Coal Oil Point Research Articles

Decadal cyclical geological atmospheric emissions for a major marine seep field, offshore Coal Oil Point, Southern California

The greenhouse gas, methane, budget has significant uncertainty for many sources, including natural geological emissions. A major uncertainty of geological methane emissions, including onshore and offshore hydrocarbon seepage from subsurface hydrocarbon reservoirs is the gas emissions’ temporal variability. Current atmospheric methane budget models assume seepage is constant; nevertheless, available data and seepage conceptual models suggest gas seepage can vary considerably on timescales from second to century. The assumption of steady-seepage is used because long-term datasets to characterize these variabilities are lacking. A 30-year air quality dataset downwind of the Coal Oil Point seep field, offshore California found methane, CH4, concentrations downwind of the seep field increased from a 1995 minimum to a 2008 peak, decreasing exponentially afterward with a 10.2-year timescale (R2 = 0.91). Atmospheric emissions, EA, were derived by a time-resolved Gaussian plume inversion model of the concentration anomaly using observed winds and gridded sonar source location maps. EA increased from 27,200 to 161,000 m3 day−1 (corresponding to 6.5–38 Gg CH4 year−1 for 91% CH4 content) for 1995–2009, respectively, with 15% uncertainty, then decreased exponentially from 2009 to 2015 before rising above the trend. 2015 corresponded to the cessation of oil and gas production, which affects the western seep field. EA varied sinusoidally with a 26.3-year period (R2 = 0.89) that largely tracked the Pacific Decadal Oscillation (PDO), which is driven on these timescales by an 18.6-year earth-tidal cycle (27.9-year beat). A similar controlling factor may underlie both, specifically varying compressional stresses on migration pathways. This also suggests the seep atmospheric budget may exhibit multi-decadal trends.

Biliary Polycyclic Aromatic Hydrocarbon Metabolite Equivalents Measured in Fish and Subtidal Invertebrates Following the Refugio Beach Oil Spill.

Monterey formation crude oil spilled from an onshore pipeline and entered the surf zone near Refugio State Beach, Santa Barbara County, CA, USA on 19 May 2015. Exposure to nearshore fish was evaluated by measuring biliary polycyclic aromatic hydrocarbon (PAH) metabolite concentrations in surfperch (Embiotocidae), collected near the release point, at a lesser oiled area, Gaviota State Beach, and near the Coal Oil Point oil seep, Campus Point, at both four days and approximately one year after the oil spill. Three to four weeks after the spill, fish, invertebrates, and kelp were collected near the same three sites for PAH analysis of edible tissues to support the fishery closure assessment. Additionally, thirteen days after the spill, vegetation, and invertebrate tissue samples from the seafloor near Refugio State Beach were analyzed for PAHs. In surfperch bile, mean naphthalene, phenanthrene and benzo(a)pyrene metabolite equivalents were significantly higher at Refugio State Beach, compared to Gaviota State Beach or Campus Point in 2015. One year later, there was no significant difference between the three sites. Spatial and depth zone patterns of PAH tissue concentrations from composited invertebrate, vegetation and fish showed highest concentrations were measured in invertebrates collected near Refugio State Beach. Overall, results show elevated PAH levels in nearshore organisms and provide a useful reference for potential PAH exposures in fish and subtidal invertebrates following a large nearshore oil spill.

Measuring Floating Thick Seep Oil from the Coal Oil Point Marine Hydrocarbon Seep Field by Quantitative Thermal Oil Slick Remote Sensing

