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Frances D. Hostettler

Publications and source records attributed to Frances D. Hostettler.

At least 19 recordsLinked to original sources

Comparison of surficial CO2 efflux to other measures of subsurface crude oil degradation

At a spill site near Bemidji, Minnesota, crude oil at the water table has been undergoing anaerobic biodegradation for over 30 years. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. To compare microbial activity measurement methods from multiple locations in the oil body, surficial carbon dioxide efflux, methanogen and methanotroph concentrations, and oil degradation state were collected. Carbon dioxide effluxes over the oil body averaged more than four times those at the background site. Methanotrophic bacteria concentrations measured using pmoA were over 10 5 times higher above the oil-contaminated sediments compared with the background site. Methanogenic archaea measured using mcrA ranged from 10 5 to over 10 7 in the oil and were below detection in the background. Methanogens correlated very well with methanotroph concentrations (r = 0.99), n-alkylcyclohexane losses as a proxy for degradation state (r = − 0.96), and somewhat less well with carbon dioxide efflux (r = 0.92). Carbon dioxide efflux similarly correlated to methanotroph concentrations (r = 0.90) and n-alkylcyclohexane losses (r = − 0.91).

Minnesota

California State Waters Map Series: Offshore of Coal Oil Point, California

In 2007, the California Ocean Protection Council initiated the California Seafloor Mapping Program (CSMP), designed to create a comprehensive seafloor map of high-resolution bathymetry, marine benthic habitats, and geology within the 3-nautical-mile limit of California’s State Waters. The CSMP approach is to create highly detailed seafloor maps through collection, integration, interpretation, and visualization of swath sonar data, acoustic backscatter, seafloor video, seafloor photography, high-resolution seismic-reflection profiles, and bottom-sediment sampling data. The map products display seafloor morphology and character, identify potential marine benthic habitats, and illustrate both the surficial seafloor geology and shallow (to about 100 m) subsurface geology. The Offshore of Coal Oil Point map area lies within the central Santa Barbara Channel region of the Southern California Bight. This geologically complex region forms a major biogeographic transition zone, separating the cold-temperate Oregonian province north of Point Conception from the warm-temperate California province to the south. The map area is in the southern part of the Western Transverse Ranges geologic province, which is north of the California Continental Borderland. Significant clockwise rotation—at least 90°—since the early Miocene has been proposed for the Western Transverse Ranges province, and geodetic studies indicate that the region is presently undergoing north-south shortening. Uplift rates (as much as 2.0 mm/yr) that are based on studies of onland marine terraces provide further evidence of significant shortening. The cities of Goleta and Isla Vista, the main population centers in the map area, are in the western part of a contiguous urban area that extends eastward through Santa Barbara to Carpinteria. This urban area is on the south flank of the east-west-trending Santa Ynez Mountains, on coalescing alluvial fans and uplifted marine terraces underlain by folded and faulted Miocene bedrock. In the map area, the relatively low-relief, elevated coastal bajada narrows from about 2.5 km wide in the east to less than 500 m wide in the west. Several beaches line the actively utilized coastal zone, including Isla Vista County Park beach, Coal Oil Point Reserve, and Goleta Beach County Park. The beaches are subject to erosion each winter during storm-wave attack, and then they undergo gradual recovery or accretion during the more gentle wave climate of the late spring, summer, and fall months. The Offshore of Coal Oil Point map area lies in the central part of the Santa Barbara littoral cell, which is characterized by littoral drift to the east-southeast. Longshore drift rates have been reported to range from about 160,000 to 800,000 tons/yr, averaging 400,000 tons/yr. Sediment supply to the western and central parts of the littoral cell, including the map area, is largely from relatively small transverse coastal watersheds. Within the map area, these coastal watersheds include (from east to west) Las Llagas Canyon, Gato Canyon, Las Varas Canyon, Dos Pueblos Canyon, Eagle Canyon, Tecolote Canyon, Winchester Canyon, Ellwood Canyon, Glen Annie Canyon, and San Jose Creek. The Santa Ynez and Santa Maria Rivers, the mouths of which are about 100 to 140 km northwest of the map area, are not significant sediment sources because Point Conception and Point Arguello provide obstacles to downcoast sediment transport and also because much of their sediment load is trapped in dams. The Ventura and Santa Clara Rivers, the mouths of which are about 45 to 55 km southeast of the map area, are much larger sediment sources. Still farther east, eastward-moving sediment in the littoral cell is trapped by Hueneme and Mugu Canyons and then transported to the deep-water Santa Monica Basin. The offshore part of the map area consists of a relatively flat and shallow continental shelf, which dips gently seaward (about 0.8° to 1.0°) so that water depths at the shelf break, roughly coincident with the California’s State Waters limit, are about 90 m. This part of the Santa Barbara Channel is relatively well protected from large Pacific swells from the north and northwest by Point Conception and from the south and southwest by offshore islands and banks. The shelf is underlain by variable amounts of upper Quaternary marine and fluvial sediments deposited as sea level fluctuated in the late Pleistocene. The large (130 km2) Goleta landslide complex lies along the shelf break in the southern part of the map area. This compound slump complex may have been initiated more than 200,000 years ago, but it also includes three recent failures that may have been generated between 8,000 to 10,000 years ago. A local, 5- to 10-m-high tsunami may have been generated from these failure events. The map area has had a long history of hydrocarbon development, which began in 1928 with discovery of the Ellwood oil field. Subsequent discoveries in the offshore include South Ellwood offshore oil field, Coal Oil Point oil field, and Naples oil and gas field. Development of South Ellwood offshore field began in 1966 from platform “Holly,” the last platform to be installed in California’s State Waters. The area also is known for “the world’s most spectacular marine hydrocarbon seeps,” and large tar seeps are exposed on beaches east of the mouth of Goleta Slough. Offshore seeps adjacent to South Ellwood oil field release about 40 tons per day of methane and about 19 tons per day of ethane, propane, butane, and higher hydrocarbons. Seafloor habitats in the broad Santa Barbara Channel region consist of significant amounts of soft sediment and isolated areas of rocky habitat that support kelp-forest communities nearshore and rocky-reef communities in deep water. The potential marine benthic habitat types mapped in the Offshore of Coal Oil Point map area are directly related to its Quaternary geologic history, geomorphology, and active sedimentary processes. These potential habitats, which lie primarily within the Shelf (continental shelf) but also partly within the Flank (basin flank or continental slope) megahabitats, range from soft, unconsolidated sediment to hard sedimentary bedrock. This heterogeneous seafloor provides promising habitat for rockfish, groundfish, crabs, shrimp, and other marine benthic organisms.

