Pohlman John W.

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Pohlman

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John W.

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0000-0002-3563-4586

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Anaerobic methane oxidation in low-organic content methane seep sediments

(Elsevier Ltd., 2013-02-04) Pohlman, John W. ; Riedel, Michael ; Bauer, James E. ; Canuel, Elizabeth A. ; Paull, Charles K. ; Lapham, Laura L. ; Grabowski, Kenneth S. ; Coffin, Richard B. ; Spence, George D.

Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8 m of sediment contains <0.4 wt.% total organic carbon (OC) and primarily consists of glacially-derived material that was deposited 14,900–15,900 yrs BP during the retreat of the late Quaternary Cordilleran Ice Sheet. We hypothesize this aged and exceptionally low-OC content sedimentary OM is biologically refractory, thereby limiting degradation of non-methane OM by sulfate reduction and maximizing methane consumption by sulfate-dependent AOM. A radiocarbon-based dissolved inorganic carbon (DIC) isotope mass balance model demonstrates that respired DIC in sediment pore fluids is derived from a fossil carbon source that is devoid of 14C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.
Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico

(Elsevier B.V., 2008-05-10) Pohlman, John W. ; Ruppel, Carolyn D. ; Hutchinson, Deborah R. ; Downer, R. ; Coffin, Richard B.

Pore waters extracted from 18 piston cores obtained on and near a salt-cored bathymetric high in Keathley Canyon lease block 151 in the northern Gulf of Mexico contain elevated concentrations of chloride (up to 838 mM) and have pore water chemical concentration profiles that exhibit extensive departures (concavity) from steady-state (linear) diffusive equilibrium with depth. Minimum δ13C dissolved inorganic carbon (DIC) values of −55.9‰ to −64.8‰ at the sulfate–methane transition (SMT) strongly suggest active anaerobic oxidation of methane (AOM) throughout the study region. However, the nonlinear pore water chemistry-depth profiles make it impossible to determine the vertical extent of active AOM or the potential role of alternate sulfate reduction pathways. Here we utilize the conservative (non-reactive) nature of dissolved chloride to differentiate the effects of biogeochemical activity (e.g., AOM and/or organoclastic sulfate reduction) relative to physical mixing in high salinity Keathley Canyon sediments. In most cases, the DIC and sulfate concentrations in pore waters are consistent with a conservative mixing model that uses chloride concentrations at the seafloor and the SMT as endmembers. Conservative mixing of pore water constituents implies that an undetermined physical process is primarily responsible for the nonlinearity of the pore water-depth profiles. In limited cases where the sulfate and DIC concentrations deviated from conservative mixing between the seafloor and SMT, the δ13C-DIC mixing diagrams suggest that the excess DIC is produced from a 13C-depleted source that could only be accounted for by microbial methane, the dominant form of methane identified during this study. We conclude that AOM is the most prevalent sink for sulfate and that it occurs primarily at the SMT at this Keathley Canyon site.
Focused fluid flow along the Nootka fault zone and continental slope, explorer-Juan de Fuca Plate Boundary

(American Geophysical Union, 2020-08-07) Riedel, Michael ; Rohr, Kristin Marie Michener ; Spence, George D. ; Kelley, Deborah S. ; Delaney, John R. ; Lapham, Laura L. ; Pohlman, John W. ; Hyndman, Roy D. ; Willoughby, Ele C.

Geophysical and geochemical data indicate there is abundant fluid expulsion in the Nootka fault zone (NFZ) between the Juan de Fuca and Explorer plates and the Nootka continental slope. Here we combine observations from >20 years of investigations to demonstrate the nature of fluid‐flow along the NFZ, which is the seismically most active region off Vancouver Island. Seismicity reaching down to the upper mantle is linked to near‐seafloor manifestation of fluid flow through a network of faults. Along the two main fault traces, seismic reflection data imaged bright spots 100–300 m below seafloor that lie above changes in basement topography. The bright spots are conformable to sediment layering, show opposite‐to‐seafloor reflection polarity, and are associated with frequency reduction and velocity push‐down indicating the presence of gas in the sediments. Two seafloor mounds ~15 km seaward of the Nootka slope are underlain by deep, nonconformable high‐amplitude reflective zones. Measurements in the water column above one mound revealed a plume of warm water, and bottom‐video observations imaged hydrothermal vent system biota. Pore fluids from a core at this mound contain predominately microbial methane (C1) with a high proportion of ethane (C2) yielding C1/C2 ratios <500 indicating a possible slight contribution from a deep source. We infer the reflective zones beneath the two mounds are basaltic intrusions that create hydrothermal circulation within the overlying sediments. Across the Nootka continental slope, gas hydrate‐related bottom‐simulating reflectors are widespread and occur at depths indicating heat flow values of 80–90 mW/m2.
Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment.

