Cameron McIntyre

Tracking Hydrocarbon Plume Transport and Biodegradation at Deepwater Horizon

Diving into Deep Water The Deepwater Horizon oil spill in the Gulf of Mexico was one of the largest oil spills on record. Its setting at the bottom of the sea floor posed an unanticipated risk as substantial amounts of hydrocarbons leaked into the deepwater column. Three separate cruises identified and sampled deep underwater hydrocarbon plumes that existed in May and June, 2010—before the well head was ultimately sealed. Camilli et al. (p. 201; published online 19 August) used an automated underwater vehicle to assess the dimensions of a stabilized, diffuse underwater plume of oil that was 22 miles long and estimated the daily quantity of oil released from the well, based on the concentration and dimensions of the plume. Hazen et al. (p. 204; published online 26 August) also observed an underwater plume at the same depth and found that hydrocarbon-degrading bacteria were enriched in the plume and were breaking down some parts of the oil. Finally, Valentine et al. (p. 208; published online 16 September) found that natural gas, including propane and ethane, were also present in hydrocarbon plumes. These gases were broken down quickly by bacteria, but primed the system for biodegradation of larger hydrocarbons, including those comprising the leaking crude oil. Differences were observed in dissolved oxygen levels in the plumes (a proxy for bacterial respiration), which may reflect differences in the location of sampling or the aging of the plumes. In late June 2010, the Deepwater Horizon oil plume stretched more than 35 kilometers at a depth of 1100 meters. The Deepwater Horizon blowout is the largest offshore oil spill in history. We present results from a subsurface hydrocarbon survey using an autonomous underwater vehicle and a ship-cabled sampler. Our findings indicate the presence of a continuous plume of oil, more than 35 kilometers in length, at approximately 1100 meters depth that persisted for months without substantial biodegradation. Samples collected from within the plume reveal monoaromatic petroleum hydrocarbon concentrations in excess of 50 micrograms per liter. These data indicate that monoaromatic input to this plume was at least 5500 kilograms per day, which is more than double the total source rate of all natural seeps of the monoaromatic petroleum hydrocarbons in the northern Gulf of Mexico. Dissolved oxygen concentrations suggest that microbial respiration rates within the plume were not appreciably more than 1 micromolar oxygen per day.

Composition and fate of gas and oil released to the water column during the Deepwater Horizon oil spill

Quantitative information regarding the endmember composition of the gas and oil that flowed from the Macondo well during the Deepwater Horizon oil spill is essential for determining the oil flow rate, total oil volume released, and trajectories and fates of hydrocarbon components in the marine environment. Using isobaric gas-tight samplers, we collected discrete samples directly above the Macondo well on June 21, 2010, and analyzed the gas and oil. We found that the fluids flowing from the Macondo well had a gas-to-oil ratio of 1,600 standard cubic feet per petroleum barrel. Based on the measured endmember gas-to-oil ratio and the Federally estimated net liquid oil release of 4.1 million barrels, the total amount of C1-C5 hydrocarbons released to the water column was 1.7 × 1011 g. The endmember gas and oil compositions then enabled us to study the fractionation of petroleum hydrocarbons in discrete water samples collected in June 2010 within a southwest trending hydrocarbon-enriched plume of neutrally buoyant water at a water depth of 1,100 m. The most abundant petroleum hydrocarbons larger than C1-C5 were benzene, toluene, ethylbenzene, and total xylenes at concentrations up to 78 μg L-1. Comparison of the endmember gas and oil composition with the composition of water column samples showed that the plume was preferentially enriched with water-soluble components, indicating that aqueous dissolution played a major role in plume formation, whereas the fates of relatively insoluble petroleum components were initially controlled by other processes.

Detecting the signature of permafrost thaw in Arctic rivers

Climate change induced permafrost thaw in the Arctic is mobilizing ancient dissolved organic carbon (DOC) into headwater streams; however, DOC exported from the mouth of major arctic rivers appears predominantly modern. Here we highlight that ancient (>20,000 years B.P.) permafrost DOC is rapidly utilized by microbes (~50% DOC loss in <7 days) and that permafrost DOC decay rates (0.12 to 0.19 day−1) exceed those for DOC in a major arctic river (Kolyma: 0.09 day−1). Permafrost DOC exhibited unique molecular signatures, including high levels of aliphatics that were rapidly utilized by microbes. As microbes processed permafrost DOC, its distinctive chemical signatures were degraded and converged toward those of DOC in the Kolyma River. The extreme biolability of permafrost DOC and the rapid loss of its distinct molecular signature may explain the apparent contradiction between observed permafrost DOC release to headwaters and the lack of a permafrost signal in DOC exported via major arctic rivers to the ocean.

Utilization of ancient permafrost carbon in headwaters of Arctic fluvial networks

Northern high-latitude rivers are major conduits of carbon from land to coastal seas and the Arctic Ocean. Arctic warming is promoting terrestrial permafrost thaw and shifting hydrologic flowpaths, leading to fluvial mobilization of ancient carbon stores. Here we describe 14C and 13C characteristics of dissolved organic carbon from fluvial networks across the Kolyma River Basin (Siberia), and isotopic changes during bioincubation experiments. Microbial communities utilized ancient carbon (11,300 to >50,000 14C years) in permafrost thaw waters and millennial-aged carbon (up to 10,000 14C years) across headwater streams. Microbial demand was supported by progressively younger (14C-enriched) carbon downstream through the network, with predominantly modern carbon pools subsidizing microorganisms in large rivers and main-stem waters. Permafrost acts as a significant and preferentially degradable source of bioavailable carbon in Arctic freshwaters, which is likely to increase as permafrost thaw intensifies causing positive climate feedbacks in response to on-going climate change.