California

Petroleum fingerprinting with organic markers

Petroleum fingerprinting is an invaluable tool in forensic geochemistry. This article summarizes applications of fingerprinting in several oil spills and natural oil seepages that we have studied during the last 25 years. It shows how each unique chemical fingerprint can be used to correlate or differentiate oils. Fingerprints can provide information about processes in the environment that impact oils such as weathering and microbial degradation. They can be used to evaluate organic matter that contributed to oils, and classify oils with regard to the geological framework of their source, such as evaluating geological facies, age, lithology, and depositional environment.

Environmental Forensics

Petroleum hydrocarbons in sediment from the northern Gulf of Mexico shoreline, Texas to Florida

Petroleum hydrocarbons were extracted and analyzed from shoreline sediment collected from the northern Gulf of Mexico (nGOM) coastline that could potentially be impacted by Macondo-1 (M-1) well oil. Sediment was collected before M-1 well oil made significant local landfall and analyzed for baseline conditions by a suite of diagnostic petroleum biomarkers. Oil residue in trace quantities was detected in 45 of 69 samples. With the aid of multivariate statistical analysis, three different oil groups, based on biomarker similarity, were identified that were distributed geographically along the nGOM from Texas to Florida. None of the sediment hydrocarbon extracts correlated with the M-1 well oil extract, however, the similarity of tarballs collected at one site (FL-18) with the M-1 well oil suggests that some oil from the Deepwater Horizon spill may have been transported to this site in the Florida Keys, perhaps by a loop current, before that site was sampled.