(Wiley Open Access, 2019-02-10) Wang, Faming ; Kroeger, Kevin D. ; Gonneea, Meagan E. ; Pohlman, John W. ; Tang, Jianwu

Coastal wetlands are a significant carbon (C) sink since they store carbon in anoxic soils. This ecosystem service is impacted by hydrologic alteration and management of these coastal habitats. Efforts to restore tidal flow to former salt marshes have increased in recent decades and are generally associated with alteration of water inundation levels and salinity. This study examined the effect of water level and salinity changes on soil organic matter decomposition during a 60‐day incubation period. Intact soil cores from impounded fresh water marsh and salt marsh were incubated after addition of either sea water or fresh water under flooded and drained water levels. Elevating fresh water marsh salinity to 6 to 9 ppt enhanced CO2 emission by 50%−80% and most typically decreased CH4 emissions, whereas, decreasing the salinity from 26 ppt to 19 ppt in salt marsh soils had no effect on CO2 or CH4 fluxes. The effect from altering water levels was more pronounced with drained soil cores emitting ~10‐fold more CO2 than the flooded treatment in both marsh sediments. Draining soil cores also increased dissolved organic carbon (DOC) concentrations. Stable carbon isotope analysis of CO2 generated during the incubations of fresh water marsh cores in drained soils demonstrates that relict peat OC that accumulated when the marsh was saline was preferentially oxidized when sea water was introduced. This study suggests that restoration of tidal flow that raises the water level from drained conditions would decrease aerobic decomposition and enhance C sequestration. It is also possible that the restoration would increase soil C decomposition of deeper deposits by anaerobic oxidation, however this impact would be minimal compared to lower emissions expected due to the return of flooding conditions.
Ideas and perspectives: a strategic assessment of methane and nitrous oxide measurements in the marine environment

(European Geosciences Union, 2020-11-26) Wilson, Samuel T. ; Al-Haj, Alia N. ; Bourbonnais, Annie ; Frey, Claudia ; Fulweiler, Robinson W. ; Kessler, John D. ; Marchant, Hannah K. ; Milucka, Jana ; Ray, Nicholas E. ; Suntharalingam, Parvadha ; Thornton, Brett F. ; Upstill-Goddard, Robert C. ; Weber, Thomas S. ; Arévalo-Martínez, Damian L. ; Bange, Hermann W. ; Benway, Heather M. ; Bianchi, Daniele ; Borges, Alberto V. ; Chang, Bonnie X. ; Crill, Patrick M. ; del Valle, Daniela A. ; Farías, Laura ; Joye, Samantha B. ; Kock, Annette ; Labidi, Jabrane ; Manning, Cara C. ; Pohlman, John W. ; Rehder, Gregor ; Sparrow, Katy J. ; Tortell, Philippe D. ; Treude, Tina ; Valentine, David L. ; Ward, Bess B. ; Yang, Simon ; Yurganov, Leonid N.

In the current era of rapid climate change, accurate characterization of climate-relevant gas dynamics – namely production, consumption, and net emissions – is required for all biomes, especially those ecosystems most susceptible to the impact of change. Marine environments include regions that act as net sources or sinks for numerous climate-active trace gases including methane (CH4) and nitrous oxide (N2O). The temporal and spatial distributions of CH4 and N2O are controlled by the interaction of complex biogeochemical and physical processes. To evaluate and quantify how these mechanisms affect marine CH4 and N2O cycling requires a combination of traditional scientific disciplines including oceanography, microbiology, and numerical modeling. Fundamental to these efforts is ensuring that the datasets produced by independent scientists are comparable and interoperable. Equally critical is transparent communication within the research community about the technical improvements required to increase our collective understanding of marine CH4 and N2O. A workshop sponsored by Ocean Carbon and Biogeochemistry (OCB) was organized to enhance dialogue and collaborations pertaining to marine CH4 and N2O. Here, we summarize the outcomes from the workshop to describe the challenges and opportunities for near-future CH4 and N2O research in the marine environment.
Oxygenation of a karst subterranean estuary during a tropical cyclone: mechanisms and implications for the carbon cycle

(Association for the Sciences of Limnology and Oceanography, 2022-09-23) Brankovits, David ; Pohlman, John W. ; Lapham, Laura L.

