Geology topics

E. Warren

Publications and source records attributed to E. Warren.

10 recordsLinked to original sources

USGS2010

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C3- and C4-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.

Journal of Contaminant Hydrology↗

USGS2005

A comparison of zero-order, first-order, and monod biotransformation models

Under some conditions, a first-order kinetic model is a poor representation of biodegradation in contaminated aquifers. Although it is well known that the assumption of first-order kinetics is valid only when substrate concentration, S, is much less than the half-saturation constant, K(s), this assumption is often made without verification of this condition. We present a formal error analysis showing that the relative error in the first-order approximation is S/K(S) and in the zero-order approximation the error is K(s)/S. We then examine the problems that arise when the first-order approximation is used outside the range for which it is valid. A series of numerical simulations comparing results of first- and zero-order rate approximations to Monod kinetics for a real data set illustrates that if concentrations observed in the field are higher than K(s), it may better to model degradation using a zero-order rate expression. Compared with Monod kinetics, extrapolation of a first-order rate to lower concentrations under-predicts the biotransformation potential, while extrapolation to higher concentrations may grossly over-predict the transformation rate. A summary of solubilities and Monod parameters for aerobic benzene, toluene, and xylene (BTX) degradation shows that the a priori assumption of first-order degradation kinetics at sites contaminated with these compounds is not valid. In particular, out of six published values of KS for toluene, only one is greater than 2 mg/L, indicating that when toluene is present in concentrations greater than about a part per million, the assumption of first-order kinetics may be invalid. Finally, we apply an existing analytical solution for steady-state one-dimensional advective transport with Monod degradation kinetics to a field data set.A formal error analysis is presented showing that the relative error in the first-order approximation is S/KS and in the zero-order approximation the error is KS/S where S is the substrate concentration and KS is the half-saturation constant. The problems that arise when the first-order approximation is used outside the range for which it is valid are examined. A series of numerical simulations comparing results of first- and zero-order rate approximations to Monod kinetics for a real data set illustrates that if concentrations observed in the field are higher than KS, it may be better to model degradation using a zero-order rate expression.

Ground Water↗

USGS2005

Progression of methanogenic degradation of crude oil in the subsurface

Our results show that subsurface crude-oil degradation rates at a long-term research site were strongly influenced by small-scale variations in hydrologic conditions. The site is a shallow glacial outwash aquifer located near Bemidji in northern Minnesota that became contaminated when oil spilled from a broken pipeline in August 1979. In the study area, separate-phase oil forms a subsurface oil body extending from land surface to about 1 m (3.3 ft) below the 6–8-m (20–26 ft)-deep water table. Oil saturation in the sediments ranges from 10–20% in the vadose zone to 30–70% near the water table. At depths below 2 m (6.6 ft), degradation of the separate-phase crude oil occurs under methanogenic conditions. The sequence of methanogenic alkane degradation depletes the longer chain n-alkanes before the shorter chain n-alkanes, which is opposite to the better known aerobic sequence. The rates of degradation vary significantly with location in the subsurface. Oil-coated soils within 1.5 m (5 ft) of land surface have experienced little degradation where soil water saturation is less than 20%. Oil located 2–8 m (6.6–26 ft) below land surface in areas of higher recharge has been substantially degraded. The best explanation for the association between recharge and enhanced degradation seems to be increased downward transport of microbial growth nutrients to the oil body. This is supported by observations of greater microbial numbers at higher elevations in the oil body and significant decreases with depth in nutrient concentrations, especially phosphorus. Our results suggest that environmental effects may cause widely diverging degradation rates in the same spill, calling into question dating methods based on degradation state.

