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Jennifer A. Dougherty

Publications and source records attributed to Jennifer A. Dougherty.

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Occurrence of herbicides and pharmaceutical and personal care products in surface water and groundwater around Liberty Bay, Puget Sound, Washington

Organic contaminants, such as pharmaceuticals and personal care products (PPCPs), pose a risk to water quality and the health of ecosystems. This study was designed to determine if a coastal community lacking point sources, such as waste water treatment plant effluent, could release PPCPs, herbicides, and plasticizers at detectable levels to their surface water and groundwater. Research was conducted in Liberty Bay, an embayment within Puget Sound, where 70% of the population (∼10,000) uses septic systems. Sampling included collection of groundwater and surface water with grab samples and the use of polar organic chemical integrative samplers (POCIS). We analyzed for a broad spectrum of 25 commonly used compounds, including PPCPs, herbicides, and a flame retardant. Twelve contaminants were detected at least once; only N,N-diethyl-meta-toluamide, caffeine, and mecoprop, a herbicide not attributed to septic systems, were detected in more than one grab sample. The use of POCIS was essential because contaminants were present at very low levels (nanograms), which is common for PPCPs in general, but particularly so in such a small community. The use of POCIS allowed the detection of five compounds that were not present in grab samples. Data suggest that the community is contaminating local water with PPCPs; this effect is likely to increase as the population and product usage increase. The results presented here are a first step toward assessing the transport of herbicides and PPCPs into this coastal system.

Washington

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

Data Report: Acetate and Hydrogen Concentrations in Pore Fluids Associated with a Large Gas Hydrate Reservoir, Southern Hydrate Ridge, offshore Oregon, USA

Acetate and hydrogen concentrations in pore fluids were measured in samples taken at seven sites from southern Hydrate Ridge (SHR) offshore Oregon, USA. Acetate concentrations ranged from 3.17 to 2515 µM. The maximum acetate concentrations occurred at Site 1251, which was drilled on a slope basin to the east of SHR at depths just above the bottom-simulating reflector (BSR) that marks the boundary of gas hydrate stability. Acetate maxima and localized high acetate concentrations occurred at the BSR at all sites and frequently corresponded with areas of gas hydrate accumulation, suggesting an empirical relationship. Acetate concentrations were typically at a minimum near the seafloor and above the sulfate/methane interface, where sulfate-reducing bacteria may consume acetate. Hydrogen concentrations in pressure core samples ranged from 16.45 to 1036 parts per million by volume (ppmv). In some cases, hydrogen and acetate concentrations were elevated concurrently, suggesting a positive correlation. However, sampling of hydrogen was limited in comparison to acetate, so any relationships between the two analytes, if present, were difficult to discern.

Oregon

Cruise summary for P-1-02-SC: acoustic imaging of natural oil and gas seeps and measurement of dissolved methane concentration in coastal waters near Pt. Conception, California

Water-column acoustic anomalies and methane concentrations were documented in coastal waters surrounding Pt. Conception, California, in March 2002. The purpose of this survey, supported by the Minerals Management Service, was to locate active oil and gas seeps in the area as a background for further studies to determine hydrocarbon flux, mainly oil, into the environment. Objectives in reaching this goal are to (1) document the locations and geochemically fingerprint natural seeps within the offshore southern Santa Maria Basin; (2) geochemically fingerprint coastal tar residues and potential sources, both onshore and offshore, in this region; (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; (5) attempt to predict transport pathways of oil from seep sources to the coastline and; (6) interpret the petroleum system history for the natural seeps. This survey, addressing objective 1, focused on the area from offshore Surf Beach to the north and Gaviota to the south in water depths ranging from 20 to 500m. In addition, nine stations were sampled outside this area to provide a regional context. Water-column methane concentrations were measured in water samples collected from the R/V Point Sur with Niskin bottles from various depths. A total of 724 water samples from 94 stations were collected.

California