Seasonal precipitation affects carbon turnover and methane accumulation in karst subterranean estuaries, the region of coastal carbonate aquifers where hydrologic and biogeochemical processes regulate material exchange between the land and ocean. However, the impact that tropical cyclones exert on subsurface carbon cycling within karst landscapes is poorly understood. Here, we present 5‐month‐long hydrologic and chemical records from 1 and 2 km inland from the coastline within the Ox Bel Ha Cave System in the northeastern Yucatan Peninsula. The record encompasses wet and dry seasons and includes the impact of rainfall during the development of Tropical Storm Hanna in October 2014. Methane accumulated in highest concentrations at the inland site, especially during the wet season preceding the storm. Intense rainfall led to episodic increases in water level and salinity shifts at both sites, indicating a spatially widespread hydrologic response. The most profound storm effect was a ~ 0.8 mg L−1 pulse of dissolved oxygen that declined to zero within 2 weeks and corresponded with a reduction of methane. A positive shift in methane's stable carbon isotope content from −62.6‰ ± 0.6‰ before the storm to −44.0‰ ± 2.4‰ after the storm indicates microbial methane oxidation was a mechanism for the loss of groundwater methane. Post‐storm methane concentrations did not recover to pre‐storm levels during the observation period, suggesting tropical cyclones have long‐lasting (months) effects on the carbon cycle. Compared to seasonal effects, mixing and oxygen inputs during storm‐induced hydrologic forcing have an outsized biogeochemical influence within stratified coastal aquifers.
Radiocarbon age-offsets in an arctic lake reveal the long-term response of permafrost carbon to climate change

(John Wiley & Sons, 2014-08-22) Gaglioti, Benjamin V. ; Mann, Daniel H. ; Jones, Benjamin M. ; Pohlman, John W. ; Kunz, Michael L. ; Wooller, Matthew J.

Continued warming of the Arctic may cause permafrost to thaw and speed the decomposition of large stores of soil organic carbon (OC), thereby accentuating global warming. However, it is unclear if recent warming has raised the current rates of permafrost OC release to anomalous levels or to what extent soil carbon release is sensitive to climate forcing. Here we use a time series of radiocarbon age-offsets (14C) between the bulk lake sediment and plant macrofossils deposited in an arctic lake as an archive for soil and permafrost OC release over the last 14,500 years. The lake traps and archives OC imported from the watershed and allows us to test whether prior warming events stimulated old carbon release and heightened age-offsets. Today, the age-offset (2 ka; thousand of calibrated years before A.D. 1950) and the depositional rate of ancient OC from the watershed into the lake are relatively low and similar to those during the Younger Dryas cold interval (occurring 12.9–11.7 ka). In contrast, age-offsets were higher (3.0–5.0 ka) when summer air temperatures were warmer than present during the Holocene Thermal Maximum (11.7–9.0 ka) and Bølling-Allerød periods (14.5–12.9 ka). During these warm times, permafrost thaw contributed to ancient OC depositional rates that were ~10 times greater than today. Although permafrost OC was vulnerable to climate warming in the past, we suggest surface soil organic horizons and peat are presently limiting summer thaw and carbon release. As a result, the temperature threshold to trigger widespread permafrost OC release is higher than during previous warming events.
Mass fractionation of noble gases in synthetic methane hydrate : implications for naturally occurring gas hydrate dissociation

(Elsevier B.V., 2012-09-29) Hunt, Andrew G. ; Stern, Laura A. ; Pohlman, John W. ; Ruppel, Carolyn D. ; Moscati, Richard J. ; Landis, Gary P.

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean–atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.
Methane sources in gas hydrate-bearing cold-seeps : evidence from radiocarbon and stable isotopes

( 2009-06-16) Pohlman, John W. ; Bauer, James E. ; Canuel, Elizabeth A. ; Grabowski, Kenneth S. ; Knies, D. L. ; Mitchell, C. S. ; Whiticar, M. J. ; Coffin, Richard B.

