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.

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.

Oil at sea-how much is too much?

The anthropogenic share of marine oil discharge is much larger than previously thought.

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.

Estimating exposure to hydrogen sulfide from animal husbandry operations using satellite ammonia as a proxy: Methodology demonstration.

Husbandry trace gases that have climate change implications such as carbon dioxide (CO2), methane (CH4) and ammonia (NH3) can be quantified through remote sensing; however, many husbandry gases with health implications such as hydrogen sulfide (H2S), cannot. This pilot study demonstrates an approach to derive H2S concentrations by coupling in situ and remote sensing data. Using AMOG (AutoMObile trace Gas) Surveyor, a mobile air quality and meteorology laboratory, we measured in situ concentrations of CH4, CO2, NH3, H2S, and wind at a southern California university research dairy. Emissions were 0.13, 1.93, 0.022 and 0.0064 Gg yr-1; emission factors (EF) were 422, 6333, 74, and 21 kg cow-1 yr-1, respectively, for the 306 head herd. Contributing to these strong EF were spillway emissions from a grate between the main cowshed and the waste lagoon identified in airborne remote sensing data acquired by the hyperspectral thermal infrared imager, Mako. NH3 emissions from the Chino Dairy Complex, also in southern California, were calculated from Infrared Atmospheric Sounding Interferometer (IASI) satellite data for 2008-2017 using average morning winds, yielding a flushing time of 2.7 h, and 8.9 Gg yr-1. The ratio of EF(H2S) to EF(NH3) for the research dairy from AMOG data were applied to IASI NH3 emissions to derive H2S exposure concentration maps for the Chino area, which ranged to 10-30 ppb H2S for many populated areas. Combining remote sensing with in situ concentrations of multiple emitted gases can allow derivation of emissions at the sub-facility, facility, and larger scales, providing spatial and temporal coverage that can translate into exposure estimates for use in epidemiology studies and regulation development. Furthermore, with high fidelity information at the sub-facility level we can identify best practices and opportunities to sustainably and holistically reduce husbandry emissions.

Validation of mobile in situ measurements of dairy husbandry emissions by fusion of airborne/surface remote sensing with seasonal context from the Chino Dairy Complex.

Mobile in situ concentration and meteorology data were collected for the Chino Dairy Complex in the Los Angeles Basin by AMOG (AutoMObile trace Gas) Surveyor on 25 June 2015 to characterize husbandry emissions in the near and far field in convoy mode with MISTIR (Mobile Infrared Sensor for Tactical Incident Response), a mobile upwards-looking, column remote sensing spectrometer. MISTIR reference flux validated AMOG plume inversions at different information levels including multiple gases, GoogleEarth imagery, and airborne trace gas remote sensing data. Long-term (9-yr.) Infrared Atmospheric Sounding Interferometer satellite data provided spatial and trace gas temporal context. For the Chino dairies, MISTIR-AMOG ammonia (NH3) agreement was within 5% (15.7 versus 14.9 Gg yr-1, respectively) using all information. Methane (CH4) emissions were 30 Gg yr-1 for a 45,200 herd size, indicating that Chino emission factors are greater than previously reported. Single dairy inversions were much less successful. AMOG-MISTIR agreement was 57% due to wind heterogeneity from downwind structures in these near-field measurements and emissions unsteadiness. AMOG CH4, NH3, and CO2 emissions were 91, 209, and 8200 Mg yr-1, implying 2480, 1870, and 1720 head using published emission factors. Plumes fingerprinting identified likely sources including manure storage, cowsheds, and a structure with likely natural gas combustion. NH3 downwind of Chino showed a seasonal variation of a factor of ten, three times larger than literature suggests. Chino husbandry practices and trends in herd size and production were reviewed and unlikely to add seasonality. Higher emission seasonality was proposed as legacy soil emissions, the results of a century of husbandry, supported by airborne remote sensing data showing widespread emissions from neighborhoods that were dairies 15 years prior, and AMOG and MISTIR observations. Seasonal variations provide insights into the implications of global climate change and must be considered when comparing surveys from different seasons.

Remote sensing and in situ measurements of methane and ammonia emissions from a megacity dairy complex: Chino, CA.