Florida;Texas

Biomarker chemistry and flux quantification methods for natural petroleum seeps and produced oils, offshore southern California

Sustained, natural oil seepage from the seafloor is common off southern California, and is of great interest to resource managers, who are tasked with distinguishing natural from anthropogenic oil sources. The major purpose of this study was to build upon the work previously funded by the Bureau of Ocean Energy Management (BOEM) and the U.S. Geological Survey (USGS) that has refined the oil-fingerprinting process to enable differentiation of the highly similar Monterey Formation oils from Outer Continental Shelf (OCS) production and adjacent natural seeps. In these initial studies, biomarker and stable carbon isotope ratios were used to infer the age, lithology, organic-matter input, and depositional environment of the source rocks for 388 samples of produced crude oil, seep oil, and tarballs mainly from coastal California. The analysis resulted in a predictive model of oil source families that could be applied to samples of unknown origin.

California

Reconnaissance of Macondo-1 well oil in sediment and tarballs from the northern Gulf of Mexico shoreline, Texas to Florida

Hydrocarbons were extracted and analyzed from sediment and tarballs collected from the northern Gulf of Mexico (nGOM) coast that is potentially impacted by Macondo-1 (M-1) well oil. The samples were analyzed for a suite of diagnostic geochemical biomarkers. Aided by multivariate statistical analysis, the M-1 well oil has been identified in sediment and tarballs collected from Louisiana, Alabama, Mississippi, and Florida. None of the sediment hydrocarbon extracts from Texas correlated with the M-1 well oil. Oil-impacted sediments are confined to the shoreline adjacent to the cumulative oil slick of the Deepwater Horizon oil spill, and no impact was observed outside of this area.

Open-File Report

Natural offshore oil seepage and related tarball accumulation on the California coastline — Santa Barbara Channel and the southern Santa Maria Basin; source identification and inventory

