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R.P. Eganhouse

Publications and source records attributed to R.P. Eganhouse.

15 recordsLinked to original sources
USGS2009

Pore-water chemistry from the ICDP-USGS coer hole in the Chesapeake Bay impact structure--Implications for paleohydrology, microbial habitat, and water resources

We investigated the groundwater system of the Chesapeake Bay impact structure by analyzing the pore-water chemistry in cores taken from a 1766-m-deep drill hole 10 km north of Cape Charles, Virginia. Pore water was extracted using high-speed centrifuges from over 100 cores sampled from a 1300 m section of the drill hole. The pore-water samples were analyzed for major cations and anions, stable isotopes of water and sulfate, dissolved and total carbon, and bioavailable iron. The results reveal a broad transition between fresh and saline water from 100 to 500 m depth in the post-impact sediment section, and an underlying syn-impact section that is almost entirely filled with brine. The presence of brine in the lowermost post-impact section and the trend in the dissolved chloride with depth suggest a transport process dominated by molecular diffusion and slow, compaction-driven, upward flow. Major ion results indicate residual effects of diagenesis from heating, and a pre-impact origin for the brine. High levels of dissolved organic carbon (6-95 mg/L) and the distribution of electron acceptors indicate an environment that may be favorable for microbial activity throughout the drilled section. The concentration and extent of the brine is much greater than had previously been observed, suggesting its occurrence may be common in the inner crater. However, groundwater flow conditions in the structure may reduce the salt-water-intrusion hazard associated with the brine.

Special Paper of the Geological Society of America↗
USGS2008

DDE in sediments of the Palos Verdes shelf, California: In situ transformation rates and geochemical fate

From 1947 to 1971 the world's largest manufacturer of DDT discharged process wastes into the sewers of Los Angeles County. Roughly 870-1450 t of DDT were released to the ocean off Palos Verdes, CA, a portion of which (???100 t) resides in sediments on the continental shelf and slope. The most abundant DDT compound in the sediments, p,p???-DDE, is degrading by reductive dechlorination, butthe rate of transformation and factors controlling it are not well understood. In order to estimate in situ transformation rates and predict the long-term fate of p,p???-DDE, box cores were collected in 1992 and 2003 from a single location on the Palos Verdes Shelf and analyzed for 8 DDT compounds and 84 polychlorinated biphenyl (PCB) congeners. The PCBs show no evidence of dechlorination, and inventories did not change between 1992 and 2003. By contrast, the inventory of p,p???-DDE decreased by 43%, whereas that of p,p???-DDMU, the putative reductive dechlorination product increased by 34%. The first-order transformation rate for p,p???-DDE at the study site is 0.051 ?? 0.006 yr-1. A multistep reaction model suggests that inventories of p,p???-DDE and p,p???-DDMU will continue to decline, whereas that of p,p???-DDNU will reach a maximum around 2014.

Environmental Science & Technology↗
USGS2003

Inverse modeling of BTEX dissolution and biodegradation at the Bemidji, MN crude-oil spill site

The U.S. Geological Survey (USGS) solute transport and biodegradation code BIOMOC was used in conjunction with the USGS universal inverse modeling code UCODE to quantify field-scale hydrocarbon dissolution and biodegradation at the USGS Toxic Substances Hydrology Program crude-oil spill research site located near Bemidji, MN. This inverse modeling effort used the extensive historical data compiled at the Bemidji site from 1986 to 1997 and incorporated a multicomponent transport and biodegradation model. Inverse modeling was successful when coupled transport and degradation processes were incorporated into the model and a single dissolution rate coefficient was used for all BTEX components. Assuming a stationary oil body, we simulated benzene, toluene, ethylbenzene, m , p -xylene, and o -xylene (BTEX) concentrations in the oil and ground water, respectively, as well as dissolved oxygen. Dissolution from the oil phase and aerobic and anaerobic degradation processes were represented. The parameters estimated were the recharge rate, hydraulic conductivity, dissolution rate coefficient, individual first-order BTEX anaerobic degradation rates, and transverse dispersivity. Results were similar for simulations obtained using several alternative conceptual models of the hydrologic system and biodegradation processes. The dissolved BTEX concentration data were not sufficient to discriminate between these conceptual models. The calibrated simulations reproduced the general large-scale evolution of the plume, but did not reproduce the observed small-scale spatial and temporal variability in concentrations. The estimated anaerobic biodegradation rates for toluene and o -xylene were greater than the dissolution rate coefficient. However, the estimated anaerobic biodegradation rates for benzene, ethylbenzene, and m , p -xylene were less than the dissolution rate coefficient. The calibrated model was used to determine the BTEX mass balance in the oil body and groundwater plume. Dissolution from the oil body was greatest for compounds with large effective solubilities (benzene) and with large degradation rates (toluene and o -xylene). Anaerobic degradation removed 77% of the BTEX that dissolved into the water phase and aerobic degradation removed 17%. Although goodness-of-fit measures for the alternative conceptual models were not significantly different, predictions made with the models were quite variable.

