USGS ScienceSearch

Geology topics

William N. Herkelrath

Publications and source records attributed to William N. Herkelrath.

13 recordsLinked to original sources

Effects of a crude-oil recovery remediation system operated 1999–2003 on groundwater plumes and unsaturated-zone vapor concentrations at a crude-oil spill site near Bemidji, Minnesota

A crude-oil spill occurred in 1979 when a pipeline burst near Bemidji, Minnesota. More than 70 percent of the 1.7 million liters of spilled crude oil was removed shortly thereafter. In response to a requirement by the State regulatory agency to remove the remaining crude to a sheen in all wells, in 1998, the pipeline company installed a dual-pump recovery system at the site. This additional remediation from 1999 to 2003 resulted in removal of about 115,000 liters of crude oil, representing between 36 and 41 percent of the volume of oil (281,000–317,000 liters) estimated to be present in 1998. Effects of the 1999–2003 remediation on groundwater plumes and unsaturated-zone vapor concentrations were evaluated by the U.S. Geological Survey using several methods including measurements of oil thicknesses in wells; field water-quality properties of dissolved oxygen, specific conductance, temperature, and pH in groundwater; and vapor concentrations of methane, carbon dioxide, nitrogen, and oxygen in the unsaturated zone. Although the recovery system decreased oil thicknesses near the remediation wells, average oil thicknesses measured in all wells at the site were not reduced substantially. Dissolved oxygen and specific conductance measurements indicate that a secondary plume was created during the remediation, caused by the disposal of pumped water from the remediation wells in an upgradient infiltration gallery. This plume expanded rapidly immediately after the start of the remediation in 1999, resulting in expansion of the anoxic zone of groundwater upgradient and beneath the existing natural attenuation plume. Beginning in 2000–1, for example, specific conductance concentrations noticeably increased in many wells at the north oil pool from about 400 to more than 700 microsiemens per centimeter. The rapid expansion of the anoxic and elevated specific conductance plume indicates that the remediation contributed substantial amounts of biodegradable dissolved organic carbon to groundwater through the infiltration gallery. The trends in vapor data collected before, during, and after the remediation generally support the research hypothesis that crude-oil removal would have an insignificant effect on vapor concentrations in the unsaturated zone. Although there were some small changes in the concentration of methane, carbon dioxide, nitrogen, and oxygen in the unsaturated zone, these changes were not coincident with the beginning or cessation of the remediation and are therefore thought to be the result of other factors affecting biodegradation rates. A decrease in methane concentrations in one representative well, for example, is thought to be the result of reduced rates of biodegradation and methane production from the increasingly more weathered crude oil. Oil-phase recovery at this site was determined to be challenging and resulted in considerable volumes of mobile and entrapped oil remaining in the subsurface despite remediation efforts.

Minnesota

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 2+ , Fe 2+ , CH 4 , and Ca 2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H + . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Minnesota

Effects of a dual-pump crude-oil recovery system, Bemidji, Minnesota, USA

A crude-oil spill occurred in 1979 when a pipeline burst near Bemidji, MN. In 1998, the pipeline company installed a dual-pump recovery system designed to remove crude oil remaining in the subsurface at the site. The remediation from 1999 to 2003 resulted in removal of about 115,000 L of crude oil, representing between 36% and 41% of the volume of oil (280,000 to 316,000 L) estimated to be present in 1998. Effects of the 1999 to 2003 remediation on the dissolved plume were evaluated using measurements of oil thicknesses in wells plus measurements of dissolved oxygen in groundwater. Although the recovery system decreased oil thicknesses in the immediate vicinity of the remediation wells, average oil thicknesses measured in wells were largely unaffected. Dissolved-oxygen measurements indicate that a secondary plume was caused by disposal of the pumped water in an upgradient infiltration gallery; this plume expanded rapidly immediately following the start of the remediation in 1999. The result was expansion of the anoxic zone of groundwater upgradient and beneath the existing natural attenuation plume. Oil-phase recovery at this site was shown to be challenging, and considerable volumes of mobile and entrapped oil remain in the subsurface despite remediation efforts.

