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Geology topics

F. D. Hostettler

Publications and source records attributed to F. D. Hostettler.

At least 19 recordsLinked to original sources

Application of organic geochemistry to coastal tar residues from central California

Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy ( 13 C-enriched) carbon isotopic compositions spanning a narrow range (δ 13 C = −22.2 to −23.4‰), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.

California

Families of miocene monterey crude oil, seep, and tarball samples, coastal California

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 to better assess their origins and distributions in coastal California. These samples were used to construct a chemometric (multivariate statistical) decision tree to classify 288 additional samples. The results identify three tribes of 13C-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 at Naples Beach near Santa Barbara. An attempt to correlate these families to rock extracts from these members in the nearby COST (continental offshore stratigraphic test) (OCS-Cal 78-164) well failed, at least in part because the rocks are thermally immature. Geochemical similarities among the oil tribes and their widespread distribution support the prograding margin model or the banktop-slope-basin model instead of the ridge-and-basin model for the deposition 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 traits intermediate between tribes 1 and 3, 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 source rock favored petroleum 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. In a test of the decision tree, 10 tarball samples collected from beaches in Monterey and San Mateo counties in early 2007 were found to originate from natural seeps representing different organofacies of Monterey Formation source rock instead from one anthropogenic pollution event. The seeps apparently became more active because of increased storm activity. Copyright ?? 2008. The American Association of Petroleum Geologists. All rights reserved.

American Association of Petroleum Geologists Bulle

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

Alkylcyclohexanes in environmental geochemistry

The n-alkylated cyclohexanes (CHs) are a homologous series of hydrocarbon compounds that are commonly present in crude oil and refinery products such as diesel fuel. These compounds exhibit specific distribution patterns for different fuel types, providing useful fingerprints for characterizing petroleum products, especially after degradation of n-alkanes has occurred. However, there are no published data to show how these compounds are altered in the environment after long-term spillage of petroleum products. This paper presents two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation. These spills are the 1979 crude-oil spill in Bemidji, Minnesota, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, North Dakota. The alkyl CHs in both spilled oil products are affected by similar biodegradative processes in which the compounds undergo a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation results in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. This pattern is the opposite of low-end loss expected with weathering and aerobic biodegradation. The enhancement of the low molecular mass alkyl CH homologs, if not recognized as a degradative pathway of diesel fuel in an anaerobic environment, can potentially be misinterpreted in fuel-oil fingerprinting as deriving from lower distillation-range fuels or admixture of diesel with other fuels.

Environmental Forensics

Hydrocarbons in recent sediment of the Monterey Bay National Marine Sanctuary

A complex mixture of hydrocarbons is present in the recent sediment of the Monterey Bay National Marine Sanctuary. Eighteen samples from the continental shelf between San Francisco and Monterey contain aliphatic and aromatic hydrocarbons showing biological contributions from both marine and terrigenous sources, with the terrigenous indicators more pronounced near Monterey. Of particular interest, however, is a low-level background of petroleum-related compounds, including 28,30-bisnorhopane and 18??+??(H)-oleanane, which are characteristic of many crude oils from the Monterey Formation of California. Thus, the sediments are overprinted by a regional chemical signature which may be derived from eroded Monterey Formation rocks and from onshore and offshore seeps releasing petroleum from Monterey Formation source rocks. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Geology

Hydrocarbon geochemistry of cold seeps in the Monterey Bay National Marine Sanctuary

Samples from four geographically and tectonically discrete cold seeps named Clam Flat, Clamfield, Horseshoe Scarp South, and Tubeworm City, within the Monterey Bay National Marine Sanctuary were analyzed for their hydrocarbon content. The sediment contains gaseous hydrocarbons and CO2, as well as high molecular weight aliphatic and aromatic hydrocarbons with various combinations of thermogenic and biogenic contributions from petroleum, marine, and terrigenous sources. Of particular interest is the cold seep site at Clamfield which is characterized by the presence of thermogenic hydrocarbons including oil that can likely be correlated with oil-saturated strata at Majors Creek near Davenport, CA, USA. At Clam Flat, the evidence for thermogenic hydrocarbons is equivocal. At Horseshoe Scarp South and Tubeworm City, hydrocarbon gases, mainly methane, are likely microbial in origin. These varied sources of hydrocarbon gases highlight the diverse chemical systems that appear at cold seep communities. ?? 2002 Elsevier Science B.V. All rights reserved.