Methane (CH4) and ammonia (NH3) directly and indirectly affect the atmospheric radiative balance with the latter leading to aerosol generation. Both have important spectral features in the Thermal InfraRed (TIR) that can be studied by remote sensing, with NH3 allowing discrimination of husbandry from other CH4 sources. Airborne hyperspectral imagery was collected for the Chino Dairy Complex in the Los Angeles Basin as well as in situ CH4, carbon dioxide (CO2) and NH3 data. TIR data showed good spatial agreement with in situ measurements and showed significant emissions heterogeneity between dairies. Airborne remote sensing mapped plume transport for ∼20 km downwind, documenting topographic effects on plume advection. Repeated multiple gas in situ measurements showed that emissions were persistent on half-year timescales. Inversion of one dairy plume found annual emissions of 4.1 × 105 kg CH4, 2.2 × 105 kg NH3, and 2.3 × 107 kg CO2, suggesting 2300, 4000, and 2100 head of cattle, respectively, and Chino Dairy Complex emissions of 42 Gg CH4 and 8.4 Gg NH3 implying ∼200k cows, ∼30% more than Peischl et al. (2013) estimated for June 2010. Far-field data showed chemical conversion and/or deposition of Chino NH3 occurs within the confines of the Los Angeles Basin on a four to six h timescale, faster than most published rates, and likely from higher Los Angeles oxidant loads. Satellite observations from 2011 to 2014 confirmed that observed in situ transport patterns were representative and suggests much of the Chino Dairy Complex emissions are driven towards eastern Orange County, with a lesser amount transported to Palm Springs, CA. Given interest in mitigating husbandry health impacts from air pollution emissions, this study highlights how satellite observations can be leveraged to understand exposure and how multiple gas in situ emissions studies can inform on best practices given that emissions reduction of one gas could increase those of others.

Oil slick morphology derived from AVIRIS measurements of the Deepwater Horizon oil spill: Implications for spatial resolution requirements of remote sensors.

Using fine spatial resolution (~7.6m) hyperspectral AVIRIS data collected over the Deepwater Horizon oil spill in the Gulf of Mexico, we statistically estimated slick lengths, widths and length/width ratios to characterize oil slick morphology for different thickness classes. For all AVIRIS-detected oil slicks (N=52,100 continuous features) binned into four thickness classes (≤50 µm but thicker than sheen, 50-200 µm, 200-1000 µm, and >1000 µm), the median lengths, widths, and length/width ratios of these classes ranged between 22 and 38 m, 7-11 m, and 2.5-3.3, respectively. The AVIRIS data were further aggregated to 30-m (Landsat resolution) and 300-m (MERIS resolution) spatial bins to determine the fractional oil coverage in each bin. Overall, if 50% fractional pixel coverage were to be required to detect oil with thickness greater than sheen for most oil containing pixels, a 30-m resolution sensor would be needed.

Performance evaluation of a 1.6-µm methane DIAL system from ground, aircraft and UAV platforms.

Methane is an efficient absorber of infrared radiation and a potent greenhouse gas with a warming potential 72 times greater than carbon dioxide on a per molecule basis. Development of methane active remote sensing capability using the differential absorption lidar (DIAL) technique enables scientific assessments of the gas emission and impacts on the climate. A performance evaluation of a pulsed DIAL system for monitoring atmospheric methane is presented. This system leverages a robust injection-seeded pulsed Nd:YAG pumped Optical Parametric Oscillator (OPO) laser technology operating in the 1.645 µm spectral band. The system also leverages an efficient low noise, commercially available, InGaAs avalanche photo-detector (APD). Lidar signals and error budget are analyzed for system operation on ground in the range-resolved DIAL mode and from airborne platforms in the integrated path DIAL (IPDA) mode. Results indicate system capability of measuring methane concentration profiles with <1.0% total error up to 4.5 km range with 5 minute averaging from ground. For airborne IPDA, the total error in the column dry mixing ratio is less than 0.3% with 0.1 sec average using ground returns. This system has a unique capability of combining signals from the atmospheric scattering from layers above the surface with ground return signals, which provides methane column measurement between the atmospheric scattering layer and the ground directly. In such case 0.5% and 1.2% total errors are achieved with 10 sec average from airborne platforms at 8 km and 15.24 km altitudes, respectively. Due to the pulsed nature of the transmitter, the system is relatively insensitive to aerosol and cloud interferences. Such DIAL system would be ideal for investigating high latitude methane releases over polar ice sheets, permafrost regions, wetlands, and over ocean during day and night. This system would have commercial potential for fossil fuel leaks detection and industrial monitoring applications.

Comment on "A persistent oxygen anomaly reveals the fate of spilled methane in the deep Gulf of Mexico".

Kessler et al. (Reports, 21 January 2011, p. 312) reported that methane released from the 2010 Deepwater Horizon blowout, approximately 40% of the total hydrocarbon discharge, was consumed quantitatively by methanotrophic bacteria in Gulf of Mexico deep waters over a 4-month period. We find the evidence explicitly linking observed oxygen anomalies to methane consumption ambiguous and extension of these observations to hydrate-derived methane climate forcing premature.