Remote sensing techniques offer significant potential for generating accurate thick oil slick maps critical for marine oil spill response. However, field validation and methodology assessment challenges remain. Here, we report on an approach to leveraging oil emissions from the Coal Oil Point (COP) natural marine hydrocarbon seepage offshore of southern California, where prolific oil seepage produces thick oil slicks stretching many kilometers. Specifically, we demonstrate and validate a remote sensing approach as part of the Seep Assessment Study (SAS). Thick oil is sufficient for effective mitigation strategies and is set at 0.15 mm. The brightness temperature of thick oil, TBO, is warmer than oil-free seawater, TBW, allowing segregation of oil from seawater. High spatial-resolution airborne thermal and visible slick imagery were acquired as part of the SAS; including along-slick “streamer” surveys and cross-slick calibration surveys. Several cross-slick survey-imaged short oil slick segments that were collected by a customized harbor oil skimmer; termed “collects”. The brightness temperature contrast, ΔTB (TBO − TBW), for oil pixels (based on a semi-supervised classification of oil pixels) and oil thickness, h, from collected oil for each collect provided the empirical calibration of ΔTB(h). The TB probability distributions provided TBO and TBW, whereas a spatial model of TBW provided ΔTB for the streamer analysis. Complicating TBW was the fact that streamers were located at current shears where two water masses intersect, leading to a TB discontinuity at the slick. This current shear arose from a persistent eddy down current of the COP that provides critical steering of oil slicks from the Coal Oil Point. The total floating thick oil in a streamer observed on 23 May and a streamer observed on 25 May 2016 was estimated at 311 (2.3 bbl) and 2671 kg (20 bbl) with mean linear floating oil 0.14 and 2.4 kg m−1 with uncertainties by Monte Carlo simulations of 25% and 7%, respectively. Based on typical currents, the average of these two streamers corresponds to 265 g s−1 (~200 bbl day−1) in a range of 60–340 bbl day−1, with significant short-term temporal variability that suggests slug flow for the seep oil emissions. Given that there are typically four or five streamers, these data are consistent with field emissions that are higher than the literature estimates.

A case study in controlled source electromagnetism: Near seabed hydrocarbon seep systems of Coal Oil Point, California, USA

Marine hydrocarbon seeps are found on all continental margins and release significant amounts of greenhouse gases and hydrocarbons into the atmosphere and hydrosphere. Most methods of studying seeps rely on seafloor or near-seafloor observations, but seepage rates and seep locations can be variable, leading to uncertainty. We exploit the fact that hydrocarbons are electrically resistive compared with surrounding sediments and use marine electromagnetic methods to study the deeper sources and accumulation sites, which are controlled by local geology and should be more stable than the seabed expressions. Our surface towed marine controlled source electromagnetic system used a horizontal electric dipole transmitter and floating electric dipole receivers spaced 100–400 m from the transmitter, collecting frequency domain amplitude and phase data at ∼2 Hz and harmonics. The survey targeted known and inferred hydrocarbon seeps within the Coal Oil Point seep field offshore Santa Barbara, California, USA. Two dimensional inversions of the data indicate that the method is sensitive to the shallowly buried (<400 m) structure of the marine hydrocarbon seeps and is an efficient and effective tool in their identification and characterization. The results show spatial variability of seafloor hydrocarbons along the Coal Oil Point seep field and indicate at least two previously unidentified intermediate depth accumulation sites. The depth and lateral extent of these hydrocarbon accumulation sites may improve seep emission models for the Coal Oil Point seep field.

An inverse planned oil release validation method for estimating oil slick thickness from thermal contrast remote sensing by in-scene calibration

This study demonstrates a method to estimate floating oil slick thickness based on remote sensing of thermal infrared contrast. The approach was demonstrated for thick oil slicks from natural seeps in the Coal Oil Point seep field, offshore southern California. Airborne thermal infrared and visible spectrum remote sensing imagery were acquired along with position and orientation data by the SeaSpires™ science package. Remote sensing data were acquired in the cross-slick direction of oil slick segments that were targeted for collection, termed “collects.” A collect consisted of booming, skimming, and offloading the oil slick segment into buckets for analysis at the laboratory. Each collect provided an in-scene calibration point of oil thickness versus brightness temperature contrast, ΔTB, where TB is the sensor-reported temperature based on the emitted thermal radiation and differs from the true temperature due to the oil's emissivity. ΔTB is the TB difference between the oil and oil-free sea surface. Thus, this study is a reverse planned oil-release experiment that demonstrates the value of natural seeps for oil spill science.• Novel approach to quantify floating oil thickness• Custom modified weir skimmer used with added floor and structural strengthening

Long-term atmospheric emissions for the Coal Oil Point natural marine hydrocarbon seep field, offshore California