Oil spillage from natural sources is very common in the waters of southern California. Active oil extraction and shipping is occurring concurrently within the region and it is of great interest to resource managers to be able to distinguish between natural seepage and anthropogenic oil spillage. The major goal of this study was to establish the geologic setting, sources, and ultimate dispersal of natural oil seeps in the offshore southern Santa Maria Basin and Santa Barbara Basins. Our surveys focused on likely areas of hydrocarbon seepage that are known to occur between Point Arguello and Ventura, California. Our approach was to 1) document the locations and geochemically fingerprint natural seep oils or tar; 2) geochemically fingerprint coastal tar residues and potential tar sources in this region, both onshore and offshore; 3) establish chemical correlations between offshore active seeps and coastal residues thus linking seep sources to oil residues; 4) measure the rate of natural seepage of individual seeps and attempt to assess regional natural oil and gas seepage rates; and 5) interpret the petroleum system history for the natural seeps. To document the location of sub-sea oil seeps, we first looked into previous studies within and near our survey area. We measured the concentration of methane gas in the water column in areas of reported seepage and found numerous gas plumes and measured high concentrations of methane in the water column. The result of this work showed that the seeps were widely distributed between Point Conception east to the vicinity of Coal Oil Point, and that they by in large occur within the 3-mile limit of California State waters. Subsequent cruises used sidescan and high resolution seismic to map the seafloor, from just south of Point Arguello, east to near Gaviota, California. The results of the methane survey guided the exploration of the area west of Point Conception east to Gaviota using a combination of seismic instruments. The seafloor was mapped by sidescan sonar, and numerous lines of high -resolution seismic surveys were conducted over areas of interest. Biomarker and stable carbon isotope ratios were used to infer the age, lithology, organic matter input, and depositional environment of the source rocks for 388 samples of produced crude oil, seep oil, and tarballs mainly from coastal California. These samples were used to construct a chemometric fingerprint (multivariate statistics) decision tree to classify 288 additional samples, including tarballs of unknown origin collected from Monterey and San Mateo County beaches after a storm in early 2007. A subset of 9 of 23 active offshore platform oils and one inactive platform oil representing a few oil reservoirs from the western Santa Barbara Channel were used in this analysis, and thus this model is not comprehensive and the findings are not conclusive. The platform oils included in this study are from west to east: Irene, Hildago, Harvest, Hermosa, Heritage, Harmony, Hondo, Holly, Platform A, and Hilda (now removed). The results identify three “tribes” of 13 C-rich oil samples inferred to originate from thermally mature equivalents of the clayey-siliceous, carbonaceous marl, and lower calcareous-siliceous members of the Monterey Formation. Tribe 1 contains four oil families having geochemical traits of clay-rich marine shale source rock deposited under suboxic conditions with substantial higher-plant input. Tribe 2 contains four oil families with intermediate traits, except for abundant 28,30-bisnorhopane, indicating suboxic to anoxic marine marl source rock with hemipelagic input. Tribe 3 contains five oil families with traits of distal marine carbonate source rock deposited under anoxic conditions with pelagic but little or no higher-plant input. Tribes 1 and 2 occur mainly south of Point Conception in paleogeographic settings where deep burial of the Monterey Formation source rock favored generation from all three members or their equivalents. In this area, oil from the clayey-siliceous and carbonaceous marl members (Tribes 1 and 2) may overwhelm that from the lower calcareous-siliceous member (Tribe 3) because the latter is thinner and less oil-prone than the overlying members. Tribe 3 occurs mainly north of Point Conception, where shallow burial caused preferential generation from the underlying lower calcareous-siliceous member or another unit with similar characteristics. It is very desirable to be able to clearly distinguish the naturally occurring seep oils from the anthropogenically derived platform oils. Within the “training set” of oils and tars (388 samples), the biomarker parameters are sometimes sufficient to allow unique discrimination of individual platform oils. More often however, platform samples and seep samples with sources geographically close to each other are too similar to each other, with respect to the biomarker parameters, to definitively differentiate them on that basis alone. In some cases other parameters can be helpful. These other parameters are related to the degree of biogeochemical degradation or weathering that the oils or tars have experienced. These components include the typical oil distribution of n-alkane hydrocarbons and isoprenoids pristane and phytane. All of the platform oils in our sample set contain these components. On the other hand, the seep oils or tars have been exposed to significant biodegradation while in the near subsurface. The majority, but not all of seep oils or tars have been biodegraded up to or beyond the loss of n-alkanes and isoprenoids. Seep oils found in the vicinity of Coal Oil Point or Arroyo Burro are apparently the least weathered and are particularly likely to retain significant n-alkanes and isoprenoids. Therefore the combination of chemometric fingerprinting and the presence or absence of n-alkanes and isoprenoids help to differentiate anthropogenic production oils versus natural seeps oils and tars. The differentiation is not always definitive because of the close chemical similarity of some samples and the variability in the biodegradation progression. This is the case near Coal Oil Point, and near Platform A (Dos Cuadros Field) where seep oils and Platform Holly and Platform A oils are genetically very similar and cannot be definitively distinguished after a period of a few days of weathering. In contrast, oils from the Point Conception platforms can be distinguished on the basis of chemometric fingerprinting alone. In the middle of this spectrum are oils from Platforms Harmony, Heritage, and Hondo, where it is expected that oil weathering would take on the order of two weeks to a month to produce tarballs similar to those seen near Point Conception. In this case there is a much greater degree of weathering needed to proceed from produced oil to the biodegraded tar characteristic of tarball stranded on the beach. Tar deposition on beaches was monitored as part of cooperative with the County of Santa Barbara Energy Division and the U.S. Geological Survey during 2001-2003. We found tar deposition varies on a seasonal basis. In general, tarballs accumulate at a faster rate or remain longer on all beaches during the summer and fall months. The reasons for this are unclear based on our limited observations, however we speculate that factors such as prevailing winds and currents combined with more quiescent wave conditions favors the accumulation and preservation of tarballs on the beach during the summer and fall months. In contrast, winter storms, with much greater wave action remove beach sand and other materials, and stormy seas tend to break up oil that might weather into tarballs. Natural seepage is affected by the spring/neap tidal cycle; however, the link to tar deposition is unclear. Longer periods of monitoring are needed to address the variability in the data and provide a more robust statistical analysis.