Widespread dispersal and aging of organic carbon in shallow marginal seas

The occurrence of pre-aged organic carbon (OC) in continental margin surface sediments is a commonly observed phenomenon, yet the nature, sources, and causes of this aged OC remain largely undetermined for many continental shelf settings. Here we present the results of an extensive survey of the abundance and radiocarbon content of OC in surface sediments from the northern Chinese marginal seas. Pre-aged OC is associated with both coarser (>63 µm) and finer (<63 µm) sedimentary components; measurements on specific grain-size fractions reveal that it is especially prevalent within the 20–63 µm fraction of inner shelf sediments. We suggest that organic matter associated with this sortable silt fraction is subject to protracted entrainment in resuspension-deposition loops during which it ages, is modified, and is laterally dispersed, most likely via entrainment within benthic nepheloid layers. This finding highlights the complex dynamics and predepositional history of organic matter accumulating in continental shelf sediments, with implications for our understanding of carbon cycling on continental shelves, development of regional carbon budgets, and interpretation of sedimentary records.

A High-Performance 14C Accelerator Mass Spectrometry System

A new and unique radiocarbon accelerator mass spectrometry (AMS) facility has been constructed at the Woods Hole Oceanographic Institution. The defining characteristic of the new system is its large-gap optical elements that provide a larger-than-standard beam acceptance. Such a system is ideally suited for high-throughput, high-precision measurements of 14C. Details and performance of the new system are presented.

Gas chromatograph-combustion system for 14C-accelerator mass spectrometry

A gas chromatograph-combustion (GC-C) system is described for the introduction of samples as CO(2) gas into a (14)C accelerator mass spectrometry (AMS) system with a microwave-plasma gas ion source. Samples are injected into a gas chromatograph fitted with a megabore capillary column that uses H(2) as the carrier gas. The gas stream from the outlet of the column is mixed with O(2) and Ar gas and passed through a combustion furnace where the H(2) carrier gas and separated components are quantitatively oxidized to CO(2) and H(2)O. Water vapor is removed using a heated nafion dryer. The Ar carries the CO(2) to the ion source. The system is able to separate and oxidize up to 10 microg of compound and transfer the products from 7.6 mL/min of H(2) carrier gas into 0.2-1.0 mL/min of Ar carrier gas. Chromatographic performance and isotopic fidelity satisfy the requirements of the (14)C-AMS system for natural abundance measurements. The system is a significant technical advance for GC-AMS and may be capable of providing an increase in sensitivity for other analytical systems such as an isotope-ratio-monitoring GC/MS.

Low photolability of yedoma permafrost dissolved organic carbon

Vast stores of arctic permafrost carbon that have remained frozen for millennia are thawing, releasing ancient dissolved organic carbon (DOC) to arctic inland waters. Once in arctic waters, DOC can be converted to CO2 and emitted to the atmosphere, accelerating climate change. Sunlight-driven photoreactions oxidize DOC, converting a portion to CO2 and leaving behind a photomodified pool of dissolved organic matter (DOM). Samples from the Kolyma River, its tributaries, and streams draining thawing yedoma permafrost were collected. Irradiation experiments and radiocarbon dating were employed to assess the photolability of ancient permafrost-DOC in natural and laboratory generated samples containing a mix of modern and ancient DOC. Photolabile DOC was always modern, with no measurable photochemical loss of ancient permafrost-DOC. However, optical and ultrahigh resolution mass spectrometric measurements revealed that both modern river DOM and ancient permafrost-DOM were photomodified during the irradiations, converting aromatic compounds to less conjugated compounds. These findings suggest that although sunlight-driven photoreactions do not directly mineralize permafrost-DOC, photomodification of permafrost-DOM chemistry may influence its fate and ecological functions in aquatic systems.

Rapid 14C analysis of dissolved organic carbon in non-saline waters

The radiocarbon content of dissolved organic carbon (DOC) in rivers, lakes, and other non-saline waters can provide valuable information on carbon cycling dynamics in the environment. DOC is typically prepared for 14 C analysis by accelerator mass spectrometry (AMS) either by ultraviolet (UV) oxidation or by freeze-drying and sealed tube combustion. We present here a new method for the rapid analysis of 14 C of DOC using wet chemical oxidation (WCO) and automated headspace sampling of CO 2 . The approach is an adaption of recently developed methods using aqueous persulfate oxidant to determine the δ 13 C of DOC in non-saline water samples and the 14 C content of volatile organic acids. One advantage of the current method over UV oxidation is higher throughput: 22 samples and 10 processing standards can be prepared in one day and analyzed in a second day, allowing a full suite of 14 C processing standards and blanks to be run in conjunction with samples. A second advantage is that there is less potential for cross-contamination between samples.

Online 13C and 14C gas measurements by EA-IRMS–AMS at ETH Zürich

Studies using carbon isotopes to understand the global carbon cycle are critical to identify and quantify sources, sinks, and processes and how humans may impact them. 13C and 14C are routinely measured individually; however, there is a need to develop instrumentation that can perform concurrent online analyses that can generate rich data sets conveniently and efficiently. To satisfy these requirements, we coupled an elemental analyzer to a stable isotope mass spectrometer and an accelerator mass spectrometer system fitted with a gas ion source. We first tested the system with standard materials and then reanalyzed a sediment core from the Bay of Bengal that had been analyzed for 14C by conventional methods. The system was able to produce %C, 13C, and 14C data that were accurate and precise, and suitable for the purposes of our biogeochemistry group. The system was compact and convenient and is appropriate for use in a range of fields of research.