Abstract. In this study, we present a novel approach for assessing nearshore seepage atmospheric emissions through modeling of air quality station data, specifically a Gaussian plume inversion model. A total of 3 decades of air quality station meteorology and total hydrocarbon concentration, THC, data were analyzed to study emissions from the Coal Oil Point marine seep field offshore California. THC in the seep field directions was significantly elevated and Gaussian with respect to wind direction, θ. An inversion model of the seep field, θ-resolved anomaly, THC′(θ)-derived atmospheric emissions is given. The model inversion is for the far field, which was satisfied by gridding the sonar seepage and treating each grid cell as a separate Gaussian plume. This assumption was validated by offshore in situ data that showed major seep area plumes were Gaussian. Plume total carbon, TC (TC = THC + carbon dioxide, CO2, + carbon monoxide), 18 % was CO2 and 82 % was THC; 85 % of THC was CH4. These compositions were similar to the seabed composition, demonstrating efficient vertical plume transport of dissolved seep gases. Air samples also measured atmospheric alkane plume composition. The inversion model used observed winds and derived the 3-decade-average (1990–2021) field-wide atmospheric emissions of 83 400 ± 12 000 m3 THC d−1 (27 Gg THC yr−1 based on 19.6 g mol−1 for THC). Based on a 50 : 50 air-to-seawater partitioning, this implies seabed emissions of 167 000 m3 THC d−1. Based on atmospheric plume composition, C1–C6 alkane emissions were 19, 1.3, 2.5, 2.2, 1.1, and 0.15 Gg yr−1, respectively. The spatially averaged CH4 emissions over the ∼ 6.3 km2 of 25 × 25 m2 bins with sonar values above noise were 5.7 µM m−2 s−1. The approach can be extended to derive emissions from other dispersed sources such as landfills, industrial sites, or terrestrial seepage if source locations are constrained spatially.

Long-term acoustic monitoring and tracking of natural hydrocarbon seeps from an offshore oil platform in the Coal Oil Point seep field

The Coal Oil Point (COP) seep field, located offshore of Santa Barbara, California, is known for its prolific, natural hydrocarbon seepage activity. The COP seep field has been active for decades and previous research indicates both spatial and temporal variability in seep activity across the area. An offshore oil platform within the COP seep field, known as Platform Holly, has extracted oil and gas in the area since the late 1960s, which has been linked to a reduction in natural seep activity. In recent years, Platform Holly has been decommissioned, and anecdotal observations indicate a subsequent resurgence in natural seep activity in the vicinity. In early September 2019, a Simrad ES200 split-beam echosounder was mounted to one of the cross-members of the platform to collect acoustic measurements of the seepage activity west of the platform. This long-term time series of acoustic measurements will provide insight on the spatial and temporal variability of seepage activity in the region and how said variability is affected by external physical processes such as atmospheric pressure, currents, and tides.

Radiocarbon in Marine Methane Reveals Patchy Impact of Seeps on Surface Waters

AbstractGeological sources of methane (CH4), such as hydrocarbon seeps, are significant yet poorly constrained sources of CH4 to seawater and the overlying atmosphere. We investigate the radiocarbon content (14C) and concentrations of dissolved CH4 in surface waters from the Coal Oil Point seep field to test the hypothesis that geological sources can dominate the regional background signal of CH4. We find that surface waters with elevated CH4 concentration were populated with seep‐CH4 and that lower concentrations of CH4 were well explained by mixing with the regional background of nongeological CH4. Substantial differences in concentration and 14C‐CH4 were observed over distances &lt;5 km, demonstrating that surface currents mix background‐CH4 into the seep field. These results indicate that even a prolific seep region like the Santa Barbara Basin exerts limited influence on the regional background of CH4 in the surface layer but is a significant driver of patchiness in oceanic CH4 biogeochemistry.

