Frances D. Hostettler

Sedimentary record of anthropogenic and biogenic polycyclic aromatic hydrocarbons in San Francisco Bay, California

Dated sediment cores collected from Richardson and San Pablo Bays in San Francisco Bay were used to reconstruct a history of polycyclic aromatic hydrocarbon (PAH) contamination. The sedimentary record of PAHs in Richardson Bay shows that anthropogenic inputs have increased since the turn of the century, presumably as a result of increasing urbanization and industrialization around the Bay Area. Concentrations range from about 0.04–6.3 μg g−1. The dominant origin of the PAHs contributing to this modern contamination is from combustion processes. Depth profiles in San Pablo Bay indicate higher concentrations of PAHs since the 1950s than during the late 1800s, also presumably resulting from an increase in urbanization and industrialization. Total PAHs in San Pablo Bay range from about 0.04–1.3 μg g−1. The ratios of methylphenanthrenes/phenanthrene and (methylfluoranthenes+methylpyrenes)/fluoranthene were sensitive indicators of anthropogenic influences in the estuary. Variations in the ratio of 1,7-dimethylphenanthrene/2,6-dimethylphenanthrene indicate a gradual replacement of wood by fossil-fuel as the main combustion source of PAHs in San Francisco Bay sediments. The profile of perylene may be an indicator of eroding peat from marshlands.

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

Abstract 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.

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 hydrocarbon-biomarker 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 carbon-isotopic compositions of the tar balls are all closely grouped (δ 13 C PDB = -23.7 ± 0.2‰), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon Valdezoil spill (δ 13 C PDB = -29.4 ± 0.1‰). 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, butthe 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.

Geochemical changes in crude oil spilled from the Exxon Valdez supertanker into Prince William Sound, Alaska

Abstract North Slope crude oil spilled from the T/V Exxon Valdez in March 1989 and contaminated about 500 km of Prince William Sound shoreline. Aliphatic and aromatic hydrocarbons in oil samples collected in August 1990 and June 1992 from beaches on six islands impacted by the spill have been compared with the hydrocarbons from North Slope crude oil taken from the stricken tanker. Degradation processes have changed the physical appearance of this residual spilled oil; the beached oil as collected ranged from a light brown color, to a heavy black viscous oil, to a black, powder-like residue. In these physically different samples, terpane, sterane, and aromatic sterane distributions, as well as carbon isotope values, are similar and correlate with the original Exxon Valdez oil. On the other hand, n -alkanes, isoprenoids, and many of the polycyclic aromatic hydrocarbons which are present in the original crude oil are dramatically altered in the oil samples collected from the beaches.

Petroleum Associated with Polymetallic Sulfide in Sediment from Gorda Ridge

A sediment sample, impregnated with asphaltic petroleum and polymetallic sulfide, was dredged from the southern end of Gorda Ridge (the Escanaba Trough) off northern California, within the offshore Exclusive Economic Zone of the United States. The molecular distributions of hydrocarbons in this petroleum show that it was probably derived from terrestrial organic matter in turbidite sediment filling the Escanaba Trough. Hydrothermal activity at the Gorda Ridge spreading center provided the heat for petroleum formation and was the source of fluids for sulfide mineralization.

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.

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.

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.

Occurrence and distribution of organochlorine compounds in sediment and livers of striped bass (Morone saxatilis) from the San Francisco Bay-Delta Estuary☆

Abstract A preliminary assessment was made in 1992 of chlorinated organic compounds in sediments and in livers of striped bass from the San Franciso Bay-Delta Estuary. Samples of sediment and striped bass livers contained DDT (ethane, 1,1,1-trichloro-2,2-bis (p-chlorophenyl)-) and its degradation products, DDD (ethane, 1,1-dichloro-2,2-bis(p-chlorophenyl)-) and DDE (ethylene, 1,1-dichloro-2,2-bis (p-chlorophenyl)-); PCBs (polychlorinated biphenyls); alpha and gamma chlordane, and cis and trans nonachlor. In addition, the livers of striped bass contained small concentrations of DCPA (dimethyl tetrachloroterephthalate), a pre-emergent herbicide. Agricultural run-off from the Sacramento and San Joaquin Rivers, as well as atmospheric deposition, are probably responsible for a low chronic background of DDT in sediments throughout San Francisco Bay. Larger concentrations of DDT in sediment near Richmond in the Central Bay, and Coyote Creek in the South Bay may be derived from point sources. Ratios of pentachloro isomers of PCBs to hexachloro isomers in the South Bay sediments were different from those in the Central and North Bay, suggesting either differences in microbial activity in the sediments or different source inputs of PCBs. Concentrations of alpha chlordane in livers of striped bass were greater than those of gamma chlordane, which suggests a greater environmental stability and persistence of alpha chlordane. Trans nonachlor, a minor component of technical chlordane, was present in greater concentrations than alpha and gamma chlordane and cis nonachlor. Trans nonachlor is more resistant to metabolism than alpha and gamma chlordane and cis nonachlor, and serves as an environmentally stable marker compound of chlordane contamination in the estuary. Chlorinated organic compounds have bioaccumulated in the livers of striped bass. These compounds may contribute to the decline of the striped bass in San Francisco Bay-Delta Estuary.

Use of geochemical biomarkers in bottom sediment to track oil from a spill, San Francisco Bay, California

In April 1988, approximately 1500 m3 of a San Joaquin Valley crude oil were accidentally released from a Shell Oil Co. refinery near Martinez, Californa. The oil flowed into Carquinez Strait and Suisun Bay in northern San Francisco Bay. Sediment and oil samples were collected within a week and analysed for geochemical marker compounds in order to track the molecular signature of the oil spill in the bottom sediment. Identification of the spilled oil in the sediment was complicated by the degraded nature of the oil and the similarity of the remaining, chromatographically resolvable constituents to those already present in the sediments from anthropogenic petroleum contamination, pyrogenic sources, and urban drainage. Ratios of hopane and sterane biomarkers, and of polycyclic aromatic hydrocarbons and their alkylated derivatives best identified the oil impingement. They showed the oil impact at this early stage to be surficial only, and to be patchy even within an area of heavy oil exposure.