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Robert J. Rosenbauer

Publications and source records attributed to Robert J. Rosenbauer.

At least 19 recordsLinked to original sources

Sedimentary organic biomarkers suggest detrimental effects of PAHs on estuarine microbial biomass during the 20th century in San Francisco Bay, CA, USA

Hydrocarbon contaminants are ubiquitous in urban aquatic ecosystems, and the ability of some microbial strains to degrade certain polycyclic aromatic hydrocarbons (PAHs) is well established. However, detrimental effects of petroleum hydrocarbon contamination on nondegrader microbial populations and photosynthetic organisms have not often been considered. In the current study, fatty acid methyl ester (FAME) biomarkers in the sediment record were used to assess historical impacts of petroleum contamination on microbial and/or algal biomass in South San Francisco Bay, CA, USA. Profiles of saturated, branched, and monounsaturated fatty acids had similar concentrations and patterns downcore. Total PAHs in a sediment core were on average greater than 20× higher above ∼200 cm than below, which corresponds roughly to the year 1900. Isomer ratios were consistent with a predominant petroleum combustion source for PAHs. Several individual PAHs exceeded sediment quality screening values. Negative correlations between petroleum contaminants and microbial and algal biomarkers – along with high trans/cis ratios of unsaturated FA, and principle component analysis of the PAH and fatty acid records – suggest a negative impacts of petroleum contamination, appearing early in the 20th century, on microbial and/or algal ecology at the site.

California

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

A combined radio- and stable-isotopic study of a California coastal aquifer system

Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na + , K + , Mg 2+ , Ca 2+ ) and anions (Cl − , SO 4 2− ), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ 18 O), dissolved inorganic carbon (δ 13 C DIC ), and radioactive isotopes ( 3 H, 222 Rn and 223,224,226,228 Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl − concentrations attained seawater-like values and in conjunction with isotopically heavier δ 18 O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3 H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14 C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ 13 C DIC in the absence of SO 4 2− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234 U/ 238 U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer characteristics, such as geochemical cycling, rock/water interactions, and subsurface transport and mixing.

California

Integration of bed characteristics, geochemical tracers, current measurements, and numerical modeling for assessing the provenance of beach sand in the San Francisco Bay Coastal System

Over 150 million m 3 of sand-sized sediment has disappeared from the central region of the San Francisco Bay Coastal System during the last half century. This enormous loss may reflect numerous anthropogenic influences, such as watershed damming, bay-fill development, aggregate mining, and dredging. The reduction in Bay sediment also appears to be linked to a reduction in sediment supply and recent widespread erosion of adjacent beaches, wetlands, and submarine environments. A unique, multi-faceted provenance study was performed to definitively establish the primary sources, sinks, and transport pathways of beach-sized sand in the region, thereby identifying the activities and processes that directly limit supply to the outer coast. This integrative program is based on comprehensive surficial sediment sampling of the San Francisco Bay Coastal System, including the seabed, Bay floor, area beaches, adjacent rock units, and major drainages. Analyses of sample morphometrics and biological composition (e.g., Foraminifera) were then integrated with a suite of tracers including 87 Sr/ 86 Sr and 143 Nd/ 144 Nd isotopes, rare earth elements, semi-quantitative X-ray diffraction mineralogy, and heavy minerals, and with process-based numerical modeling, in situ current measurements, and bedform asymmetry to robustly determine the provenance of beach-sized sand in the region.

California

A Sr-Nd isotopic study of sand-sized sediment provenance and transport for the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87 Sr/ 86 Sr and 143 Nd/ 144 Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143 Nd/ 144 Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects

California

Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

Basaltic rocks are potential repositories for sequestering carbon dioxide (CO 2 ) because of their capacity for trapping CO 2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO 2 -charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO 2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO 2 , an average basaltic MgO content of 8% is equivalent to 2.6 × 10 8 metric ton CO 2 /km 3 basalt.

Geochimica et Cosmochimica Acta

Sequestration of non-pure carbon dioxide streams in iron oxyhydroxide-containing saline repositories

Iron oxyhydroxide, goethite (α-FeOOH), was evaluated as a potential formation mineral reactant for trapping CO 2 in a mineral phase such as siderite (FeCO 3 ), when a mixture of CO 2 -SO 2 flue gas is injected into a saline aquifer. Two thermodynamic simulations were conducted, equilibrating a CO 2 -SO 2 fluid mixture with a NaCl-brine and Fe-rich rocks at 150 °C and 300 bar. The modeling studies evaluated mineral and fluid composition at equilibrium and the influence of pH buffering in the system. Results show siderite precipitates both in the buffered and unbuffered system; however, the presence of an alkaline pH buffer enhances the stability of the carbonate. Based on the model, an experiment was designed to compare with thermodynamic predictions. A CO 2 -SO 2 gas mixture was reacted in 150 ml of NaCl-NaOH brine containing 10 g of goethite at 150 °C and 300 bar for 24 days. Mineralogical and brine chemistry confirmed siderite as the predominant reaction product in the system. Seventy-six mg of CO 2 are sequestered in siderite per 10 g of goethite.

