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Isabelle M. Cozzarelli

Publications and source records attributed to Isabelle M. Cozzarelli.

At least 91 records · Page 5Linked to original sources
USGS2010

Simulation of aerobic and anaerobic biodegradation processes at a crude oil spill site

A two-dimensional, multispecies reactive solute transport model with sequential aerobic and anaerobic degradation processes was developed and tested. The model was used to study the field-scale solute transport and degradation processes at the Bemidji, Minnesota, crude oil spill site. The simulations included the biodegradation of volatile and nonvolatile fractions of dissolved organic carbon by aerobic processes, manganese and iron reduction, and methanogenesis. Model parameter estimates were constrained by published Monod kinetic parameters, theoretical yield estimates, and field biomass measurements. Despite the considerable uncertainty in the model parameter estimates, results of simulations reproduced the general features of the observed groundwater plume and the measured bacterial concentrations. In the simulation, 46% of the total dissolved organic carbon (TDOC) introduced into the aquifer was degraded. Aerobic degradation accounted for 40% of the TDOC degraded. Anaerobic processes accounted for the remaining 60% of degradation of TDOC: 5% by Mn reduction, 19% by Fe reduction, and 36% by methanogenesis. Thus anaerobic processes account for more than half of the removal of DOC at this site.

Water Resources Research↗
USGS2010

The mobilization of aluminum in a natural soil system: Effects of hydrologic pathways

A two-component soil water flow model was used in conjunction with an equilibrium speciation model WATEQF to study aluminum mobility in soils of a forested watershed, White Oak Run, in the Shenandoah National Park, Virginia. Soil solution samples, taken from the O, E, B, C 1 , and C 2 horizons, were collected from zero-tension lysimeters designed to collect faster gravitational macropore flow and tension lysimeters designed to collect slower capillary micropore flow. Dissolved aluminum was fractionated into acid-soluble, inorganic monomeric, and organic monomeric aluminum. Soil water aluminum concentrations decreased with depth indicating that the deep soil is a sink for aluminum. All waters contained significant concentrations of acid-soluble aluminum and exhibited a negative correlation between p H and the inorganic monomeric aluminum concentrations. Water in the shallow soil showed distinctly different chemical compositions for the two flow types, while C horizon micropore and macropore waters were more similar. Because of its shorter residence time, water flowing in deep soil macropores underwent less extensive neutralization and immobilization of aqueous aluminum than micropore water. The O horizon macropore waters were undersaturated for all hydroxide, silicate, and sulfate mineral phases considered. The C horizon samples from both flow types were near equilibrium with respect to kaolinite and synthetic gibbsite, indicating that mineral solubility controls water chemistry in the deep soil, while organic substances are the key control in the shallow macropore waters.

Water Resources Research↗
USGS2010

Fate and transport of petroleum hydrocarbons in the subsurface near Cass Lake, Minnesota

The U.S. Geological Survey (USGS) investigated the natural attenuation of subsurface petroleum hydrocarbons leaked over an unknown number of years from an oil pipeline under the Enbridge Energy Limited Partnership South Cass Lake Pumping Station, in Cass Lake, Minnesota. Three weeks of field work conducted between May 2007 and July 2008 delineated a dissolved plume of aromatic hydrocarbons and characterized the biodegradation processes of the petroleum. Field activities included installing monitoring wells, collecting sediment cores, sampling water from wells, and measuring water-table elevations. Geochemical measurements included concentrations of constituents in both spilled and pipeline oil, dissolved alkylbenzenes and redox constituents, sediment bioavailable iron, and aquifer microbial populations. Groundwater in this area flows east-southeast at approximately 26 meters per year. Results from the oil analyses indicate a high degree of biodegradation, characterized by nearly complete absence of n-alkanes. Cass Lake oil samples were more degraded than two oil samples collected in 2008 from the similarly contaminated USGS Bemidji, Minnesota, research site 40 kilometers away. Based on 19 ratios developed for comparing oil sources, the conclusion is that the oils at the two sites appear to be from the same hydrocarbon source. In the Cass Lake groundwater plume, benzene concentrations decrease by three orders of magnitude within 150 meters (m) downgradient from the oil body floating on the water table (between well MW-10 and USGS-4 well nest). The depths of the highest benzene concentrations increase with distance downgradient from the oil, a condition typical of plumes in shallow, unconfined aquifers. Background groundwater, which is nearly saturated with oxygen, becomes almost entirely anaerobic in the plume. As at the Bemidji site, the most important biodegradation processes are anaerobic and dominated by iron reduction. The similarity between the Cass Lake and Bemidji benzene degradation rates, redox conditions, and aquifer material all support a hypothesis that the Cass Lake plume, like the Bemidji plume, is decades old. As concentrations of alkylbenzenes in the oil decrease over time, the benzene concentrations in the groundwater plume will also decrease and the plume is expected to shrink. The Fox Creek wetland, about 250 m south of the Cass Lake site, is the nearest receptor to the south.

