Elevated levels of radiocarbon in methane dissolved in seawater reveal likely local contamination from nuclear powered vessels.

Measurements of the natural radiocarbon content of methane (14C-CH4) dissolved in seawater and freshwater have been used to investigate sources and dynamics of methane. However, during investigations along the Atlantic, Pacific, and Arctic Ocean Margins of the United States, as well as in the North American Great Lakes, some samples revealed highly elevated 14C-CH4 values, as much as 4-5 times above contemporary atmospheric 14C-CH4 levels. Natural production of the 14CH4 isotopologue is too low to cause these observations nor can it explain the variations in location and depth. Numerous lab and field validation tests and blanks, as well as the relatively small number of samples that display these elevated values, all suggest that these signals are not derived from an unknown procedural issue. Here we suggest that the byproducts of nuclear power generation include localized discharges of the 14CH4 isotopologue into marine and aquatic environments, severely altering the measured 14C-CH4 isotopic signals. Since several of our sample sites are distant from on-land nuclear powerplants, we conduct further calculations concluding that the most elevated anomalies in 14C-CH4 likely originate with discharge from nuclear-powered vessels.

Limited contribution of ancient methane to surface waters of the U.S. Beaufort Sea shelf.

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon-sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere.

Aqueous Mesocosm Techniques Enabling the Real-Time Measurement of the Chemical and Isotopic Kinetics of Dissolved Methane and Carbon Dioxide.

Previous studies of microbially mediated methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on what factor(s) are limiting in these types of environments. These factors include the availability of methane, O2, trace metals, nutrients, the density of cell population, and the influence that CO2 production may have on pH. To look at this process in its entirety, we developed an automated mesocosm incubation system with a Dissolved Gas Analysis System (DGAS) coupled to a myriad of analytical tools to monitor chemical changes during methane oxidation. Here, we present new high temporal resolution techniques for investigating dissolved methane and carbon dioxide concentrations and stable isotopic dynamics during aqueous mesocosm and pure culture incubations. These techniques enable us to analyze the gases dissolved in solution and are nondestructive to both the liquid media and the analyzed gases enabling the investigation of a mesocosm or pure culture experiment in a completely closed system, if so desired.

Current Magnitude and Mechanisms of Groundwater Discharge in the Arctic: Case Study from Alaska.

To better understand groundwater-surface water dynamics in high latitude areas, we conducted a field study at three sites in Alaska with varying permafrost coverage. The natural groundwater tracer ((222)Rn, radon) was used to evaluate groundwater discharge, and electrical resistivity tomography (ERT) was used to examine subsurface mixing dynamics. Different controls govern groundwater discharge at these sites. In areas with sporadic permafrost (Kasitsna Bay), the major driver of submarine groundwater discharge is tidal pumping, due to the large tidal oscillations, whereas at Point Barrow, a site with continuous permafrost and small tidal amplitudes, fluxes are mostly affected by seasonal permafrost thawing. Extended areas of low resistivity in the subsurface alongshore combined with high radon in surface water suggests that groundwater-surface water interactions might enhance heat transport into deeper permafrost layers promoting permafrost thawing, thereby enhancing groundwater discharge.

Methane transport from the active layer to lakes in the Arctic using Toolik Lake, Alaska, as a case study.

Methane emissions in the Arctic are important, and may be contributing to global warming. While methane emission rates from Arctic lakes are well documented, methods are needed to quantify the relative contribution of active layer groundwater to the overall lake methane budget. Here we report measurements of natural tracers of soil/groundwater, radon, and radium, along with methane concentration in Toolik Lake, Alaska, to evaluate the role active layer water plays as an exogenous source for lake methane. Average concentrations of methane, radium, and radon were all elevated in the active layer compared with lake water (1.6 × 10(4) nM, 61.6 dpm⋅m(-3), and 4.5 × 10(5) dpm⋅m(-3) compared with 1.3 × 10(2) nM, 5.7 dpm⋅m(-3), and 4.4 × 10(3) dpm⋅m(-3), respectively). Methane transport from the active layer to Toolik Lake based on the geochemical tracer radon (up to 2.9 g⋅m(-2)⋅y(-1)) can account for a large fraction of methane emissions from this lake. Strong but spatially and temporally variable correlations between radon activity and methane concentrations (r(2) > 0.69) in lake water suggest that the parameters that control methane discharge from the active layer also vary. Warming in the Arctic may expand the active layer and increase the discharge, thereby increasing the methane flux to lakes and from lakes to the atmosphere, exacerbating global warming. More work is needed to quantify and elucidate the processes that control methane fluxes from the active layer to predict how this flux might change in the future and to evaluate the regional and global contribution of active layer water associated methane inputs.