International Journal of Greenhouse Gas Control

Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO 2 –SO 2 gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO 3 ) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO 2 with CO 2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe 2 O 3 ) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO 2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO 2 -bearing CO 2 -dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH) 2 CO 3 ), siderite (FeCO 3 ) and quartz (SiO 2 ). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al 2 Si 2 O 5 (OH) 4 ) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

Energy Procedia

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

Carbon dioxide (CO 2 ) sequestration in deep saline aquifers and formations: Chapter 3

Carbon dioxide (CO 2 ) capture and sequestration in geologic media is one among many emerging strategies to reduce atmospheric emissions of anthropogenic CO 2 . This chapter looks at the potential of deep saline aquifers – based on their capacity and close proximity to large point sources of CO 2 – as repositories for the geologic sequestration of CO 2 . The petrochemical characteristics which impact on the suitability of saline aquifers for CO 2 sequestration and the role of coupled geochemical transport models and numerical tools in evaluating site feasibility are also examined. The full-scale commercial CO 2 sequestration project at Sleipner is described together with ongoing pilot and demonstration projects.

Book chapter

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

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

Extraction of organic compounds from organic-rich rocks during geologic CO2 sequestration at supercritical conditions

At reservoir conditionscarbon dioxide is a supercritical fluid capable of extraction of naturallyoccurring neutral compounds from formation materials, including carboxylicacids at low pH. We performed a series of experiments designed to quantify theextractable carboxylic acid and neutral aromatic yield from coal of the WilcoxGroup in Louisiana. We determined concentrations of organic species in both the aqueous phase and carbon dioxide phases during batch reactions of rock with the two fluid phases. The concentration patterns observed following preliminary experiments indicate that high concentrations of aromatic acids are observed preferentially in the supercritical phase whereas aliphatic short-chain and dicarboxylic acids are preferentially found in the aqueousphase. We conclude that organic-rich rocks such as coal will be sources of organic acids following geologic CO 2 sequestration. Organic compound liberation from rocks has important implications for the subsurface microbial community and weathering rates of seal and reservoir silicates.

Conference Paper

Radiocarbon ages and age models for the past 30,000 years in Bear Lake, Utah and Idaho

Radiocarbon analyses of pollen, ostracodes, and total organic carbon (TOC) provide a reliable chronology for the sediments deposited in Bear Lake over the past 30,000 years. The differences in apparent age between TOC, pollen, and carbonate fractions are consistent and in accord with the origins of these fractions. Comparisons among different fractions indicate that pollen sample ages are the most reliable, at least for the past 15,000 years. The post-glacial radiocarbon data also agree with ages independently estimated from aspartic acid racemization in ostracodes. Ages in the red, siliclastic unit, inferred to be of last glacial age, appear to be several thousand years too old, probably because of a high proportion of reworked, refractory organic carbon in the pollen samples. Age-depth models for five piston cores and the Bear Lake drill core (BL00-1) were constructed by using two methods: quadratic equations and smooth cubic-spline fits. The two types of age models differ only in detail for individual cores, and each approach has its own advantages. Specific lithological horizons were dated in several cores and correlated among them, producing robust average ages for these horizons. The age of the correlated horizons in the red, siliclastic unit can be estimated from the age model for BL00-1, which is controlled by ages above and below the red, siliclastic unit. These ages were then transferred to the correlative horizons in the shorter piston cores, providing control for the sections of the age models in those cores in the red, siliclastic unit. These age models are the backbone for reconstructions of past environmental conditions in Bear Lake. In general, sedimentation rates in Bear Lake have been quite uniform, mostly between 0.3 and 0.8 mm yr ‒1 in the Holocene, and close to 0.5 mm yr ‒1 for the longer sedimentary record in the drill core from the deepest part of the lake.

Idaho, Utah

Stratigraphic controls on saltwater intrusion in the Dominguez Gap area of coastal Los Angeles

The Los Angeles Basin is a densely populated coastal area that significantly depends on groundwater. A part of this groundwater supply is at risk from saltwater intrusion—the impetus for this study. High-resolution seismic-reflection data collected from the Los Angeles–Long Beach Harbor Complex have been combined with borehole geophysical and descriptive geological data from four nearby ~400-m-deep continuously cored wells and with borehole geophysical data from adjacent water and oil wells to characterize the Pliocene to Holocene stratigraphy of the Dominguez Gap coastal aquifer system. The new data are shown as a north-south, two- dimensional, sequence-stratigraphic model that is compared to existing lithostratigraphic models of the Los Angeles Basin in an attempt to better understand pathways of saltwater intrusion into coastal aquifers.

California

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