Marine Geology

Alkylcyclohexanes in environmental geochemistry

Two case studies of oil spills that demonstrate the changing distribution patterns resulting from long-term anaerobic microbial degradation were presented. These spills were the 1979 crude-oil spill in Bemidji, MN, and a chronic diesel-fuel spillage from 1953-1991 at Mandan, ND. The alkylcyclohexanes in both spilled oil products were affected by similar biodegradative processes in which the compounds underwent a consistent pattern of loss from the high molecular weight end of the homolog distribution. Degradation resulted in a measurable increase in the concentrations of the homologs in the lower molecular weight range, a gradual lowering in carbon number of the homolog maximum, and a gradual decrease of the total homolog range from the high molecular weight end. The Mandan diesel fuel spill showed that the progressive enhancement of the low-molecular-mass n-alkane and n-alkylcyclohexane homologs reflected an absolute increase in their concentrations as the high-molecular-mass homologs were diminishing. These degradation patterns were different from those observed in aerobic or physically weathered systems, where loss of n-alkenes and other aliphatic homologs occurred from the low molecular weight end of the distributions. Spilled diesel and other mid-cut refinery fuels were defined by the range and distribution of the n-alkylcyclohexanes. If the biodegradation has progressed well into or beyond n-alkane loss and to the stage of low-molecular-mass n-alkylcyclohexane enhancement and high-molecular-mass loss, the hydrocarbon pattern could be erroneously attributed to other lower-range middle distillate fuels or admixtures of fuels. This is an abstract presented at the 25th Arctic and Marine OilSpill Program Technical Seminar (Calgary, Alberta, 6/11-13/2002).

Conference Paper

Accumulation of butyltins in sediments and lipid tissues of the Asian clam, Potamocorbula amurensis, near Mare Island Naval Shipyard, San Francisco Bay

Studies of butyltin compounds in soil, benthic sediments and the Asian clam Potamocorbula amurensis were conducted at the former Mare Island Naval Shipyard, and nearby Mare Island and Carquinez Straits in San Francisco Bay, California. Soils from a sandblast abrasives dump site at the shipyard contained low concentrations of mono-, di- and tributyltin (0.3-52 ng/g, total butyltin). Similarly, concentrations of total butyltin in benthic sediments from nearby Mare Island and Carquinez Straits ranged from 1.3 to 8.1 ng/g. In contrast, clams accumulated much greater concentrations (152-307 ng/g, total butyltin). Tributyltin (TBT) and dibutyltin (DBT) made up from 54-85% to 15-46%, respectively, of the total butyltin body burden of the clams. Biota Sediment Accumulation Factors (BSAFs) for butyltins in Potamocorbula were in reasonable agreement with literature values; they are greater than those of neutral hydrophobic compounds, suggesting that partitioning and binding processes may be involved in bioaccumulation. Tributyltin is a potent endocrine disrupting chemical. There is potential for long-term chronic effects of TBT in San Francisco Bay.

Marine Pollution Bulletin

PAH refractory index as a source discriminant of hydrocarbon input from crude oil and coal in Prince William Sound, Alaska

Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty. A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.

Conference Paper

A record of hydrocarbon input to San Francisco Bay as traced by biomarker profiles in surface sediment and sediment cores

San Francisco Bay is one of the world's largest urbanized estuarine systems. Its water and sediment receive organic input from a wide variety of sources; much of this organic material is anthropogenically derived. To document the spatial and historical record of the organic contaminant input, surficial sediment from 17 sites throughout San Francisco Bay and sediment cores from two locations Richardson Bay and San Pablo Bay were analyzed for biomarker constituents. Biomarkers, that is, 'molecular fossils', primarily hopanes, steranes, and n-alkanes, provide information on anthropogenic contamination, especially that related to petrogenic sources, as well as on recent input of biogenic material. The biomarker parameters from the surficial sediment and the upper horizons of the cores show a dominance of anthropogenic input, whereas the biomarker profiles at the lower horizons of the cores indicate primarily biogenic input. In the Richardson Bay core the gradual upcore transition from lower maturity background organics to a dominance of anthropogenic contamination occurred about 70-100 years ago and corresponds to the industrial development of the San Francisco Bay area. In San Pablo Bay, the transition was very abrupt, reflecting the complex depositional history of the area. This sharp transition, perhaps indicating a depositional hiatus or erosional period, dated at pre-1952, is clearly visible. Below, the hiatus the biomarker parameters are immature; above, they are mature and show an anthropogenic overlay. Higher concentrations of terrigenous n-alkanes in the upper horizons in this core are indicative of an increase in terrigenous organic matter input in San Pablo Bay, possibly a result of water diversion projects and changes in the fresh water flow into the Bay from the Delta. Alternatively, it could reflect a dilution of organic material in the lower core sections with hydraulic mining debris.