Minnesota↗
USGS2002

Aqueous solubilities, vapor pressures, and 1-octanol-water partition coefficients for C9-C14 linear alkylbenzenes

Measurements and estimates of aqueous solubilities, 1-octanol-water partition coefficients (Kow), and vapor pressures were made for 29 linear alkylbenzenes having alkyl chain lengths of 9-14 carbons. The ranges of values observed were vapor pressures from 0.002 to 0.418 Pa, log Kow, from 6.83 to 9.95, and aqueous solubilities from 4 to 38 nmol??L-1. Measured values exhibited a relationship to both the alkyl chain length and the position of phenyl substitution on the alkyl chain. Measurement of the aqueous concentrations resulting from equilibration of a mixture of alkylbenzenes yielded higher than expected values, indicating cosolute or other interactive effects caused enhanced aqueous concentrations of these compounds. ?? 1992 American Chemical Society.

Journal of Chemical and Engineering Data↗
USGS2001

Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho -xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe 2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.

Journal of Contaminant Hydrology↗
USGS2001

The search for reliable aqueous solubility (Sw) and octanol-water partition coefficient (Kow) data for hydrophobic organic compounds; DDT and DDE as a case study

The accurate determination of an organic contaminant’s physico-chemical properties is essential for predicting its environmental impact and fate. Approximately 700 publications (1944–2001) were reviewed and all known aqueous solubilities (S w ) and octanol-water partition coefficients (K ow ) for the organochlorine pesticide, DDT, and its persistent metabolite, DDE were compiled and examined. Two problems are evident with the available database: 1) egregious errors in reporting data and references, and 2) poor data quality and/or inadequate documentation of procedures. The published literature (particularly the collative literature such as compilation articles and handbooks) is characterized by a preponderance of unnecessary data duplication. Numerous data and citation errors are also present in the literature. The percentage of original S w and K ow data in compilations has decreased with time, and in the most recent publications (1994–97) it composes only 6–26 percent of the reported data. The variability of original DDT/DDE S w and K ow data spans 2–4 orders of magnitude, and there is little indication that the uncertainty in these properties has declined over the last 5 decades. A criteria-based evaluation of DDT/DDE S w and K ow data sources shows that 95–100 percent of the database literature is of poor or unevaluatable quality. The accuracy and reliability of the vast majority of the data are unknown due to inadequate documentation of the methods of determination used by the authors. [For example, estimates of precision have been reported for only 20 percent of experimental S w data and 10 percent of experimental K ow data.] Computational methods for estimating these parameters have been increasingly substituted for direct or indirect experimental determination despite the fact that the data used for model development and validation may be of unknown reliability. Because of the prevalence of errors, the lack of methodological documentation, and unsatisfactory data quality, the reliability of the DDT/ DDE S w and K ow database is questionable. The nature and extent of the errors documented in this study are probably indicative of a more general problem in the literature of hydrophobic organic compounds. Under these circumstances, estimation of critical environmental parameters on the basis of S w and K ow (for example, bioconcentration factors, equilibrium partition coefficients) is inadvisable because it will likely lead to incorrect environmental risk assessments. The current state of the database indicates that much greater efforts are needed to: 1) halt the proliferation of erroneous data and references, 2) initiate a coordinated program to develop improved methods of property determination, 3) establish and maintain consistent reporting requirements for physico-chemical property data, and 4) create a mechanism for archiving reliable data for widespread use in the scientific/regulatory community.

Water-Resources Investigations Report↗
USGS2000

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↗
USGS1996

Processes affecting the fate of monoaromatic hydrocarbons in an aquifer contaminated by crude oil

Crude oil spilled from a subsurface pipeline in north-central Minnesota has dissolved in the groundwater, resulting in the formation of a plume of aliphatic, aromatic, and alicyclic hydrocarbons. Comparison of paired oil and groundwater samples collected along the central axis of the residual oil body shows that the trailing edge of the oil is depleted in the more soluble aromatic hydrocarbons (e.g., benzene, toluene, etc.) when compared with the leading edge. At the same time, concentrations of monoaromatic hydrocarbons in groundwater beneath the oil increase as the water moves toward the leading edge of the oil. Immediately downgradient from the leading edge of the oil body, certain aromatic hydrocarbons (e.g., benzene) are found at concentrations near those expected of a system at equilibrium, and the concentrations exhibit little variation over time (???8-20%). Other compounds (e.g., toluene) appear to be undersaturated, and their concentrations show considerably more temporal variation (???20-130%). The former are persistent within the anoxic zone downgradient from the oil, whereas concentrations of the latter decrease rapidly. Together, these observations suggest that the volatile hydrocarbon composition of the anoxic groundwater near the oil body is controlled by a balance between dissolution and removal rates with only the most persistent compounds reaching saturation. Examination of the distributions of homologous series and isomeric assemblages of alkylbenzenes reveals that microbial degradation is the dominant process controlling the fate of these compounds once groundwater moves away from the oil. For all but the most persistent compounds, the distal boundary of the plume at the water table extends no more than 10-15 m down-gradient from the oxic/anoxic transition zone. Thus, transport of the monoaromatic hydrocarbons is limited by redox conditions that are tightly coupled to biological degradation processes.