California

Profiling refined hydrocarbon fuels using polar components

Identification of a fuel released into the environment can be difficult due to biodegradation or weathering. Negative electrospray ionization/mass spectrometry was used to screen for unique polar components in a wide variety of commercial hydrocarbon products and mixtures. These fuels produced unique and relatively simple spectra. When applied to hydrocarbon samples from a large, long-term fuel spill in a relatively cool climate in which the alkane, isoprenoid, and alkylcyclohexane portions had begun to biodegrade or weather, the polar components in these samples had changed little over time. This technique provided rapid fuel identification on hydrocarbons released into the environment, without sample preparation, fractionation, or chromatography.

Environmental Forensics

Geochemistry of coastal tarballs in southern California—A tribute to I. R. Kaplan

In the southern offshore California borderland, natural oil seeps occur mainly in the Santa Barbara Channel and Santa Monica Bay. Coastal tar residues (tarballs) from beaches bordering these water bodies were analyzed for six geochemical parameters: stable carbon isotopic compositions (δ 13 C) and four biomarker ratios (C 28 IC 29 hopane, sterane/hopane, refractory index, bisnorhopane index), and the presence or absence of trisnorhopane. The objectives of this study were to group these residues and infer possible sources and transport directions. Three major groups were established. Two groups are likely from natural seeps near the Channel Islands, whereas the third group probably comes from seeps within Santa Monica Bay. Residues from all groups occur on the Channel Islands and on mainland beaches from as far south as San Diego to Point Reyes north of San Francisco.

California

Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound, Alaska

Although the shorelines of Prince William Sound still bear traces of the 1989 Exxon Valdez oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Instead, the carbon-isotopic and hydrocarbonbiomarker signatures of 61 tar ball samples, collected from shorelines throughout the northern and western parts of the sound, are all remarkably similar and have characteristics consistent with those of oil products that originated from the Monterey Formation source rocks of California. The carbonisotopic compositions of the tar balls are all closely grouped (<513Cpdb = -23.7 ± 0.2%o), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon ValdezoW spill (<513Cpdb = -29.4 ± 0.1%o). Likewise, values for selected biomarker ratios in the tar balls are all similar but distinct from values of residues from the 1989 oil spill. Carbon-isotopic and biomarker signatures generally relate the tar balls to oil products used in Alaska before ~1970 for construction and pavements. How these tar balls with such similar geochemical characteristics became so widely dispersed throughout the northern and western parts of the sound is not known with certainty, but the great 1964 Alaska earthquake was undoubtedly an important trigger, causing spills from ruptured storage facilities of California-sourced asphalt and fuel oil into Prince William Sound.

Alaska

Subsurface and petroleum geology of the southwestern Santa Clara Valley ("Silicon Valley"), California