California

Distributions and fate of chlorinated pesticides, biomarkers and polycyclic aromatic hydrocarbons in sediments along a contamination gradient from a point-source in San Francisco Bay, California

The distribution and fate of chlorinated pesticides, biomarkers, and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments along a contamination gradient in the Lauritzen Canal and Richmond Harbor in San Francisco Bay was investigated. Compounds were identified and quantified using gas chromatography-ion trap mass spectrometry. Biomarkers and PAHs were derived primarily from weathered petroleum. DDT was reductively dechlorinated under anoxic conditions to DDD and several minor degradation products, DDMU, DDMS, and DDNU. Under aerobic conditions, DDT was dehydrochlorinated to DDE and DBP. Aerobic degradation of DDT was diminished or inhibited in zones of high concentration, and increased significantly in zones of lower concentration: Other chlorinated pesticides identified in sediment included dieldrin and chlordane isomers. Multivariate analysis of the distributions of the DDTs suggested that there are probably two sources of DDD. In addition, DDE and DDMU are probably formed by similar mechanisms, i.e. dehydrochlorination. A steep concentration gradient existed from the Canal to the Outer Richmond Harbor, but higher levels of DDD than those found in the remainder of the Bay indicated that these contaminants are transported on particulates and colloidal organic matter from this source into San Francisco Bay. Chlorinated pesticides and PAHs may pose a potential problem to biota in San Francisco Bay.

Marine Environmental Research

Occurrence and accumulation of pesticides and organic contaminants in river sediment, water and clam tissues from the San Joaquin River and tributaries, California

A study was conducted in 1992 to assess the effects of anthropogenic activities and land use on the water quality of the San Joaquin River and its major tributaries. This study focused on pesticides and organic contaminants, looking at distributions of contaminants in water, bed and suspended sediment, and the bivalve Corbicula fluminea. Results indicated that this river system is affected by agricultural practices and urban runoff. Sediments from Dry Creek contained elevated concentrations of polycyclic aromatic hydrocarbons (PAHs), possibly derived from urban runoff from the city of Modesto; suspended sediments contained elevated amounts of chlordane. Trace levels of triazine herbicides atrazine and simazine were present in water at most sites. Sediments, water, and bivalves from Orestimba Creek, a westside tributary draining agricultural areas, contained the greatest levels of DDT (1,1,1-trichloro-2-2-bis[p-chlorophenyl]ethane), and its degradates DDD (1,1-dichloro-2,2-bis[p-chlorophenyl]ethane), and DDE (1,1-dichloro-2,2- bis[p-chlorophenyl]ethylene). Sediment adsorption co efficients (K(oc)), and bioconcentration factors (BCF) in Corbicula of DDT, DDD, and DDE at Orestimba Creek were greater than predicted values. Streams of the western San Joaquin Valley can potentially transport significant amounts of chlorinated pesticides to the San Joaquin River, the delta, and San Francisco Bay. Organochlorine compounds accumulate in bivalves and sediment and may pose a problem to other biotic species in this watershed.

California

Hydrocarbons in oil residues on beaches of islands of Prince William Sound, Alaska

Aliphatic and aromatic hydrocarbons were measured on oil residues from beaches on six islands in Prince William Sound, Alaska. In addition to altered products from the Exxon Valdez oil spill of 1989, we also found, at two widely separated locations, residues that are similar to each other but chemically distinct from the spilled oil. Terpanes, steranes, monoaromatic steranes, and carbon isotopic compositions of total extracts were most useful in correlating the altered products of the spilled oil. These same parameters revealed that the two non-Valdez samples are likely residues of oil originally produced in California. The results indicate that oil residues currently on the beaches of this estuary have at least two quite different origins.

Marine Pollution Bulletin

Organic markers as source discriminants and sediment transport indicators in south San Francisco Bay, California

Sediment samples from nearshore sites in south San Francisco Bay and from streams flowing into that section of the Bay have been characterized in terms of their content of biogenic and anthropogenic molecular marker compounds. The distributions, input sources, and applicability of these compounds in determining sediment movement are discussed. By means of inspection and multivariate analysis, the compounds were grouped according to probable input sources and the sampling stations according to the relative importance of source contributions. A suite of polycyclic aromatic hydrocarbons (PAHs) dominated by pyrene, fluoranthene and phenanthrene, typical of estuarine environments worldwide, and suites of mature sterane and hopane biomarkers were found to be most suitable as background markers for the Bay. A homologous series of long-chain n-aldehydes (C12-C32) with a strong even-over-odd carbon number dominance in the higher molecular weight range and the ubiquitous n-alkanes (n-C24-C34) with a strong odd-over-even carbon number dominance were utilized as terrigenous markers. Several ratios of these terrigenous and Bay markers were calculated for each station. These ratios and the statistical indicators from the multivariate analysis point toward a strong terrigenous signal in the terminus of South Bay and indicate net directional movement of recently introduced sediment where nontidal currents had been considered to be minimal or nonexistent and tidal currents had been assumed to be dominant.

California