Environmental Geosciences↗

USGS2003

The role of microbial reductive dechlorination of TCE at a phytoremediation site

In April 1996, a phytoremediation field demonstration site at the Naval Air Station, Fort Worth, Texas, was developed to remediate shallow oxic ground water (<3.7 m deep) contaminated with chlorinated ethenes. Microbial populations were sampled in February and June 1998. The populations under the newly planted cottonwood trees had not yet matured to an anaerobic community that could dechlorinate trichloroethene (TCE) to cis -1,2-dichloroethene (DCE); however, the microbial population under a mature (∼22-year-old) cottonwood tree about 30 m southwest of the plantings had a mature anaerobic population capable of dechlorinating TCE to DCE, and DCE to vinyl chloride (VC). Oxygen-free sediment incubations with contaminated groundwater also demonstrated that resident microorganisms were capable of the dechlorination of TCE to DCE. This suggests that a sufficient amount of organic material is present for microbial dechlorination in aquifer microniches where dissolved O 2 concentrations are low. Phenol, benzoic acid, acetic acid, and a cyclic hydrocarbon, compounds consistent with the degradation of root exudates and complex aromatic compounds, were identified by gas chromatography/mass spectrometry (GC/MS) in sediment samples under the mature cottonwood tree. Elsewhere at the site, transpiration and degradation by the cottonwood trees appears to be responsible for loss of chlorinated ethenes.

Texas↗

USGS2003

Inhibition of acetoclastic methanogenesis in crude oil- and creosote-contaminated groundwater

The inhibition of acetoclastic methanogenesis in crude oil- and creosote-contaminated groundwater was studied. The crude oil and water-soluble components of creosote contributed to the inhibition of acetoclastic methanogens. Acetoclastic methanogenesis was much more susceptible to the toxic inhibition of crude oil and creosote than either hydrogen- or formate-utilizing methanogenesis. The effect of this toxic inhibition was apparent in the population of the methanogenic trophic groups near nonaqueous crude oil at the Bemidji, MN, site. At a crude oil-contaminated site, numbers of acetoclastic methanogens found close to crude oil were 100 times fewer than those of hydrogen- and formate-utilizing methanogens. In laboratory toxicity assays, crude oil collected from the site inhibited methane production from acetate but not from formate or hydrogen. Toxicity assays with aqueous creosote extract completely inhibited acetate utilization over the range of tested dilutions but only mildly affected formate and hydrogen utilization. Wastewater reactor studies indicated that this toxicity would result in a decrease in the biodegradation rate of contaminants at sites where toxic compounds are present.

Florida, Minnesota↗

USGS2002

Microbial ecology of a crude oil contaminated aquifer

Detailed microbial analyses of a glacial outwash aquifer contaminated by crude oil provide insights into the pattern of microbial succession from iron reducing to methanogenic in the anaerobic portion of the contaminant plume. We analysed sediments from this area for populations of aerobes, iron reducers, fermenters and methanogens, using the most probable number method. On the basis of the microbial data the anaerobic area can be divided into distinct physiological zones dominated by either iron-reducers or a consortium of fermenters and methanogens. Chemistry and permeability data show that methanogenic conditions develop first in areas of high hydrocarbon flux. Thus, we find methanogens both in high permeability horizons and also where separate-phase crude oil is present in either the saturated or unsaturated zone. Microbial numbers peak at the top of the separate-phase oil suggesting that growth is most rapid in locations with access to both hydrocarbons and nutrients infiltrating from the surface.

IAHS-AISH Publication↗

USGS2001

Progression of natural attenuation processes at a crude oil spill site: II. Controls on spatial distribution of microbial populations

