skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Investigations of Aerobic Methane Oxidation in Two Marine Seep Environments: Part 2—Isotopic Kinetics
Abstract During aerobic oxidation of methane (CH4) in seawater, a process which mitigates atmospheric emissions, the12C‐isotopologue reacts with a slightly greater rate constant than the13C‐isotopologue, leaving the residual CH4isotopically fractionated. Prior studies have attempted to exploit this systematic isotopic fractionation from methane oxidation to quantify the extent that a CH4pool has been oxidized in seawater. However, cultivation‐based studies have suggested that isotopic fractionation fundamentally changes as a microbial population blooms in response to an influx of reactive substrates. Using a systematic mesocosm incubation study with recently collected seawater, here we investigate the fundamental isotopic kinetics of aerobic CH4oxidation during a microbial bloom. As detailed in a companion paper, seawater samples were collected from seep fields in Hudson Canyon, U.S. Atlantic Margin, and atop Woolsey Mound (also known as Sleeping Dragon) which is part of lease block MC118 in the northern Gulf of Mexico, and used in these investigations. The results from both Hudson Canyon and MC118 show that in these natural environments isotopic fraction for CH4oxidation follows a first‐order kinetic process. The results also show that the isotopic fractionation factor remains constant during this methanotrophic bloom once rapid CH4oxidation begins and that the magnitude of the fractionation factor appears correlated with the first‐order reaction rate constant. These findings greatly simplify the use of natural stable isotope changes in CH4to assess the extent that CH4is oxidized in seawater following seafloor release.  more » « less
Award ID(s):
1756947
PAR ID:
10455351
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Journal of Geophysical Research: Oceans
Volume:
124
Issue:
11
ISSN:
2169-9275
Page Range / eLocation ID:
p. 8392-8399
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Microbial aerobic oxidation is known to be a significant sink of marine methane (CH4), contributing to the relatively minor atmospheric release of this greenhouse gas over vast stretches of the ocean. However, the chemical kinetics of aerobic CH4oxidation are not well established, making it difficult to predict and assess the extent that CH4is oxidized in seawater following seafloor release. Here we investigate the kinetics of aerobic CH4oxidation using mesocosm incubations of fresh seawater samples collected from seep fields in Hudson Canyon, U.S. Atlantic Margin and MC118, Gulf of Mexico to gain a fundamental chemical understanding of this CH4sink. The goals of this investigation were to determine the response or lag time following CH4release until more rapid oxidation begins, the reaction order, and the stoichiometry of reactants utilized (i.e., CH4, oxygen, nitrate, phosphate, trace metals) during CH4oxidation. The results for both Hudson Canyon and MC118 environments show that CH4oxidation rates sharply increased within less than one month following the CH4inoculation of seawater. However, the exact temporal characteristics of this more rapid CH4oxidation varied based on location, possibly dependent on the local circulation and biogeochemical conditions at the point of seawater collection. The data further suggest that methane oxidation behaves as a first‐order kinetic process and that the reaction rate constant remains constant once rapid CH4oxidation begins. 
    more » « less
  2. Abstract Microbial aerobic methane oxidation is an important sink for aquatic methane worldwide. Despite its importance to global methane fluxes, few aerobic methane oxidation rates have been obtained in freshwater or marine environments without imposing changes to the microbial community through use of ex situ methods. A novel in situ incubation method for continuous time‐series measurements was used in Jordan Lake, North Carolina, during 2020–2021, to determine reaction kinetics for aerobic methane oxidation rates across a wide range of naturally varying methane (55–1833 nM) and dissolved oxygen (DO; 28–366 μM) concentrations and temperatures (17–30°C). Methane oxidation began immediately at the start of each of 21 incubations and methane oxidation rates were 1storder with respect to methane. The data density allowed for accurate calculation of 1st‐order rate constants,k, that ranged from 0.018 to 0.462 h−1(R2 > 0.967). Addition of ammonium (20–45 μM) to natural concentrations ranging from 0.057 to 2.4 μM did not change aerobic methane oxidation rate kinetics, suggesting that the natural population of aerobic methane oxidizers in this eutrophic lake was not nitrogen limited. Values ofkinversely correlated most strongly with initial DO concentrations (R2 = 0.82) rather than temperature. Values forkincreased with Julian day throughout our sampling period, suggesting seasonal influences on methane oxidation via responses to geochemical changes or shifts in microbial community abundance and composition. These experiments demonstrate a high variability in the enzymatic capacity for 1st‐order methane oxidation rates in this eutrophic lake that is tightly and inversely coupled to oxygen concentrations. Measurements of in situ aerobic methane oxidation rate constants allow for the direct quantification and modeling of the microbial community's capacity for methane oxidation over a wide range of natural methane concentrations. 