Bubble-mediated transport of benthic microorganisms into the water column: Identification of methanotrophs and implication of seepage intensity on transport efficiency

Benthic microorganisms transported into the water column potentially influence biogeochemical cycles and the pelagic food web structure. In the present study six gas-releasing vent sites in the Coal Oil Point seep field (California) were investigated, and the dislocation of microorganisms from the sediment into the water column via gas bubbles released from the seabed was documented. It was found that the methanotrophs transport efficiency was dependent on the volumetric gas flow, with the highest transport rate of 22.7 × 103 cells mLgas−1 at a volumetric gas flow of 0.07 mLgas s−1, and the lowest rate of 0.2 × 103 cells mLgas−1 at a gas flow of 2.2 mLgas s−1. A simple budget approach showed that this bubble-mediated transport has the potential to maintain a relevant part of the water-column methanotrophs in the seep field. The bubble-mediated link between the benthic and pelagic environment was further supported by genetic analyses, indicating a transportation of methanotrophs of the family Methylomonaceae and oil degrading bacteria of the genus Cycloclasticus from the sediment into the water column. These findings demonstrate that the bubble-mediated transport of microorganisms influences the pelagic microbial abundance and community composition at gas-releasing seep sites.

A Synthesis Review of Emissions and Fates for the Coal Oil Point Marine Hydrocarbon Seep Field and California Marine Seepage

Anthropogenic oil in the ocean is of great concern due to its potential immediate and long-term impacts on the ecosystem, economy, and society, leading to intense societal efforts to mitigate and reduce inputs. Sources of oil in the ocean (in the order of importance) are natural marine seepage, run-off from anthropogenic sources, and oil spills, yet uncertainty and variability in these budgets are large, particularly for natural seepage, which exhibits large spatial and temporal heterogeneity on local to regional scales. When source inputs are comparable, discriminating impacts is complicated, because petroleum is both a bioavailable, chemosynthetic energy source to the marine ecosystem and a potential toxic stressor depending on concentration, composition, and period of time. This synthesis review investigates the phenomena underlying this complexity and identifies knowledge gaps. Its focus is on the Coal Oil Point (COP) seep field, arguably the best-studied example, of strong natural marine hydrocarbon seepage, located in the nearshore, shallow waters of the Northern Santa Barbara Channel, Southern California, where coastal processes complicate oceanography and meteorology. Many of our understandings of seep processes globally are based on insights learned from studies of the oil and gas emissions from the COP seep field. As one of the largest seep fields in the world, its impacts spread far as oil drifts on the sea surface and subsurface, yet much remains unknown of its impacts.

Modern Assessment of Natural Hydrocarbon Gas Flux at the Coal Oil Point Seep Field, Santa Barbara, California

AbstractThe Coal Oil Point seep field is among the most active and studied hydrocarbon seep fields in the world. The water column of the Coal Oil Point seep field was acoustically surveyed from 31 August to 14 September 2016 with a 200‐kHz split‐beam echo sounder to map the distribution of natural hydrocarbons in the region. An in situ direct capture device was used to measure the volumetric gas flux of natural hydrocarbons for three localized seep sites while simultaneously collecting acoustic volume backscatter measurements of the hydrocarbons within the water column. The acoustic volume backscatter was calibrated with the measured volumetric gas flux, and the resulting relationship was used to determine flux over the entire seep field. The estimate of integrated volumetric gas flow rate over a survey area of approximately 4.1 km2 was 23,800 m3/day. The estimates of integrated volumetric gas flow rate and volumetric gas flux were compared to measurements reported in previous studies and were 2 to 7 times smaller than results obtained by Hornafius et al. (1999, https://doi.org/10.1029/1999JC900148), which had a total survey area of 18 km2. However, differences between methodologies limit the ability to assess natural variability in the Coal Oil Point seep field.

Reduced Methane Emissions from Santa Barbara Marine Seeps

Airborne in situ and remote sensing measurements of methane were performed over the marine seeps in the Santa Barbara Channel close to the Coal Oil Point in California on two days in June and August 2014 with the aim to re-assess their methane emissions. During this period, methane column averaged dry air mole fractions derived from airborne remote sensing measurements in the short-wave infrared and airborne in situ measurements of methane indicate that emissions are 2–6 kt CH 4 y − 1 , significantly lower than expected from previous publications. This is also confirmed by the on ground in situ measurement time series recorded at the onshore West Campus Monitoring Station in Santa Barbara. Using a time series of methane data, a decline in methane concentrations between 2008 and 2015 of more than a factor of two was derived for air masses originating from the seep field direction.

