43Linked to original sources
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↗
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↗
USGS1998

Anaerobic benzene oxidation in the Fe(III) reduction zone of petroleum-contaminated aquifers

The potential for anaerobic benzene oxidation in the Fe(III)-reduction zone of petroleum-contaminated aquifers was evaluated. Sediments were incubated under strict anaerobic conditions without any amendments in order to simulate in situ conditions. [ 14 C]Benzene was not oxidized to 14 CO 2 at most sites examined, which is consistent with previous studies that have found that benzene tends to persist in unamended, anaerobic aquifer materials and/or long periods of time are required in order to adapt the microbial population for benzene degradation. However, at one site located in Bemidji, MN, [ 14 C]benzene was oxidized to 14 CO 2 in unamended sediments without an apparent lag, suggesting that benzene was anaerobically degraded in situ. Benzene was not significantly oxidized in sediments from nearby Fe(III)-reducing sites nor in sediments collected from an uncontaminated background site in the same aquifer. Culturing and 16S rRNA-based molecular studies of the Bemidji aquifer demonstrated that while all sites contained similar numbers of Fe(III)-reducing microorganisms closely related to Geothrix fermentens , the site at which anaerobic benzene degradation was observed was greatly enriched with microorganisms in the family Geobacteraceae . This study provides the first data consistent with in situ anaerobic oxidation of benzene to carbon dioxide in the Fe(III)-reducing zone of a petroleum-contaminated aquifer and suggests that comparative studies on the size of the Geobacteraceae community in petroleum-contaminated aquifers might aid in the location of zones in which benzene degradation coupled to Fe(III) reduction is taking place.

Environmental Science & Technology↗
USGS1997

Sequestration of hydrophobic organic contaminants by geosorbents

The chemical interactions of hydrophobic organic contaminants (HOCs) with soils and sediments (geosorbents) may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. The underlying physical and chemical phenomena potentially responsible for this apparent sequestration of HOCs by geosorbents are not well understood. This challenges our concepts for assessing exposure and toxicity and for setting environmental quality criteria. Currently there are no direct observational data revealing the molecular-scale locations in which nonpolar organic compounds accumulate when associated with natural soils or sediments. Hence macroscopic observations are used to make inferences about sorption mechanisms and the chemical factors affecting the sequestration of HOCs by geosorbents. Recent observations suggest that HOC interactions with geosorbents comprise different inorganic and organic surfaces and matrices, and distinctions may be drawn along these lines, particularly with regard to the roles of inorganic micropores, natural sorbent organic matter components, combustion residue particulate carbon, and spilled organic liquids. Certain manipulations of sorbates or sorbent media may help reveal sorption mechanisms, but mixed sorption phenomena complicate the interpretation of macroscopic data regarding diffusion of HOCs into and out of different matrices and the hysteretic sorption and aging effects commonly observed for geosorbents. Analytical characterizations at the microscale, and mechanistic models derived therefrom, are needed to advance scientific knowledge of HOC sequestration, release, and environmental risk.

Environmental Science & Technology↗
USGS1997

Method for determination of methyl tert-butyl ether and its degradation products in water

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

Environmental Science & Technology↗
USGS1998

Polychlorinated dibenzo-p-dioxin and dibenzofuran concentration profiles in sediment and fish tissue of the Willamette Basin, Oregon

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) are highly hydrophobic compounds that have been implicated as carcinogens and, more recently, as estrogen disrupters. An occurrence and distribution study of these compounds in the Willamette Basin, Oregon, was conducted by the U.S. Geological Survey as part of the National Water-Quality Assessment Program. Bed sediment was collected from 22 sites; fish tissue was collected from eight sites. PCDD/F were found to be ubiquitous in Willamette Basin sediment. A distinct homolog profile, dominated by octachlorodibenzo-p-dioxin, was observed in sediment throughout the basin. The PCDD homolog profile was consistent at all sites, regardless of total PCDD/F concentration, presence of point sources, subbasin size, geographic location or land use. Principal components analysis revealed a gradient among the homolog profiles that showed increasing dominance of highly chlorinated congeners where human and industrial activity increased. Tissue and bed sediment obtained from the same site did not have similar PCDD/F concentrations or homolog profiles. Fish tissue showed enrichment in less chlorinated congeners and congeners with chlorine substitutions in the 2, 3, 7 and 8 positions.

Environmental Science & Technology↗
USGS1998

Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments

The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., K(oc) values) are relatively invariant either for the 'clean' (uncontaminated) soils or for the clean sediments; however, the mean K(oc) values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in K(oc) are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher K(oc) values. At given K(ow) values (octanol-water), the PAHs exhibit much higher K(oc) values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower K(ow) values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log K(oc) and log K(ow) for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., Koc values) are relatively invariant either for the `clean' (uncontaminated) soils or for the clean sediments; however, the mean Koc values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in Koc are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher Koc values. At given Kow values (octanol-water), the PAHs exhibit much higher Koc values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower Kow values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log Koc and log Kow for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.

Environmental Science & Technology↗