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.

Assessment of the spatial and temporal variability of bulk hydrocarbon respiration following the Deepwater Horizon oil spill.

Following the Deepwater Horizon blowout, the respiration of hydrocarbons dissolved and trapped in the deep and intermediate waters of the Gulf of Mexico imparted a significant reduction in dissolved oxygen (DO) concentration and stimulated a bloom of bacteria biomass. The investigation of 1316 DO profiles measured from 11 May until 20 September 2010 revealed the spatial and temporal variability of bulk hydrocarbon respiration in these deep and intermediate plumes. These analyses suggest that while there were occasional reversals in direction, the general movement of these plumes was toward the southwest and that the cumulative loss of DO peaked from 14 August through 18 September at a value of 18.9 ± 3.8 Gmol. These oxygen-based analyses were extended to determine a first-order estimate of the total release of hydrocarbon mass to the environment that must be less than or equal to the true release based on the inherent assumptions; these analyses estimate a total environmental release of 0.47 ± 0.09 Tg of hydrocarbons. These analyses estimate a total mass of 0.18 ± 0.05 Tg hydrocarbons in the plume layers fully respired to CO(2), 0.10 ± 0.08 Tg hydrocarbons incorporated into biomass, and the biomass/hydrocarbon conversion efficiency of 0.36 ± 0.11 mg biomass/mg hydrocarbon. These analyses also suggest that methane was the dominant hydrocarbon controlling the bulk respiration rates, that the rates peaked around 11 July, and that the addition of dispersants to the wellhead effectively accelerated hydrocarbon respiration.

Chemical data quantify Deepwater Horizon hydrocarbon flow rate and environmental distribution.

Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways (i.e., in deep subsurface plumes, in the initial surface slick, and in the atmosphere) during the Deepwater Horizon oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. Although readily soluble hydrocarbons made up ∼25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ∼69% of the deep plume mass; only ∼31% of the deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to assess release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8 ± 1.9) × 10(6) kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) × 10(6) kg/d derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) × 10(6) kg/d derived using physical and optical methods.

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

Methane was the most abundant hydrocarbon released during the 2010 Deepwater Horizon oil spill in the Gulf of Mexico. Beyond relevancy to this anthropogenic event, this methane release simulates a rapid and relatively short-term natural release from hydrates into deep water. Based on methane and oxygen distributions measured at 207 stations throughout the affected region, we find that within ~120 days from the onset of release ~3.0 × 10(10) to 3.9 × 10(10) moles of oxygen were respired, primarily by methanotrophs, and left behind a residual microbial community containing methanotrophic bacteria. We suggest that a vigorous deepwater bacterial bloom respired nearly all the released methane within this time, and that by analogy, large-scale releases of methane from hydrate in the deep ocean are likely to be met by a similarly rapid methanotrophic response.

Propane respiration jump-starts microbial response to a deep oil spill.

The Deepwater Horizon event resulted in suspension of oil in the Gulf of Mexico water column because the leakage occurred at great depth. The distribution and fate of other abundant hydrocarbon constituents, such as natural gases, are also important in determining the impact of the leakage but are not yet well understood. From 11 to 21 June 2010, we investigated dissolved hydrocarbon gases at depth using chemical and isotopic surveys and on-site biodegradation studies. Propane and ethane were the primary drivers of microbial respiration, accounting for up to 70% of the observed oxygen depletion in fresh plumes. Propane and ethane trapped in the deep water may therefore promote rapid hydrocarbon respiration by low-diversity bacterial blooms, priming bacterial populations for degradation of other hydrocarbons in the aging plume.