Evidence of low-frequency multiple scattering of methane gas bubbles at Coal Oil Point, Santa Barbara, California

Coal Oil Point, located in the Santa Barbara Channel, CA, is known for its prolific natural hydrocarbon seepage. These hydrocarbons are released at depths between 30 and 80 m, shallow enough that the hydrocarbons reach the surface. Transport via bubbles and droplets through the water column enables the exchange of hydrocarbons between the ocean and the atmosphere. Hydroacoustic observations from previous surveys have been used to map hydrocarbon seep distributions and estimate the flux of hydrocarbons from the seafloor in Coal Oil Point. On September 14, 2016, this area was revisited and surveyed using low-frequency sub-bottom profilers operating from 1 to 10 kHz. The goal is to estimate the gas flux of hydrocarbons from the hydroacoustic measurements and compare them to historic estimates for this area. Visual observations of dense bubble cloud structures of these seeps were seen and evidence of multiple scattering effects were observed in the hydroacoustic measurements. We examine how acoustic scattering of natural hydrocarbon gas bubbles is effected by multiple scattering and how this process affects the quantification of gas flux.

Challenges in Methane Column Retrievals from AVIRIS-NG Imagery over Spectrally Cluttered Surfaces: A Sensitivity Analysis

A comparison between efforts to detect methane anomalies by a simple band ratio approach from the Airborne Visual Infrared Imaging Spectrometer-Classic (AVIRIS-C) data for the Kern Front oil field, Central California, and the Coal Oil Point marine hydrocarbon seep field, offshore southern California, was conducted. The detection succeeded for the marine source and failed for the terrestrial source, despite these sources being of comparable strength. Scene differences were investigated in higher spectral and spatial resolution collected by the AVIRIS-C successor instrument, AVIRIS Next Generation (AVIRIS-NG), by a sensitivity study. Sensitivity to factors including water vapor, aerosol, planetary boundary layer (PBL) structure, illumination and viewing angle, and surface albedo clutter were explored. The study used the residual radiance method, with sensitivity derived from MODTRAN (MODerate resolution atmospheric correction TRANsmission) simulations of column methane (XCH4). Simulations used the spectral specifications and geometries of AVIRIS-NG and were based on a uniform or an in situ vertical CH4 profile, which was measured concurrent with the AVIRIS-NG data. Small but significant sensitivity was found for PBL structure and water vapor; however, highly non-linear, extremely strong sensitivity was found for surface albedo error. For example, a 10% decrease in the surface albedo corresponded to a 300% XCH4 increase over background XCH4 to compensate for the total signal, less so for stronger plumes. This strong non-linear sensitivity resulted from the high percentage of surface-reflected radiance in the airborne at-sensor total radiance. Coarse spectral resolution and feedback from interferents like water vapor underlay this sensitivity. Imaging spectrometry like AVIRIS and the Hyperspectral InfraRed Imager (HyspIRI) candidate satellite mission, have the advantages of contextual spatial information and greater at-sensor total radiance. However, they also face challenges due to their relatively broad spectral resolution compared to trace gas specific orbital sensors, e.g., the Greenhouse gases Observing SATellite (GOSAT), which is especially applicable to trace gas retrievals over scenes with high spectral albedo variability. Results of the sensitivity analysis are applicable for the residual radiance method and CH4 profiles used in the analysis, but they illustrate potential significant challenges in CH4 retrievals using other approaches.

