Table of Contents

• Coverage
• Dataset Description
  • Methods & Sampling
  • Data Processing Description
• Data Files
• Related Publications
• Parameters
• Instruments
• Deployments
• Project Information
• Funding

Measurements of natural radiocarbon of DIC, DIC concentration, pH, and [CH4] in Hudson Canyon, northern US Atlantic Margin.

Methane concentration data was published by Weinstein et al. (2016) and Leonte et al., (2017).
The DIC and pH data are published as: Garcia-Tigreros, F. and Kessler, J.D. (2018)

Underway data for cruise EN541 was published and can be access at R2R: https://doi.org/10.7284/903242

Methodology:
Dissolved inorganic carbon concentration ([DIC]) samples were measured by acidification and subsequent release of CO2 with a CO2 cavity-ringdown spectrometer (CRDS; Picarro G1101-i) detector to an accuracy and precision better than ± 3 umol/kg. Precision is based on a set of 15 duplicates. Accuracy is based on certified reference materials prepared at the Scripps Institution of Oceanography of the University of California, San Diego.

Samples for pH were measured spectrophotometrically on board using an Agilent Cary 100 UV-Visible spectrophotometer and m-cresol purple dye (Clayton and Byrne, 1993; Liu et al., 2011). The pH values are reported on the total scale with a precision better than 0.0002 based on duplicate measurements. The estimated accuracy of spectrophotometric pH is better than 0.002.

Natural radiocarbon samples of DIC (∆14C-DIC) were analyzed at the W. M. Keck Carbon Cycle Accelerator Mass Spectrometry Laboratory at the University of California, Irvine. The accuracy and precision of the ∆14C-DIC measurements is 0.1‰ and 1.7‰, respectively.

Sampling and analytical procedures: 
Discrete seawater samples were collected inside Hudson Canyon, US Atlantic Margin aboard the R/V Endeavor from 9 - 13 of July 2014. A total 19 stations and 216 samples were collected along Hudson Canyon and another station was sampled outside the canyon (station E2-HC2). Samples were collected from a bottle Rosette following the procedures in SOP 1 and 6b in Dickson et al., (2007).

[DIC] samples were collected in acid washed and combusted 120 mL serum vials. Vials were allowed to overflow three times their volume, poisoned with 50 uL of a 55 uM HgCl2, capped, and store at 4 degrees C until analysis.

∆14C-DIC samples were collected in combusted 1L borosilicate bottles, poisoned with 200 uL of a 55 uM HgCl2, sealed and stored in the dark at room temperature until isotope analysis.

CH4 concentration analyses were collected by filling 60, 120, or 160 mL glass serum vials. Vials were filled from the bottom with a length of 1/4" Tygon tubing. Vials were flushed with seven vial volumes of seawater to expel any bubbles and ensure collection of a clean sample, and then were sealed with butyl rubber stoppers taking care not to introduce bubbles during sealing. Immediately after sealing, a 10 mL headspace of ultrahigh purity nitrogen was introduced, displacing an equal volume of water, and the samples were preserved by adding 25 uL of a saturated solution of mercuric chloride. The vials were stored inverted to minimize diffusive gas exchange through the butyl rubber stopper.

CH4 concentration measurements were performed using an Agilent 6850 gas chromatograph with a flame ionization detector (GC-FID) following established protocols reported in Weinstein et al. (2016). The uncertainty associated with these measurements was 5.2% based on duplicate measurements.

BCO-DMO Processing:
- modified parameter names to conform with BCO-DMO naming conventions;
- created date/time column formatted to ISO8601 standard.

NSF Award Abstract:
Roughly 8 billion moles of methane (CH4) were emitted in 83 days during the Deepwater Horizon disaster in the northern Gulf of Mexico in 2010. Interestingly, none of this CH4 was emitted to the atmosphere, but instead stayed dissolved and suspended as "plume" or "intrusion" layers approximately 1000m below the ocean surface. Based on measurements of CH4 concentration and oxidation rates, dissolved oxygen anomalies, and microbial community structure as well as a CH4 geochemical model, it was determined that all the CH4 emitted during this disaster was respired within 120 days of the initial well blowout. In addition, the methanotrophic bacteria responsible for the oxidation of this CH4 appeared to experience all stages of microbial growth, limited only by the availability of CH4. This finding suggests that releases of CH4 into deepwater, be them anthropogenic or natural, will have minimal direct influence on the radiative budget of the atmosphere.

The major weakness in these previous investigations is that CH4 related parameters were only measured at the beginning (May - June 2010) and end (September - October 2010) of this massive CH4 feast, primarily because the rapid demise of CH4 was unanticipated. Thus, the time- and growth phase-dependent understanding of the kinetics of this bloom response is only based on model interpolation between endpoints. A more complete, and measurement-based, understanding of the chemical kinetics is necessary to predict an oceanographic environment's ability to respire large CH4 perturbations. And while measurements of CH4 stable isotopes in theory can be used to assess the extent that the released CH4 has been oxidized, this kinetic isotope effect can only be used in a quantitative fashion if it is known how the isotopic fractionation factor changes with varying chemical and temperature conditions and throughout all stages of the microbial bloom.

In this study, researchers at the Texas A & M University will test two fundamental hypotheses relating to aerobic CH4 oxidation and ultimately produce a thorough characterization of the time-, growth phase-, and temperature-dependency of CH4 oxidation rates, oxidation rate constants, and isotopic fractionation factors. Hypothesis 1: Excluding mixing processes, the bacterial response to a large CH4 perturbation will be limited primarily by the availability of CH4 or dissolved oxygen. Hypothesis 2: Without knowing the stage of microbial growth, measurements of natural stable isotopes of CH4 and dissolved carbon (organic and/or inorganic) cannot be used to assess the extent of CH4 oxidation in situations of large CH4 perturbations. In order to test these hypotheses, with the goal of disproving hypothesis 2, a suite of mesocosm and pure culture incubations will be conducted. Throughout these incubations, concentrations of CH4 and dissolved inorganic carbon as well as their 13C isotopes will be measured in extremely high resolution with new equipment and experimental designs. In addition, dissolved oxygen, nutrient concentrations, trace metals, CH4 oxidation rates, and microbial community structure will be measured.

Broader Impacts. In addition to the normal dissemination of results in publications, meeting presentations, and on a project web site, this work will have strong educational and research impacts with close interactions between the PIs, postdoctoral scholar, graduate student, and undergraduate researchers with collaborations between Texas A&M University and the University of California Santa Barbara. The students will have extended visits at each lab for skill development, knowledge transfer, and general academic growth. During 2010, an informal collaboration was established with Ms. Vicki Soutar, a high school science teacher in Watkinsville, GA, to develop high school science laboratory exercises using real scientific data. This proposed project will involve Ms. Soutar to formalize, enhance, extend, and disseminate the products of this collaboration