Environmental Science & Technology↗
USGS1994

The geochemical evolution of low-molecular-weight organic acids derived from the degradation of petroleum contaminants in groundwater

The geochemical evolution of low-molecular-weight organic acids in groundwater downgradient from a crude-oil spill near Bemidji, Minnesota, was studied over a five year period (1986–1990). The organic acids are metabolic intermediates of the degradation of components of the crude oil and are structurally related to hydrocarbon precursors. The concentrations of organic acids, particularly aliphatic acids, increase as the microbial alteration of hydrocarbons progresses. The organic-acid pool changes in composition and concentration over time and in space as the degradation processes shift from Fe(III) reduction to methanogenesis. Over time, the aquifer system evolves into one in which the groundwater contains more oxidized products of hydrocarbon degradation and the reduced forms of iron, manganese, and nitrogen. Laboratory microcosm experiments with aquifer material support the hypothesis that organic acids observed in the groundwater originate from the microbial degradation of aromatic hydrocarbons under anoxic conditions. The geochemistry of two other shallow aquifers in coastal plain sediments, one contaminated with creosote waste and the other with gasoline, were compared to the Bemidji site. The geochemical evolution of the low-molecular-weight organic acid pool in these systems is controlled, in part, by the presence of electron acceptors available for microbially mediated electron-transfer reactions. The depletion of electron acceptors in aquifers leads to the accumulation of aliphatic organic acids in anoxic groundwater.

Geochimica et Cosmochimica Acta↗
USGS1993

Determination of C6-C10 aromatic hydrocarbons in water by purge-and-trap capillary gas chromatography

A method is described for the determination of the C6-C10 aromatic hydrocarbons in water based on purge-and-trap capillary gas chromatography with flame ionization and mass spectrometric detection. Retention time data and 70 eV mass spectra were obtained for benzene and all 35 C7-C10 aromatic hydrocarbons. With optimized chromatographic conditions and mass spectrometric detection, benzene and 33 of the 35 alkylbenzenes can be identified and measured in a 45-min run. Use of a flame ionization detector permits the simultaneous determination of benzene and 26 alkylbenzenes.

Journal of Chromatography↗
USGS1993

Crude oil in a shallow sand and gravel aquifer-II. Organic geochemistry

Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O 2 concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.

Applied Geochemistry↗
USGS1993

Crude oil in a shallow sand and gravel aquifer-III. Biogeochemical reactions and mass balance modeling in anoxic groundwater

Crude oil floating on the water table in a sand and gravel aquifer provides a constant source of hydrocarbons to the groundwater at a site near Bemidji, Minnesota. The degradation of hydrocarbons affects the concentrations of oxidized and reduced aqueous species in the anoxic part of the contaminant plume that developed downgradient from the oil body. The concentrations of Fe 2+ , Mn 2+ and CH 4 , Eh measurements, and the δ 13 C ratios of the total inorganic C indicate that the plume became more reducing ver a 5-a period. However, the size of the contaminant plume remained stable during this time. Field data coupled with laboratory microcosm experiments indicate that benzene and the alkylbenzenes are degraded in an anoxic environment. In anaerobic microcosm experiments conducted under field conditions, almost complete degradation (98%) was observed for benzene in 125 d and for toluene in 45 d. Concentrations of aqueous Fe 2+ and Mn 2+ increased in these experiments, indicating that the primary reactions were hydrocarbon degradation coupled with Fe and Mn reduction. Mass transfer calculations on a 40-m flowpath in the anoxic zone, downgradient from the oil body, indicated that the primary reactions in the anoxic zone are oxidation of organic compounds, precipitation of siderite and a ferroan calcite, dissolution of iron oxide and outgassing of CH 4 and CO 2 . The major difference in the two models presented is the ratio of CO 2 and CH 4 that outgasses. Both models indicate quantitatively that large amounts of Fe are dissolved and reprecipitated as ferrous iron in the anoxic zone of the contaminant plume.

Minnesota↗
USGS1990

Transformation of Monoaromatic hydrocarbons to organic acids in anoxic groundwater environment

The transformation of benzene and a series of alkylbenzenes was studied in anoxic groundwater of a shallow glacial-outwash aquifer near Bemidji, Minnesota, U.S.A. Monoaromatic hydrocarbons, the most water-soluble components of crude oil, were transported downgradient of an oil spill, forming a plume of contaminated groundwater. Organic acids that were not original components of the oil were identified in the anoxic groundwater. The highest concentrations of these oxidized organic compounds were found in the anoxic plume where a decrease in concentrations of structurally related alkylbenzenes was observed. These results suggest that biological transformation of benzene and alkylbenzenes to organic acid intermediates may be an important attenuation process in anoxic environments. The transformation of a complex mixture of hydrocarbons to a series of corresponding oxidation products in an anoxic subsurface environment provides new insight into in situ anaerobic degradation processes.

Minnesota↗