Gravity anomalies, historical records of exploratory oil wells and oil seeps, new organic-geochemical results, and new stratigraphic and structural data indicate the presence of a concealed, oil-bearing sedimentary basin beneath a highly urbanized part of the Santa Clara Valley, Calif. A conspicuous isostatic-gravity low that extends about 35 km from Palo Alto southeastward to near Los Gatos reflects an asymmetric, northwest-trending sedimentary basin comprising low-density strata, principally of Miocene age, that rest on higher-density rocks of Mesozoic and Paleogene(?) age. Both gravity and well data show that the low-density rocks thin gradually to the northeast over a distance of about 10 km. The thickest (approx 4 km thick) accumulation of low-density material occurs along the basin's steep southwestern margin, which may be controlled by buried, northeast-dipping normal faults that were active during the Miocene. Movement along these hypothetical normal faults may been contemporaneous (approx 17–14 Ma) with sedimentation and local dacitic and basaltic volcanism, possibly in response to crustal extension related to passage of the northwestward-migrating Mendocino triple junction. During the Pliocene and Quaternary, the normal faults and Miocene strata were overridden by Mesozoic rocks, including the Franciscan Complex, along northeastward-vergent reverse and thrust faults of the Berrocal, Shannon, and Monte Vista Fault zones. Movement along these fault zones was accompanied by folding and tilting of strata as young as Quaternary and by uplift of the modern Santa Cruz Mountains; the fault zones remain seismically active. We attribute the Pliocene and Quaternary reverse and thrust faulting, folding, and uplift to compression caused by local San Andreas Fault tectonics and regional transpression along the Pacific-North American Plate boundary. Near the southwestern margin of the Santa Clara Valley, as many as 20 exploratory oil wells were drilled between 1891 and 1929 to total depths as great as 840 m. At least one pump unit is still standing. Although no lithologic or paleontologic samples are available from the wells, driller's logs indicate the presence of thick intervals of brown shale and sandstone resembling nearby outcrops of the Miocene Monterey Formation. Small amounts of oil and gas were observed in several wells, but commercial production was never established. Oil from the Peck well in Los Gatos is highly biodegraded, contains biomarkers commonly found in oils derived from the Monterey Formation, and has a stable-C-isotopic (d13C) composition of –23.32 permil, indicating derivation from a Miocene Monterey Formation source rock. Preliminary calculations suggest that about 1 billion barrels of oil may have been generated from source rocks within the Monterey Formation in the deepest part of the subsurface sedimentary basin between Los Gatos and Cupertino. Most of this oil was probably lost to biodegradation, oxidation, and leakage to the surface, but some oil may have accumulated in as-yet-undiscovered structural and stratigraphic traps along the complex structural boundary between the Santa Clara Valley and the Santa Cruz Mountains. Although some of these undiscovered accumulations of oil may be of commercial size, future petroleum exploration is unlikely because most of the area is currently devoted to residential, recreational, commercial, and industrial uses.

California

Environmental impacts of petroleum production: The fate of petroleum and other organics associated with produced water from the Osage-Skiatook Petroleum Environmental Research sites, Osage County, OK

We are involved in a multidisciplinary investigation to study the transport, fate, and natural attenuation of inorganic salts, trace metals, radionuclides and organic compounds present in produced water, and their impacts on soil, surface and ground water and the local ecosystem at the Osage-Skiatook Petroleum Environmental Research (OSPER) A and B sites, located in Osage County, OK. About one hectare of land at each of the OSPER A and B sites is affected by salt scarring, soil salinization and brine and petroleum contamination. The main environmental concern results because the sites are adjacent to Skiatook Lake, a 4250-hectare reservoir that provides drinking water to the local communities and is a major recreational fishery. Petroleum wells and tank batteries at the A site have been inactive for some time and the bulk of the hydrocarbon (now degraded and weathered oil) and produced water releases occurred more than 60 years ago. One pit at this site however, contains relatively fresh asphaltic oil and high salinity brine. The B site includes an active production tank battery and adjacent brine and oil pit, an inactive tank battery and an injection well with a small brine pit. For this study oil, gas and/or brine samples were obtained from several oil wells at the B site and areas adjoining the A and B sites, from the two active brine pits at the B site, from the asphaltic pit and adjacent weathered oil pit at the A site and from several of the 40 boreholes (1-71 m deep), recently drilled and completed. Water samples for dissolved organics were obtained from selected boreholes with high salinity water and measurable hydrocarbon gases in the unsaturated zone. Soil and rock core samples were obtained from these selected boreholes to determine the amount and composition of oil sorbed onto the sediments. Finally samples of sediments and/or water from these selected boreholes and from the brine and oil pits were obtained for bacterial characterization. Chemical analysis and bacterial determinations on the collected samples are continuing. Results completed to date show the crude oil source (samples from B and adjacent production wells) is a typical paraffinic-naphthenic light (API gravity of ~35) oil, containing n-alkanes as the dominant components. The four samples examined are identical in their maturity and chemical characteristics. Even though petroleum production is from shallow sandstones (300-600 m depth), these fresh oils show no sign of biodegradation, indicating that bacteria are unable to survive in the associated high salinity (~150,000 mg/L total dissolved solids) brine. Bacterial action, volatilization and water washing are likely responsible for the transformation of source oil to the surficial asphaltic and weathered oil observed at the A site. The leakage of oil with brine from the main active pit at the B site is indicated by the detection of a thin, but discrete oil phase in at least one borehole, the presence of hydrocarbon gases in several boreholes and the smell of oil in many sediment cores from the impacted area located down gradient from this pit. The measured concentrations of DOC, acetate and other organic acid anions, BTEX, phenols and other organics in the source brine are relatively low, but their values in water samples from the impacted areas are not yet available.