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (14C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its 14C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (≤1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations. In combination with δ13C- and δD-methane measurements, we also determine the extent to which the low, but detectable, amounts of 14C (~ 1-2 percent modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A 14C mass balance approach using fossil methane and 14C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6 meters of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.
Rapid sea level rise and ice sheet response to 8,200-year climate event

(American Geophysical Union, 2007-10-24) Cronin, Thomas M. ; Vogt, P. R. ; Willard, Debra A. ; Thunell, Robert C. ; Halka, J. ; Berke, M. ; Pohlman, John W.

The largest abrupt climatic reversal of the Holocene interglacial, the cooling event 8.6–8.2 thousand years ago (ka), was probably caused by catastrophic release of glacial Lake Agassiz-Ojibway, which slowed Atlantic meridional overturning circulation (AMOC) and cooled global climate. Geophysical surveys and sediment cores from Chesapeake Bay reveal the pattern of sea level rise during this event. Sea level rose ~14 m between 9.5 to 7.5 ka, a pattern consistent with coral records and the ICE-5G glacio-isostatic adjustment model. There were two distinct periods at ~8.9–8.8 and ~8.2–7.6 ka when Chesapeake marshes were drown as sea level rose rapidly at least ~12 mm yr−1. The latter event occurred after the 8.6–8.2 ka cooling event, coincided with extreme warming and vigorous AMOC centered on 7.9 ka, and may have been due to Antarctic Ice Sheet decay.
Nonequilibrium clumped isotope signals in microbial methane

( 2015-02-09) Wang, David T. ; Gruen, Danielle S. ; Lollar, Barbara Sherwood ; Hinrichs, Kai-Uwe ; Stewart, Lucy C. ; Holden, James F. ; Hristov, Alexander N. ; Pohlman, John W. ; Morrill, Penny L. ; Konneke, Martin ; Delwiche, Kyle B. ; Reeves, Eoghan P. ; Sutcliffe, Chelsea N. ; Ritter, Daniel J. ; Seewald, Jeffrey S. ; McIntosh, Jennifer C. ; Hemond, Harold F. ; Kubo, Michael D. Y. ; Cardace, Dawn ; Hoehler, Tori M. ; Ono, Shuhei

Methane is a key component in the global carbon cycle with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply-substituted “clumped” isotopologues, e.g., 13CH3D, has recently emerged as a proxy for determining methane-formation temperatures; however, the impact of biological processes on methane’s clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on 13CH3D abundances and results in anomalously elevated formation temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters.
Hydrologic controls of methane dynamics in Karst subterranean estuaries

(American Geophysical Union, 2018-11-09) Brankovits, David ; Pohlman, John W. ; Ganju, Neil K. ; Iliffe, Thomas ; Lowell, Nick ; Roth, Erich ; Sylva, Sean P. ; Emmert, Jake ; Lapham, Laura L.

Karst subterranean estuaries (KSEs) extend into carbonate platforms along 12% of all coastlines. A recent study has shown that microbial methane (CH4) consumption is an important component of the carbon cycle and food web dynamics within flooded caves that permeate KSEs. In this study, we obtained high‐resolution (~2.5‐day) temporal records of dissolved methane concentrations and its stable isotopic content (δ13C) to evaluate how regional meteorology and hydrology control methane dynamics in KSEs. Our records show that less methane was present in the anoxic fresh water during the wet season (4,361 ± 89 nM) than during the dry season (5,949 ± 132 nM), suggesting that the wet season hydrologic regime enhances mixing of methane and other constituents into the underlying brackish water. The δ13C of the methane (−38.1 ± 1.7‰) in the brackish water was consistently more 13C‐enriched than fresh water methane (−65.4 ± 0.4‰), implying persistent methane oxidation in the cave. Using a hydrologically based mass balance model, we calculate that methane consumption in the KSE was 21–28 mg CH4·m−2·year−1 during the 6‐month dry period, which equates to ~1.4 t of methane consumed within the 102‐ to 138‐km2 catchment basin for the cave. Unless wet season methane consumption is much greater, the magnitude of methane oxidized within KSEs is not likely to affect the global methane budget. However, our estimates constrain the contribution of a critical resource for this widely distributed subterranean ecosystem.
Modeling sulfate reduction in methane hydrate-bearing continental margin sediments : does a sulfate-methane transition require anaerobic oxidation of methane?