Scientific Investigations Report↗
USGS2009

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The δ 34 S and δ 18 O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ 34 S SO4 and δ 18 O SO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO 4 concentrations) and isotopic composition (δ 2 H H2O and δ 18 O H2O ) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ 34 S SO4 and δ 18 O SO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ 34 S SO4 = 8–12‰ and δ 18 O SO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ 34 S SO4 = − 16‰ and δ 18 O SO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ 34 S SO4 = 8‰ and δ 18 O SO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ 34 S SO4 and δ 18 O SO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by ε H2S–SO4 = − 23‰) results in the steady increase of δ 34 S SO4 values to greater than 70‰. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ 18 O SO4 values asymptotically approaching 21‰, the value predicted for conditions at the study site ( ε SO4–H2O = 27‰). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ 34 S SO4 and δ 18 O SO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Oklahoma↗
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

Biodegradation in contaminated aquifers: Incorporating microbial/molecular methods

In order to evaluate natural attenuation in contaminated aquifers, there has been a recent recognition that a multidisciplinary approach, incorporating microbial and molecular methods, is required. Observed decreases in contaminant mass and identified footprints of biogeochemical reactions are often used as evidence of intrinsic bioremediation, but characterizing the structure and function of the microbial populations at contaminated sites is needed. In this paper, we review the experimental approaches and microbial methods that are available as tools to evaluate the controls on microbially mediated degradation processes in contaminated aquifers. We discuss the emerging technologies used in biogeochemical studies and present a synthesis of recent studies that serve as models of integrating microbiological approaches with more traditional geochemical and hydrogeologic approaches in order to address important biogeochemical questions about contaminant fate.

Groundwater↗
USGS2008

Results of the chemical and isotopic analyses of sediment and ground water from alluvium of the Canadian River near a closed municipal landfill, Norman, Oklahoma, part 2

Analytical results on sediment and associated ground water from the Canadian River alluvium collected subsequent to those described in Breit and others (2005) are presented in this report. The data presented herein were collected primarily to evaluate the iron and sulfur species within the sediment at well sites IC 36, IC 54, and IC South located at the USGS Norman Landfill study site. Cored sediment and water samples were collected during October 2004 and April 2005. The 52 sediment samples collected by coring were analyzed to determine grain size, the abundance of extractable iron species, and the abundance of sulfur forms and their isotopic compositions. Ground water was collected from cluster wells that sampled ground water from 11 to 15 screened intervals at each of the three sites. The depth range of the wells overlapped the interval of cored sediment. Concentrations of major ions, dissolved organic carbon (DOC), ammonium, and iron are reported with pH, specific conductance, and the isotopic composition of the water for the 75 water samples analyzed. Dissolved sulfate in selected water samples was analyzed to determine its sulfur and oxygen isotope composition.