Cooperation between Response Crews and Land Managers Protects Snowy Plovers during the Refugio Oil Spill

ABSTRACT During the Refugio oil spill of May 2015 along the southern California coast, thousands of cleanup crews scoured beaches for oil, tar patties, and oiled wrack (washed-up kelp and seaweed). At the same time, federally threatened Western Snowy Plovers were feeding with their recently hatched chicks. Because they primarily forage on invertebrates in the wrack and wave-washed swash zone, they were directly threatened by both the oil and the actions of the cleanup crews. At several sites, land managers worked cooperatively to educate cleanup crews, monitor the birds, and develop cleanup strategies that balanced the benefits and impacts of the response actions. This included limiting the presence of cleanup crews to allow time for the birds to forage at regular intervals, and adopting techniques that left some unoiled wrack in place. This careful management served to minimize impacts to the birds. At Coal Oil Point Reserve, the effects of the oil and response actions on the nesting plovers and their chicks were closely studied. The results suggest that the oil and the presence of cleanup crews both affected the birds. The birds were directly oiled and suffered reduced fertility a year later. During the spill, nest attendance and feeding behavior were impacted by the presence of response crews. Careful management and coordination between biologists and response crews helps to minimize the negative effects of disturbance while achieving the benefits of removing oil from the beaches.

Predation on transmission stages reduces parasitism: sea anemones consume transmission stages of a barnacle parasite

While parasites serve as prey, it is unclear how the spatial distribution of parasite predators provides transmission control and influences patterns of parasitism. Because many of its organisms are sessile, the rocky intertidal zone is a valuable but little used system to understand spatial patterns of parasitism and elucidate the underlying mechanisms driving these patterns. Sea anemones and barnacles are important space competitors in the rocky intertidal zone along the Pacific coast of North America. Anemones are voracious, indiscriminate predators; thus, they may intercept infectious stages of parasites before they reach a host. We investigate whether a sea anemone protects an associated barnacle from parasitism by Hemioniscus balani, an isopod parasitic castrator. At Coal Oil Point, Santa Barbara, California USA, 29% of barnacles were within 1 cm from an anemone at the surveyed tidal height. Barnacles associated with anemones had reduced parasite prevalence and higher reproductive productivity than those remote from sea anemones. In the laboratory, anemones readily consumed the transmission stage of the parasite. Hence, anemone consumption of parasite transmission stages may provide a mechanism by which community context regulates parasite prevalence at a local scale. Our results suggest predation may be an important process providing parasite transmission control.

Methane-Oxidizing Bacteria Shunt Carbon to Microbial Mats at a Marine Hydrocarbon Seep.

The marine subsurface is a reservoir of the greenhouse gas methane. While microorganisms living in water column and seafloor ecosystems are known to be a major sink limiting net methane transport from the marine subsurface to the atmosphere, few studies have assessed the flow of methane-derived carbon through the benthic mat communities that line the seafloor on the continental shelf where methane is emitted. We analyzed the abundance and isotope composition of fatty acids in microbial mats grown in the shallow Coal Oil Point seep field off Santa Barbara, CA, USA, where seep gas is a mixture of methane and CO2. We further used stable isotope probing (SIP) to track methane incorporation into mat biomass. We found evidence that multiple allochthonous substrates supported the rich growth of these mats, with notable contributions from bacterial methanotrophs and sulfur-oxidizers as well as eukaryotic phototrophs. Fatty acids characteristic of methanotrophs were shown to be abundant and 13C-enriched in SIP samples, and DNA-SIP identified members of the methanotrophic family Methylococcaceae as major 13CH4 consumers. Members of Sulfuricurvaceae, Sulfurospirillaceae, and Sulfurovumaceae are implicated in fixation of seep CO2. The mats’ autotrophs support a diverse assemblage of co-occurring bacteria and protozoa, with Methylophaga as key consumers of methane-derived organic matter. This study identifies the taxa contributing to the flow of seep-derived carbon through microbial mat biomass, revealing the bacterial and eukaryotic diversity of these remarkable ecosystems.