A multidisciplinary study of a crude-oil contaminated aquifer shows that the distribution of microbial physiologic types is strongly controlled by the aquifer properties and crude oil location. The microbial populations of four physiologic types were analyzed together with permeability, pore-water chemistry, nonaqueous oil content, and extractable sediment iron. Microbial data from three vertical profiles through the anaerobic portion of the contaminated aquifer clearly show areas that have progressed from iron-reduction to methanogenesis. These locations contain lower numbers of iron reducers, and increased numbers of fermenters with detectable methanogens. Methanogenic conditions exist both in the area contaminated by nonaqueous oil and also below the oil where high hydrocarbon concentrations correspond to local increases in aquifer permeability. The results indicate that high contaminant flux either from local dissolution or by advective transport plays a key role in determining which areas first become methanogenic. Other factors besides flux that are important include the sediment Fe(II) content and proximity to the water table. In locations near a seasonally oscillating water table, methanogenic conditions exist only below the lowest typical water table elevation. During 20 years since the oil spill occurred, a laterally continuous methanogenic zone has developed along a narrow horizon extending from the source area to 50–60 m downgradient. A companion paper [J. Contam. Hydrol. 53, 369–386] documents how the growth of the methanogenic zone results in expansion of the aquifer volume contaminated with the highest concentrations of benzene, toluene, ethylbenzene, and xylenes.

Journal of Contaminant Hydrology↗

USGS2001

Compound-specific carbon isotope analysis of a contaminant plume in Kingsford, Michigan, USA

Compound-specific isotope analysis was used to study a contaminated site near Kingsford, Michigan, USA. Organic compounds at three of the sites studied had similar 13C values indicating that the contaminant source is the same for all sites. At a fourth site, chemical and 13C values had evolved due to microbial degradation of organics, with the 13C being much heavier than the starting materials. A microcosm experiment was run to observe isotopic changes with time in the methane evolved and in compounds remaining in the water during degradation. The 13C values of the methane became heavier during the initial period of the run when volatile fatty acids were being consumed. There was an abrupt decrease in the 13C values when fatty acids had been consumed and phenols began to be utilized. The 13C value of the propionate remaining in solution also increased, similar to the results found in the field.

Michigan↗

USGS2001

Methanogenic biodegradation of charcoal production wastes in groundwater at Kingsford, Michigan, USA

A house exploded in the City of Kingsford, Michigan USA. The explosion was caused by CH4 that leaked into the basement from the surrounding soil. Evidence suggests that biodegradation of products from the distillation and spillage at or near a former wood carbonization plant site was the major source of CH4 and CO2 in the groundwater system. The plant area is directly upgradient from deep groundwater, samples of which are green-yellow in colour, have a very strong odour of burnt wood, contain high concentrations of mononuclear aromatic and phenolic compounds, and extremely high concentrations of volatile fatty acids. The majority of the dissolved compounds in these groundwater samples have been shown, using laboratory microcosms, to be anaerobically biodegradable to CH4 and CO2. The biodegradable compounds, and the amounts of CH4 and CO2 produced in the microcosms, are consistent with observations from field samples.

Michigan↗

USGS1999

Distribution of microbial physiologic types in an aquifer contaminated by crude oil

We conducted a plume-scale study of the microbial ecology in the anaerobic portion of an aquifer contaminated by crude-oil compounds. The data provide insight into the patterns of ecological succession, microbial nutrient demands, and the relative importance of free-living versus attached microbial populations. The most probable number (MPN) method was used to characterize the spatial distribution of six physiologic types: aerobes, denitrifiers, iron-reducers, heterotrophic fermenters, sulfate-reducers, and methanogens. Both free-living and attached numbers were determined over a broad cross-section of the aquifer extending horizontally from the source of the plume at a nonaqueous oil body to 66 m downgradient, and vertically from above the water table to the base of the plume below the water table. Point samples from widely spaced locations were combined with three closely spaced vertical profiles to create a map of physiologic zones for a cross-section of the plume. Although some estimates suggest that less than 1% of the subsurface microbial population can be grown in laboratory cultures, the MPN results presented here provide a comprehensive qualitative picture of the microbial ecology at the plume scale. Areas in the plume that are evolving from iron-reducing to methanogenic conditions are clearly delineated and generally occupy 25-50% of the plume thickness. Lower microbial numbers below the water table compared to the unsaturated zone suggest that nutrient limitations may be important in limiting growth in the saturated zone. Finally, the data indicate that an average of 15% of the total population is suspended.

Microbial Ecology↗