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I.M. Cozzarelli

Publications and source records attributed to I.M. Cozzarelli.

17 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

Determination of dominant biogeochemical processes in a contaminated aquifer-wetland system using multivariate statistical analysis

Determining the processes governing aqueous biogeochemistry in a wetland hydrologically linked to an underlying contaminated aquifer is challenging due to the complex exchange between the systems and their distinct responses to changes in precipitation, recharge, and biological activities. To evaluate temporal and spatial processes in the wetland-aquifer system, water samples were collected using cm-scale multi-chambered passive diffusion samplers (peepers) to span the wetland-aquifer interface over a period of 3 yr. Samples were analyzed for major cations and anions, methane, and a suite of organic acids resulting in a large dataset of over 8000 points, which was evaluated using multivariate statistics. Principal component analysis (PCA) was chosen with the purpose of exploring the sources of variation in the dataset to expose related variables and provide insight into the biogeochemical processes that control the water chemistry of the system. Factor scores computed from PCA were mapped by date and depth. Patterns observed suggest that (i) fermentation is the process controlling the greatest variability in the dataset and it peaks in May; (ii) iron and sulfate reduction were the dominant terminal electron-accepting processes in the system and were associated with fermentation but had more complex seasonal variability than fermentation; (iii) methanogenesis was also important and associated with bacterial utilization of minerals as a source of electron acceptors (e.g., barite BaSO 4 ); and (iv) seasonal hydrological patterns (wet and dry periods) control the availability of electron acceptors through the reoxidation of reduced iron-sulfur species enhancing iron and sulfate reduction.

Journal of Environmental Quality↗
USGS2006

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for δ 18 O, δ 2 H, non-volatile dissolved organic carbon (NVDOC), SO 4 2− , NO 3 − and Cl − . Monthly recharge amounts were quantified using the offset of the δ 18 O or δ 2 H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO 4 2− in the top 1 to 2 m of the saturated zone was associated with recharge; SO 4 2− averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of δ 2 H and SO 4 2− showed that vertical transport of recharge carried SO 4 2− to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of δ 34 S in SO 4 2− indicated both SO 4 2− reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO 4 2− reduction rates, calculated using the natural Cl − gradient as a conservative tracer, ranged from 7.5 × 10 − 3 to 0.61 mM·d − 1 (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO 4 2− reduction rates were higher at the contaminated site. Although estimated SO 4 2− reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO 4 2− reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO 4 2− reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.

Journal of Contaminant Hydrology↗
USGS2005

A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one‐dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one‐sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth‐rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.

Ground Water↗
USGS2003

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35 S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis−Menten-like relationship with an apparent K m and V max of approximately 80 and 0.83 μM SO 4 - 2 ·day - 1 , respectively. The concentration of sulfate in the core of the leachate plume was well below 20 μM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (∼100 μM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.

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

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 . 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

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↗
USGS1999

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.

Applied Geochemistry↗
USGS1998

Ground water contamination by crude oil near Bemidji, Minnesota

Ground-water contamination by crude oil, and other petroleum-based liquids, is a widespread problem. An average of 83 crude-oil spills occurred per year during 1994-96 in the United States, each spilling about 50,000 barrels of crude oil (U.S. Office of Pipeline Safety, electronic commun., 1997). An understanding of the fate of organic contaminants (such as oil and gasoline) in the subsurface is needed to design innovative and cost-effective remedial solutions at contaminated sites.

Minnesota↗
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

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↗
USGS1989

Oxidation of aromatic contaminants coupled to microbial iron reduction

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically.

Nature↗