The tidal influence on oil and gas emissions from an abandoned oil well: Nearshore Summerland, California.

Oil and gas emissions were quantified for natural and human sources in nearshore waters off Summerland, California through deployment of custom designed collection tents. Seepage was measured at a repeatedly abandoned well, on the seabed from a caisson located along the historical location of the Treadwell Wharf, where the world's first off-shore oil wells were drilled at the end of the 19th century. Seepage rates at the capped T-10 Well, located in approximately 5m water, showed high correlation to tides. Site emissions were 2.4 and 38.7Lday(-1) oil and gas, respectively. Emissions were measured from two areas of seepage at the T-10 Well Site. Oil and gas ratios were inversely correlated between the two seepage areas, demonstrating connectivity. Data were interpreted in terms of an electronic circuit model of seepage with respect to the time lag between local low tide and peak oil emissions.

Beach tar accumulation, transport mechanisms, and sources of variability at Coal Oil Point, California.

A new field method for tar quantification was used at Coal Oil Point (COP), California to study the mechanisms transporting oil/tar from the nearby COP natural marine hydrocarbon seep field. This method segregates tar pieces into six size classes and assigns them an average mass based on laboratory or direct field measurements. Tar accumulation on the 19,927m(2) survey area was well resolved spatially by recording tar mass along twelve transects segmented into 4-m(2) blocks and then integrating over the survey area. A seasonal trend was apparent in total tar in which summer accumulations were an order of magnitude higher than winter accumulations. Based on multiple regression analyses between environmental data and tar accumulation, 34% of tar variability is explained by a combination of onshore advection via wind and low swell height inhibiting slick dispersion.

Bacterial diversity in marine hydrocarbon seep sediments.

Marine seeps introduce significant amounts of hydrocarbons into oceans and create unusual habitats for microfauna and -flora. In the vicinity of chronic seeps, microbes likely exert control on carbon quality entering the marine food chain and, in turn, hydrocarbons could influence microbial community composition and diversity. To determine the effects of seep oil on marine sediment bacterial communities, we collected sediment piston cores within an active marine hydrocarbon seep zone in the Coal Oil Point Seep Field, at a depth of 22 m in the Santa Barbara Channel, California. Cores were taken adjacent to an active seep vent in a hydrocarbon volcano, on the edge of the volcano, and at the periphery of the area of active seepage. Bacterial community profiles were determined by terminal restriction fragment length polymorphisms (TRFLPs) of 16S ribosomal genes that were polymerase chain reaction (PCR)-amplified with eubacterial primers. Sediment carbon content and C/N ratio increased with oil content. Terminal restriction fragment length polymorphisms suggested that bacterial communities varied both with depth into sediments and with oil concentration. Whereas the apparent abundance of several peaks correlated positively with hydrocarbon content, overall bacterial diversity and richness decreased with increasing sediment hydrocarbon content. Sequence analysis of a clone library generated from sediments collected at the periphery of the seep suggested that oil-sensitive species belong to the gamma Proteobacteria and Holophaga groups. These sequences were closely related to sequences previously recovered from uncontaminated marine sediments. Our results suggest that seep hydrocarbons exert a strong selective pressure on bacterial communities in marine sediments. This selective pressure could, in turn, control the effects of oil on other biota in the vicinity of marine hydrocarbon seeps.

Biochemical effects of petroleum exposure in hornyhead turbot (Pleuronichthys verticalis) exposed to a gradient of sediments collected from a natural petroleum seep in CA, USA.

Concentrations of serum/plasma estradiol, biliary fluorescent aromatic compounds (FACs), levels of hepatic CYP1A expression, and DNA damage were measured in sexually mature hornyhead turbot (Pleuronichthys verticalis) exposed in the laboratory for 7 days to a gradient of sediments collected from a natural petroleum seep in the Santa Barbara Channel. Coal oil point (COP) sediments were homogenized and divided into four treatments containing 0 (sediment from the Orange County Sanitation District's reference location), 33, 66, and 100% (COP) sediments. Sediment concentrations of 20 PAHs ranged from below the detection limit for the 0% COP sediment treatments to 105 microg/g in the 100% treatments with lower molecular weight compounds predominating. Concentrations of biliary FACs were not linear with COP treatment but levels of hepatic DNA damage increased linearly with increasing concentrations of high molecular weight PAHs. Hepatic CYP1A expression was elevated only in the 100% treatments. A reduction of plasma estradiol in male and female fish was observed in all COP exposures. These results demonstrate that acute sediment-only exposure of flatfish to naturally-derived PAHs elicits alterations in biochemical endpoints indicative of PAH bioavailability and adverse effects with different sensitivities.