Bubble Transport Mechanism: Indications for a gas bubble-mediated inoculation of benthic methanotrophs into the water column

The importance of methanotrophic microorganisms in the sediment and water column for balancing marine methane budgets is well accepted. However, whether methanotrophic populations are distinct for benthic and pelagic environments or are the result of exchange processes between the two remains an area of active research. We conducted a field pilot study at the Rostocker Seep site (Coal Oil Point seep field, offshore California, USA) to test the hypothesis that bubble-mediated transport of methane-oxidizing microorganisms from the sediment into the water column is quantifiable. Measurements included dissolved methane concentration showed a strong influence of methane seepage on the water-column methane distribution with strongly elevated sea surface concentrations with respect to atmospheric equilibrium (saturation ratio ~17,000%).Using Catalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD FISH) analysis, aerobic methane oxidizing bacteria (MOB) were detected in the sediment and the water column, whereas anaerobic methanotrophs (ANME-2) were detected exclusively in the sediment. Critical data for testing the hypothesis were collected using a novel bubble catcher that trapped naturally emanating seep gas bubbles and any attached particles approximately 15cm above the seafloor. Bubble catcher experiments were carried out directly above a natural bubble seep vent and at a nearby reference site, for which an “engineered” nitrogen bubble vent without sediment contact was created. Our experiments indicate the existence of a “Bubble Transport Mechanism”, which transports MOB from the sediment into the water column. In contrast, ANME-2 were not detected in the bubble catcher. The Bubble Transport Mechanism could have important implications for the connectivity between benthic and pelagic methanotrophic communities at methane seep sites.

Marine microbes rapidly adapt to consume ethane, propane, and butane within the dissolved hydrocarbon plume of a natural seep

AbstractSimple hydrocarbon gases containing two to four carbons (ethane, propane, and butane) are among the most abundant compounds present in petroleum reservoirs, and are introduced into the ocean through natural seepage and industrial discharge. Yet little is known about the bacterial consumption of these compounds in ocean waters. To assess the timing by which microbes metabolize these gases, we conducted a three‐phase study that tested and applied a radiotracer‐based method to quantify the oxidation rates of ethane, propane, and butane in fresh seawater samples. Phase 1 involved the synthesis of tritiated ethane, propane, and butane using Grignard reagents and tritiated water. Phase 2 was a systematic assessment of experimental conditions, wherein the indigenous microbial community was found to rapidly oxidize ethane, propane, and butane. Phase 3 was the application of this tritium method near the Coal Oil Point seeps, offshore California. Spatial and temporal patterns of ethane, propane, and butane oxidation down current from the hydrocarbon seeps demonstrated that &gt;99% of these gases are metabolized within 1.3 days following initial exposure. The oxidation of ethane outpaced oxidation of propane and butane with patterns indicating the microbial community responded to these gases by rapid adaptation or growth. Methane oxidation responded the slowest in plume waters. Estimates based on the observed metabolic rates and carbon mass balance suggest that ethane, propane, and butane‐consuming microorganisms may transiently account for a majority of the total microbial community in these impacted waters.

High resolution measurements of methane and carbon dioxide in surface waters over a natural seep reveal dynamics of dissolved phase air-sea flux.

Marine hydrocarbon seeps are sources of methane and carbon dioxide to the ocean, and potentially to the atmosphere, though the magnitude of the fluxes and dynamics of these systems are poorly defined. To better constrain these variables in natural environments, we conducted the first high-resolution measurements of sea surface methane and carbon dioxide concentrations in the massive natural seep field near Coal Oil Point (COP), California. The corresponding high resolution fluxes were calculated, and the total dissolved phase air-sea fluxes over the surveyed plume area (∼363 km(2)) were 6.66 × 10(4) to 6.71 × 10(4) mol day(-1) with respect to CH4 and -6.01 × 10(5) to -5.99 × 10(5) mol day(-1) with respect to CO2. The mean and standard deviation of the dissolved phase air-sea fluxes of methane and carbon dioxide from the contour gridding analysis were estimated to be 0.18 ± 0.19 and -1.65 ± 1.23 mmol m(-2) day(-1), respectively. This methane flux is consistent with previous, lower-resolution estimates and was used, in part, to conservatively estimate the total area of the dissolved methane plume at 8400 km(2). The influx of carbon dioxide to the surface water refutes the hypothesis that COP seep methane appreciably influences carbon dioxide dynamics. Seeing that the COP seep field is one of the biggest natural seeps, a logical conclusion could be drawn that microbial oxidation of methane from natural seeps is of insufficient magnitude to change the resulting plume area from a sink of atmospheric carbon dioxide to a source.