Oklahoma

Hydrologic setting and geochemical characterization of free-phase hydrocarbons in the alluvial aquifer at Mandan, North Dakota, November 2000

Free-phase hydrocarbons are present in the alluvial aquifer at Mandan, North Dakota. A large contaminant body of the hydrocarbons [light nonaqueous phase liquid (LNAPL)] floats on the water table about 20 feet below land surface. The main LNAPL body is about 6 feet thick, and the areal extent is about 657,000 square feet. A study was conducted to describe the hydrologic setting and characterize the geochemical composition of the free-phase hydrocarbons in the alluvial aquifer. Most of the study area is underlain by alluvium of the Heart River Valley that ranges in thickness from about 25 to 109 feet. The alluvium can be divided into three stratigraphic units silty clay, silty sand, and sand and is underlain by shales and sandstones. Monitoring wells were installed prior to this study, to an average depth of about 29 feet. Regional ground-water flow in the Heart River aquifer generally may be from west-northwest to eastsoutheast and is influenced by hydraulic connections to the river. Hydraulic connections also are probable between the aquifer and the Missouri River. Ground-water flow across the north boundary of the aquifer is minimal because of adjacent shales and sandstones of relatively low permeability. Recharge occurs from infiltration of precipitation and is spatially variable depending on the thickness of overlying clays and silts. Although the general water-table gradient may be from west-northwest to east-southeast, the flow directions can vary depending on the river stage and recharge events. Any movement of the LNAPL is influenced by the gradients created by changes in water-level altitudes. LNAPL samples were collected from monitoring wells using dedicated bailers. The samples were transferred to glass containers, stored in the dark, and refrigerated before shipment for analysis by a variety of analytical techniques. For comparison purposes, reference-fuel samples provided by the refinery in Mandan also were analyzed. These reference-fuel samples included a current diesel fuel, a closely related but slightly broader refinery-cut fuel, a crude-oil composite, unleaded regular gasoline, and additives. Four principal analytical techniques were used for geochemical characterization: Purge-and-trap gas chromatography/mass spectrometry (volatile components); capillary gas chromatography/mass spectrometry (semivolatile components); isotope ratio mass spectrometry (carbon isotopes; whole oils); and liquid chromatography/mass spectrometry with electrospray ionization (additives and other organic components). Volatile analytes included solvents, disinfection byproducts, halogenated hydrocarbons, and alkylbenzenes, including benzene, toluene, ethylbenzene, and meta-, para-, and orf/zo-xylenes. Semivolatile analytes included rt-alkanes, isoprenoid alkanes, cycloalkanes, and polycyclic aromatic hydrocarbons and related compounds (naphthalenes, phenanthrenes, and dibenzothiophenes and their alkylated derivatives). Of the additives, only the diesel-fuel additive with the red dye marker was amenable to electrospray ionization. Results indicate the LNAPL consists of closely correlatable diesel fuel at various stages of degradation. All LNAPL samples contained the red dye marker for diesel fuel. None of the samples contained chlorinated solvents associated with industries such as drycleaning or automotive maintenance. Solvents such as acetone, dimethyl ether, and methylene chloride and the gasoline additives methyl-t-butyl ether (MTBE), ethyl-t-butyl ether (ETBE), and t-amyl-methyl ether (TAME) were not found. With one possible exception, no evidence of a different diesel or other hydrocarbon fuel contribution was identified. At one site near the north edge of the main LNAPL body, evidence exists for traces of possible gasoline components in addition to the diesel fuel. The geochemical analysis of the LNAPL and correlations with other fuel products and additives strongly suggest episodic releases of a single, local-source, diesel fuel into the aquifer over an extended period of time.

North Dakota