    more » « less
  3. Inland waters are the largest natural source of methane (CH 4 ) to the atmosphere, yet the contribution from small streams to this flux is not clearly defined. To fully understand CH 4 emissions from streams and rivers, we must consider the relative importance of CH 4 emission pathways, the prominence of microbially-mediated production and oxidation of CH 4 , and the isotopic signature of emitted CH 4 . Here, we construct a complete CH 4 emission budgets for four lowland headwater streams by quantifying diffusive CH 4 emissions and comparing them to previously published rates of ebullitive emissions. We also examine the isotopic composition of CH 4 along with the sediment microbial community to investigate production and oxidation across the streams. We find that all four streams are supersaturated with respect to CH 4 with diffusive emissions accounting for approximately 78–100% of total CH 4 emissions. Isotopic and microbial data suggest CH 4 oxidation is prevalent across the streams, depleting approximately half of the dissolved CH 4 pool before emission. We propose a conceptual model of CH 4 production, oxidation, and emission from small streams, where the dominance of diffusive emissions is greater compared to other aquatic ecosystems, and the impact of CH 4 oxidation is observable in the emitted isotopic values. As a result, we suggest the CH 4 emitted from small streams is isotopically heavy compared to lentic ecosystems. Our results further demonstrate streams are important components of the global CH 4 cycle yet may be characterized by a unique pattern of cycling and emission that differentiate them from other aquatic ecosystems. 
    more » « less
  4. Abstract The ongoing global temperature rise enhances permafrost thaw in the Arctic, allowing Pleistocene‐aged frozen soil organic matter to become available for microbial degradation and production of greenhouse gases, particularly methane. Here, we examined the extent and mechanism of anaerobic oxidation of methane (AOM) in the sediments of four interior Alaska thermokarst lakes, which formed and continue to expand as a result of ice‐rich permafrost thaw. In cores of surface (~ 1 m) lake sediments we quantified methane production (methanogenesis) and AOM rates using anaerobic incubation experiments in low (4°C) and high (16°C) temperatures. Methanogenesis rates were measured by the accumulation of methane over ~ 90 d, whereas AOM rates were measured by adding labeled‐13CH4and measuring the produced dissolved inorganic13C. Our results demonstrate that while methanogenesis was vigorous in these anoxic sediments, AOM was lower by two orders of magnitude. In almost all sediment depths and temperatures, AOM rates remained less than 2% of the methanogenesis rates. Experimental evidence indicates that the AOM is strongly related to methanogens, as the addition of a methanogens' inhibitor prevented AOM. Variety of electron acceptor additions did not stimulate AOM, and methanotrophs were scarcely detected. These observations suggest that the AOM signals in the incubation experiments might be a result of enzymatic reversibility (“back‐flux”) during CH4production, rather than thermodynamically favorable AOM. Regardless of the mechanism, the quantitative results show that near surface (< 1‐m) thermokarst sediments in interior Alaska have little to no buffer mechanisms capable of attenuating methane production in a warming climate. 
    more » « less
  5. Carbon dioxide (CO 2 ) supersaturation in lakes and rivers worldwide is commonly attributed to terrestrial–aquatic transfers of organic and inorganic carbon (C) and subsequent, in situ aerobic respiration. Methane (CH 4 ) production and oxidation also contribute CO 2 to freshwaters, yet this remains largely unquantified. Flood pulse lakes and rivers in the tropics are hypothesized to receive large inputs of dissolved CO 2 and CH 4 from floodplains characterized by hypoxia and reducing conditions. We measured stable C isotopes of CO 2 and CH 4 , aerobic respiration, and CH 4 production and oxidation during two flood stages in Tonle Sap Lake (Cambodia) to determine whether dissolved CO 2 in this tropical flood pulse ecosystem has a methanogenic origin. Mean CO 2 supersaturation of 11,000 ± 9,000 μ atm could not be explained by aerobic respiration alone. 13 C depletion of dissolved CO 2 relative to other sources of organic and inorganic C, together with corresponding 13 C enrichment of CH 4 , suggested extensive CH 4 oxidation. A stable isotope-mixing model shows that the oxidation of 13 C depleted CH 4 to CO 2 contributes between 47 and 67% of dissolved CO 2 in Tonle Sap Lake. 13 C depletion of dissolved CO 2 was correlated to independently measured rates of CH 4 production and oxidation within the water column and underlying lake sediments. However, mass balance indicates that most of this CH 4 production and oxidation occurs elsewhere, within inundated soils and other floodplain habitats. Seasonal inundation of floodplains is a common feature of tropical freshwaters, where high reported CO 2 supersaturation and atmospheric emissions may be explained in part by coupled CH 4 production and oxidation. 
    more » « less