(American Geophysical Union, 2011-07-12) Malinverno, Alberto ; Pohlman, John W.

The sulfate-methane transition (SMT), a biogeochemical zone where sulfate and methane are metabolized, is commonly observed at shallow depths (1–30 mbsf) in methane-bearing marine sediments. Two processes consume sulfate at and above the SMT, anaerobic oxidation of methane (AOM) and organoclastic sulfate reduction (OSR). Differentiating the relative contribution of each process is critical to estimate methane flux into the SMT, which, in turn, is necessary to predict deeper occurrences of gas hydrates in continental margin sediments. To evaluate the relative importance of these two sulfate reduction pathways, we developed a diagenetic model to compute the pore water concentrations of sulfate, methane, and dissolved inorganic carbon (DIC). By separately tracking DIC containing 12C and 13C, the model also computes δ13C-DIC values. The model reproduces common observations from methane-rich sediments: a well-defined SMT with no methane above and no sulfate below and a δ13C-DIC minimum at the SMT. The model also highlights the role of upward diffusing 13C-enriched DIC in contributing to the carbon isotope mass balance of DIC. A combination of OSR and AOM, each consuming similar amounts of sulfate, matches observations from Site U1325 (Integrated Ocean Drilling Program Expedition 311, northern Cascadia margin). Without AOM, methane diffuses above the SMT, which contradicts existing field data. The modeling results are generalized with a dimensional analysis to the range of SMT depths and sedimentation rates typical of continental margins. The modeling shows that AOM must be active to establish an SMT wherein methane is quantitatively consumed and the δ13C-DIC minimum occurs. The presence of an SMT generally requires active AOM.
Diversity and biogeochemical structuring of bacterial communities across the Porangahau ridge accretionary prism, New Zealand

( 2011-07-04) Hamdan, Leila J. ; Gillevet, Patrick M. ; Pohlman, John W. ; Sikaroodi, Masoumeh ; Greinert, Jens ; Coffin, Richard B.

Sediments from the Porangahau ridge, located off the northeastern coast of New Zealand, were studied to describe bacterial community structure in conjunction with differing biogeochemical regimes across the ridge. Low diversity was observed in sediments from an eroded basin seaward of the ridge and the community was dominated by uncultured members of the Burkholderiales. Chloroflexi/GNS and Deltaproteobacteria were abundant in sediments from a methane seep located landward of the ridge. Gas-charged and organic rich sediments further landward had the highest overall diversity. Surface sediments, with the exception of those from the basin, were dominated by Rhodobacterales sequences associated with organic matter deposition. Taxa related to the Desulfosarcina/Desulfococcus and the JS1 candidates were highly abundant at the sulfate-methane transition zone (SMTZ) at three sites. To determine how community structure was influenced by terrestrial, pelagic, and in situ substrates, sequence data were was statistically analyzed against geochemical data (e.g., sulfate, chloride, nitrogen, phosphorous, methane, bulk inorganic and organic carbon pools) using the Biota-Environmental matching procedure. Landward of the ridge, sulfate was among the most significant structuring factors. Seaward of the ridge, silica and ammonium were important structuring factors. Regardless of the transect location, methane was the principal structuring factor on SMTZ communities.
Methane- and dissolved organic carbon-fueled microbial loop supports a tropical subterranean estuary ecosystem

(Nature Publishing Group, 2017-11-28) Brankovits, David ; Pohlman, John W. ; Niemann, Helge ; Leigh, Mary Beth ; Leewis, Mary-Cathrine ; Becker, Kevin W. ; Iliffe, Thomas ; Alvarez, Fernando ; Lehmann, Moritz F. ; Phillips, Bil

Subterranean estuaries extend inland into density-stratified coastal carbonate aquifers containing a surprising diversity of endemic animals (mostly crustaceans) within a highly oligotrophic habitat. How complex ecosystems (termed anchialine) thrive in this globally distributed, cryptic environment is poorly understood. Here, we demonstrate that a microbial loop shuttles methane and dissolved organic carbon (DOC) to higher trophic levels of the anchialine food web in the Yucatan Peninsula (Mexico). Methane and DOC production and consumption within the coastal groundwater correspond with a microbial community capable of methanotrophy, heterotrophy, and chemoautotrophy, based on characterization by 16S rRNA gene amplicon sequencing and respiratory quinone composition. Fatty acid and bulk stable carbon isotope values of cave-adapted shrimp suggest that carbon from methanotrophic bacteria comprises 21% of their diet, on average. These findings reveal a heretofore unrecognized subterranean methane sink and contribute to our understanding of the carbon cycle and ecosystem function of karst subterranean estuaries.
Colored dissolved organic matter in shallow estuaries : relationships between carbon sources and light attenuation

(Copernicus Publications on behalf of the European Geosciences Union, 2016-02-02) Oestreich, William K. ; Ganju, Neil K. ; Pohlman, John W. ; Suttles, Steven E.