Oklahoma↗
USGS2007

Biogeochemistry of aquifer systems

Many studies have examined the differences in bacterial numbers, composition, and activity between groundwater and sediment samples. The majority of the literature has suggested higher percentages of attached bacteria than of unattached bacteria in aquifer systems, including in pristine aquifers and in aquifers contaminated with petroleum, creosote, sewage, and landfill leachate. In studies of aquifer biogeochemistry, much useful information regarding the microbial ecology of the system can be obtained by looking at organic compound and electron acceptor concentrations. An overview of approaches for identifying the redox characteristics of sediment is given in Christensen et al., and methods specific for determining reactive iron species in aquifers are reviewed by Heron et al. and Tuccillo et al. Other solid-phase electron acceptors that are important in aquifer systems include Mn(IV) oxides and barite. Important biogeochemical reactions catalyzed by indigenous microorganisms also are studied using a variety of experimental approaches including laboratory batch and column experiments as well as field-based in situ microcosms, tracer tests, and push-pull tests. The advantage of using a radiolabeled tracer in a study was that the reaction rates could be determined for the different steps in the denitrification pathway. Historically, researchers trained in geochemistry and hydrology created and tested hypotheses about aquifer biogeochemistry through laboratory assays and field-based geo-chemical measurements and experiments. Jeon et al. extended this research by using push-pull tests combined with stable-isotope probing to identify the specific members of the microbial community actively degrading naphthalene and rates of naphthalene degradation.

Book chapter↗
USGS2007

Centimeter-scale characterization of biogeochemical gradients at a wetland-aquifer interface using capillary electrophoresis

Steep biogeochemical gradients were measured at mixing interfaces in a wetland-aquifer system impacted by landfill leachate in Norman, Oklahoma. The system lies within a reworked alluvial plain and is characterized by layered low hydraulic conductivity wetland sediments interbedded with sandy aquifer material. Using cm-scale passive diffusion samplers, "peepers", water samples were collected in a depth profile to span interfaces between surface water and a sequence of deeper sedimentary layers. Geochemical indicators including electron acceptors, low-molecular-weight organic acids, base cations, and NH4+ were analyzed by capillary electrophoresis (CE) and field techniques to maximize the small sample volumes available from the centimeter-scale peepers. Steep concentration gradients of biogeochemical indicators were observed at various interfaces including those created at sedimentary boundaries and boundaries created by heterogeneities in organic C and available electron acceptors. At the sediment-water interface, chemical profiles with depth suggest that SO42 - and Fe reduction dominate driven by inputs of organic C from the wetland and availability of electron acceptors. Deeper in the sediments (not associated with a lithologic boundary), a steep gradient of organic acids (acetate maximum 8.8 mM) and NH4+ (maximum 36 mM) is observed due to a localized source of organic matter coupled with the lack of electron acceptor inputs. These findings highlight the importance of quantifying the redox reactions occurring in small interface zones and assessing their role on biogeochemical cycling at the system scale.

Oklahoma↗
USGS2007

Evaluation of sulfate reduction at experimentally induced mixing interfaces using small-scale push-pull tests in an aquifer-wetland system

This paper presents small-scale push–pull tests designed to evaluate the kinetic controls on SO 4 2 - "> SO42- reduction in situ at mixing interfaces between a wetland and aquifer impacted by landfill leachate at the Norman Landfill research site, Norman, OK. Quantifying the rates of redox reactions initiated at interfaces is of great interest because interfaces have been shown to be zones of increased biogeochemical transformations and thus may play an important role in natural attenuation. To mimic the aquifer–wetland interface and evaluate reaction rates, SO 4 2 - "> SO42- -rich anaerobic aquifer water ( ∼ 100 mg / L SO 4 2 - ) "> (∼100mg/LSO42-) was introduced into SO 4 2 - "> SO42- -depleted wetland porewater via push–pull tests. Results showed SO 4 2 - "> SO42- reduction was stimulated by the mixing of these waters and first-order rate coefficients were comparable to those measured in other push–pull studies. However, rate data were complex involving either multiple first-order rate coefficients or a more complex rate order. In addition, a lag phase was observed prior to SO 4 2 - "> SO42- reduction that persisted until the mixing interface between test solution and native water was recovered, irrespective of temporal and spatial constraints. The lag phase was not eliminated by the addition of electron donor (acetate) to the injected test solution. Subsequent push–pull tests designed to elucidate the nature of the lag phase support the importance of the mixing interface in controlling terminal electron accepting processes. These data suggest redox reactions may occur rapidly at the mixing interface between injected and native waters but not in the injected bulk water mass. Under these circumstances, push–pull test data should be evaluated to ensure the apparent rate is actually a function of time and that complexities in rate data be considered.