Minnesota

Geochemical modeling of changes in shallow groundwater chemistry observed during the MSU-ZERT CO2 injection experiment

A field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer was conducted near Bozeman, Montana, during the summer of 2008, to investigate the potential groundwater quality impacts in the case of leakage of CO 2 from deep geological storage. As an essential part of the Montana State University Zero Emission Research and Technology (MSU-ZERT) field program, food-grade CO 2 was injected over a 30 day period into a horizontal perforated pipe a few feet below the water table of a shallow aquifer. The impact of elevated CO 2 concentrations on groundwater quality was investigated by analyzing water samples taken before, during, and following CO 2 injection, from observation wells located in the vicinity of the injection pipe, and from two distant monitoring wells. Field measurements and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of naturally occurring major and trace element species. The geochemical data were evaluated using principal component analysis (PCA) to (1) understand potential correlations between aqueous species, and (2) to identify minerals controlling the chemical composition of the groundwater prior to CO 2 injection. These evaluations were used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents, and to simulate these processes using a multicomponent reaction path model. Reasonable agreement between observed and modeled data suggests that (1) calcite dissolution was the primary pH buffer, yielding increased Ca +2 concentrations in the groundwater, (2) increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions, (3) the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions, and (4) the dissolution of reactive Fe minerals (presumed ferrihydrite and fougerite, from thermodynamic analyses) could explain increases in total Fe concentration. Highlights ► Because the possibility of CO 2 leakage cannot be completely ruled out, the potential impact of CO 2 intrusion on the quality of fresh water aquifers overlying CO 2 storage sites needs to be investigated. ► Geochemical data from a field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer were evaluated. ► Geochemical model used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents. ► Reasonable agreement between observed and modeled data suggests that increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions and the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions.

Montana

Long-term natural attenuation of crude oil in the subsurface

The time frame for natural attenuation of crude oil contamination in the subsurface has been studied for the last 27 years at a spill site located near Bemidji, Minnesota, USA. Data from the groundwater contaminant plume show that dissolved benzene concentrations adjacent to the oil decreased by 50% between 1993 and 2007. To assess how this decrease is related to benzene concentrations in the crude oil, samples of oil were bailed from floating oil in five wells and analysed for volatile components. Compared to reference oil collected from the pipeline in 1984, benzene concentrations in the well located farthest downgradient in the oil have decreased an average of 50%. Benzene and ethylbenzene depletion are linearly correlated with oil saturation in the pore space suggesting that dissolution is the primary removal mechanism and biodegradation within the oil body is insignificant.

Conference Paper

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

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO 2 was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO 2 . As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO 2 injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO 2 injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO 2 leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO 2 intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO 3 ), and electrical conductance (600–1,800 μS/cm) following CO 2 injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO 2 injection. These chemical changes could provide early detection of CO 2 leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO 2 injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO 2 injection. CO 2 injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.

Montana

Crude oil at the Bemidji Site: 25 years of monitoring, modeling, and understanding

The fate of hydrocarbons in the subsurface near Bemidji, Minnesota, has been investigated by a multidisciplinary group of scientists for over a quarter century. Research at Bemidji has involved extensive investigations of multiphase flow and transport, volatilization, dissolution, geochemical interactions, microbial populations, and biodegradation with the goal of providing an improved understanding of the natural processes limiting the extent of hydrocarbon contamination. A considerable volume of oil remains in the subsurface today despite 30 years of natural attenuation and 5 years of pump‐and‐skim remediation. Studies at Bemidji were among the first to document the importance of anaerobic biodegradation processes for hydrocarbon removal and remediation by natural attenuation. Spatial variability of hydraulic properties was observed to influence subsurface oil and water flow, vapor diffusion, and the progression of biodegradation. Pore‐scale capillary pressure‐saturation hysteresis and the presence of fine‐grained sediments impeded oil flow, causing entrapment and relatively large residual oil saturations. Hydrocarbon attenuation and plume extent was a function of groundwater flow, compound‐specific volatilization, dissolution and biodegradation rates, and availability of electron acceptors. Simulation of hydrocarbon fate and transport affirmed concepts developed from field observations, and provided estimates of field‐scale reaction rates and hydrocarbon mass balance. Long‐term field studies at Bemidji have illustrated that the fate of hydrocarbons evolves with time, and a snap‐shot study of a hydrocarbon plume may not provide information that is of relevance to the long‐term behavior of the plume during natural attenuation.

Minnesota

Development of a probabilistic assessment methodology for evaluation of carbon dioxide storage

This report describes a probabilistic assessment methodology developed by the U.S. Geological Survey (USGS) for evaluation of the resource potential for storage of carbon dioxide (CO 2 ) in the subsurface of the United States as authorized by the Energy Independence and Security Act (Public Law 110-140, 2007). The methodology is based on USGS assessment methodologies for oil and gas resources created and refined over the last 30 years. The resource that is evaluated is the volume of pore space in the subsurface in the depth range of 3,000 to 13,000 feet that can be described within a geologically defined storage assessment unit consisting of a storage formation and an enclosing seal formation. Storage assessment units are divided into physical traps (PTs), which in most cases are oil and gas reservoirs, and the surrounding saline formation (SF), which encompasses the remainder of the storage formation. The storage resource is determined separately for these two types of storage. Monte Carlo simulation methods are used to calculate a distribution of the potential storage size for individual PTs and the SF. To estimate the aggregate storage resource of all PTs, a second Monte Carlo simulation step is used to sample the size and number of PTs. The probability of successful storage for individual PTs or the entire SF, defined in this methodology by the likelihood that the amount of CO 2 stored will be greater than a prescribed minimum, is based on an estimate of the probability of containment using present-day geologic knowledge. The report concludes with a brief discussion of needed research data that could be used to refine assessment methodologies for CO 2 sequestration.