Light availability is of primary importance to the ecological function of shallow estuaries. For example, benthic primary production by submerged aquatic vegetation is contingent upon light penetration to the seabed. A major component that attenuates light in estuaries is colored dissolved organic matter (CDOM). CDOM is often measured via a proxy, fluorescing dissolved organic matter (fDOM), due to the ease of in situ fDOM sensor measurements. Fluorescence must be converted to CDOM absorbance for use in light attenuation calculations. However, this CDOM–fDOM relationship varies among and within estuaries. We quantified the variability in this relationship within three estuaries along the mid-Atlantic margin of the eastern United States: West Falmouth Harbor (MA), Barnegat Bay (NJ), and Chincoteague Bay (MD/VA). Land use surrounding these estuaries ranges from urban to developed, with varying sources of nutrients and organic matter. Measurements of fDOM (excitation and emission wavelengths of 365 nm (±5 nm) and 460 nm (±40 nm), respectively) and CDOM absorbance were taken along a terrestrial-to-marine gradient in all three estuaries. The ratio of the absorption coefficient at 340 nm (m−1) to fDOM (QSU) was higher in West Falmouth Harbor (1.22) than in Barnegat Bay (0.22) and Chincoteague Bay (0.17). The CDOM : fDOM absorption ratio was variable between sites within West Falmouth Harbor and Barnegat Bay, but consistent between sites within Chincoteague Bay. Stable carbon isotope analysis for constraining the source of dissolved organic matter (DOM) in West Falmouth Harbor and Barnegat Bay yielded δ13C values ranging from −19.7 to −26.1 ‰ and −20.8 to −26.7 ‰, respectively. Concentration and stable carbon isotope mixing models of DOC (dissolved organic carbon) indicate a contribution of 13C-enriched DOC in the estuaries. The most likely source of 13C-enriched DOC for the systems we investigated is Spartina cordgrass. Comparison of DOC source to CDOM : fDOM absorption ratios at each site demonstrates the relationship between source and optical properties. Samples with 13C-enriched carbon isotope values, indicating a greater contribution from marsh organic material, had higher CDOM : fDOM absorption ratios than samples with greater contribution from terrestrial organic material. Applying a uniform CDOM : fDOM absorption ratio and spectral slope within a given estuary yields errors in modeled light attenuation ranging from 11 to 33 % depending on estuary. The application of a uniform absorption ratio across all estuaries doubles this error. This study demonstrates that light attenuation coefficients for CDOM based on continuous fDOM records are highly dependent on the source of DOM present in the estuary. Thus, light attenuation models for estuaries would be improved by quantification of CDOM absorption and DOM source identification.
An intercomparison of oceanic methane and nitrous oxide measurements

(Copernicus Publications on behalf of the European Geosciences Union, 2018-10-05) Wilson, Samuel T. ; Bange, Hermann W. ; Arévalo-Martínez, Damian L. ; Barnes, Jonathan ; Borges, Alberto V. ; Brown, Ian ; Bullister, John L. ; Burgos, Macarena ; Capelle, David W. ; Casso, Michael A. ; de la Paz, Mercedes ; Farías, Laura ; Fenwick, Lindsay ; Ferrón, Sara ; Garcia, Gerardo ; Glockzin, Michael ; Karl, David M. ; Kock, Annette ; Laperriere, Sarah ; Law, Cliff S. ; Manning, Cara C. ; Marriner, Andrew ; Myllykangas, Jukka-Pekka ; Pohlman, John W. ; Rees, Andrew P. ; Santoro, Alyson E. ; Tortell, Philippe D. ; Upstill-Goddard, Robert C. ; Wisegarver, David P. ; Zhang, Gui-Ling ; Rehder, Gregor

Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36% for methane and 27% for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.

Pohlman John W.

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