Oklahoma↗
USGS2005

Natural attenuation of volatile organic compounds (VOCs) in the leachate plume of a municipal landfill: Using alkylbenzenes as process probes

More than 70 individual VOCs were identified in the leachate plume of a closed municipal landfill. Concentrations were low when compared with data published for other landfills, and total VOCs accounted for less than 0.1% of the total dissolved organic carbon. The VOC concentrations in the core of the anoxic leachate plume are variable, but in all cases they were found to be near or below detection limits within 200 m of the landfall. In contrast to the VOCs, the distributions of chloride ion, a conservative tracer, and nonvolatile dissolved organic carbon, indicate little dilution over the same distance. Thus, natural attentuation processes are effectively limiting migration of the VOC plume. The distribution of C2-3-benzenes, paired on the basis of their octanol-water partition coefficients and Henry's law constants, were systematically evaluated to assess the relative importance of volatilization, sorption, and biodegradation as attenuation mechanisms. Based on our data, biodegradation appears to be the process primarily responsible for the observed attenuation of VOCs at this site. We believe that the alkylbenzenes are powerful process probes that can and should be exploited in studies of natural attenuation in contaminated ground water systems.

Groundwater↗
USGS2005

Results of chemical and isotopic analyses of sediment and water from alluvium of the Canadian River near a closed municipal landfill, Norman, Oklahoma

Results of physical and chemical analyses of sediment and water collected near a closed municipal landfill at Norman, Oklahoma are presented in this report. Sediment analyses are from 40 samples obtained by freeze-shoe coring at 5 sites, and 14 shallow (depth <1.3 m) sediment samples. The sediment was analyzed to determine grain size, the abundance of extractable iron species and the abundances and isotopic compositions of forms of sulfur. Water samples included pore water from the freeze-shoe core, ground water, and surface water. Pore water from 23 intervals of the core was collected and analyzed for major and trace dissolved species. Thirteen ground-water samples obtained from wells within a few meters of the freeze-shoe core sites and one from the landfill were analyzed for major and trace elements as well as the sulfur and oxygen isotope composition of dissolved sulfate. Samples of surface water were collected at 10 sites along the Canadian River from New Mexico to central Oklahoma. These river-water samples were analyzed for major elements, trace elements, and the isotopic composition of dissolved sulfate.

Oklahoma↗
USGS2002

Anaerobic methane oxidation in a landfill-leachate plume

The alluvial aquifer adjacent to Norman Landfill, OK, provides an excellent natural laboratory for the study of anaerobic processes impacting landfill-leachate contaminated aquifers. We collected groundwaters from a transect of seven multilevel wells ranging in depth from 1.3 to 11 m that were oriented parallel to the flow path. The center of the leachate plume was characterized by (1) high alkalinity and elevated concentrations of total dissolved organic carbon, reduced iron, and methane, and (2) negligible oxygen, nitrate, and sulfate concentrations. Methane concentrations and stable carbon isotope (δ 13 C) values suggest anaerobic methane oxidation was occurring within the plume and at its margins. Methane δ 13 C values increased from about −54‰ near the source to >−10‰ downgradient and at the plume margins. The isotopic fractionation associated with this methane oxidation was −13.6 ± 1.0‰. Methane 13 C enrichment indicated that 80−90% of the original landfill methane was oxidized over the 210-m transect. First-order rate constants ranged from 0.06 to 0.23 per year, and oxidation rates ranged from 18 to 230 μM/y. Overall, hydrochemical data suggest that a sulfate reducer-methanogen consortium may mediate this methane oxidation. These results demonstrate that natural attenuation through anaerobic methane oxidation can be an important sink for landfill methane in aquifer systems.

Environmental Science & Technology↗