Open-File Report

Physically based estimation of soil water retention from textural data: General framework, new models, and streamlined existing models

Numerous models are in widespread use for the estimation of soil water retention from more easily measured textural data. Improved models are needed for better prediction and wider applicability. We developed a basic framework from which new and existing models can be derived to facilitate improvements. Starting from the assumption that every particle has a characteristic dimension R associated uniquely with a matric pressure ψ and that the form of the ψ– R relation is the defining characteristic of each model, this framework leads to particular models by specification of geometric relationships between pores and particles. Typical assumptions are that particles are spheres, pores are cylinders with volume equal to the associated particle volume times the void ratio, and that the capillary inverse proportionality between radius and matric pressure is valid. Examples include fixed-pore-shape and fixed-pore-length models. We also developed alternative versions of the model of Arya and Paris that eliminate its interval-size dependence and other problems. The alternative models are calculable by direct application of algebraic formulas rather than manipulation of data tables and intermediate results, and they easily combine with other models (e.g., incorporating structural effects) that are formulated on a continuous basis. Additionally, we developed a family of models based on the same pore geometry as the widely used unsaturated hydraulic conductivity model of Mualem. Predictions of measurements for different suitable media show that some of the models provide consistently good results and can be chosen based on ease of calculations and other factors.

Vadose Zone Journal

Hydrologic controls on the subsurface transport of oil-field brine at the Osage-Skiatook Petroleum Environmental Research (OSPER) B Site, Oklahoma

As a part of a multidisciplinary study of the impact of oil wells and oil production on the environment, we are investigating the hydrology of the OSPER B site, which is located at Skiatook Lake in Osage County, Oklahoma. Salt and crude oil from oil well brine pits and accidental releases from oil tank batteries have contaminated soil, ground water, and surface water at this site. Preliminary coring near a brine pit at the site showed that beneath 0.5-2 meters of surficial deposits (fill, soil, colluvium, and alluvium), a layer of tight shale that is at least 6 meters thick underlies the site. The land slopes down from the pit at about a 1:10 slope to the lake, which is located about 20 meters from the pit. We found no evidence to date that the brine has penetrated into the shale. Field cores and water level measurements in boreholes indicated that the surficial deposits were often saturated above the shale, which was powder dry. We hypothesize that water from precipitation infiltrates into the permeable surficial deposits, ponds above the low-permeability shale, and moves laterally toward the lake in the surface layer. Dissolved salt from prior spills present in the surface layer is transported down slope to the lake during and following precipitation events. Chemical analyses of water samples collected from boreholes indicate that salt water that collects in the brine pit also moves into the surface layer and flows to the lake. Overland flow and transport of brine also occurs in response to intense rainfall events. Evapotranspiration concentrates the subsurface brine in dry periods. Our field work indicates that the surfacial deposits are very heterogeneous, and as a result there are preferential pathways for subsurface transport of water and contaminants from the pit to the lake. Our results indicate that near-surface, transient processes dominate the contaminant hydrology at this site.

Oklahoma

Multiphase flow modeling of a crude-oil spill site with a bimodal permeability distribution

Fluid saturation, particle-size distribution, and porosity measurements were obtained from 269 core samples collected from six boreholes along a 90-m transect at a subregion of a crude-oil spill site, the north pool, near Bemidji, Minnesota. The oil saturation data, collected 11 years after the spill, showed an irregularly shaped oil body that appeared to be affected by sediment spatial variability. The particle-size distribution data were used to estimate the permeability ( k ) and retention curves for each sample. An additional 344 k estimates were obtained from samples previously collected at the north pool. The 613 k estimates were distributed bimodal lognormally with the two population distributions corresponding to the two predominant lithologies: a coarse glacial outwash deposit and fine-grained interbedded lenses. A two-step geostatistical approach was used to generate a conditioned realization of k representing the bimodal heterogeneity. A cross-sectional multiphase flow model was used to simulate the flow of oil and water in the presence of air along the north pool transect for an 11-year period. The inclusion of a representation of the bimodal aquifer heterogeneity was crucial for reproduction of general features of the observed oil body. If the bimodal heterogeneity was characterized, hysteresis did not have to be incorporated into the model because a hysteretic effect was produced by the sediment spatial variability. By revising the relative permeability functional relation, an improved reproduction of the observed oil saturation distribution was achieved. The inclusion of water table fluctuations in the model did not significantly affect the simulated oil saturation distribution.

Water Resources Research