Sediment biogeochemistry of northern Cascadia margin shallow gas hydrate systems

Methane contained in gas hydrate is a significant component of the global organic carbon inventory. Describing the methane sources supporting these systems and the mechanisms that control the distribution of methane in marine sediments are critical elements in evaluating the resource potential, climate change implications and geologic hazards associated with gas hydrate. The northern Cascadia margin (offshore Vancouver Island, Canada) is a convergent margin with gas hydrate-bearing cold seeps composed of both thermogenic (Barkley Canyon) and microbial (Bullseye vent) gas sources. Gas hydrate and sediment cores were collected from each of these settings to examine the sources that sustain the gas hydrate and the biogeochemical processes that control the flux and cycling of methane carbon within the cold seep system. Gas hydrate bound methane from Barkley Canyon, Bullseye vent and four other oceanic locations was primarily synthesized from fossil organic matter devoid of radiocarbon. Recognizing that the global gas hydrate reservoir is comprised of fossil carbon may alter our understanding of how gas hydrate methane influences the radiocarbon content of other ocean carbon pools (e.g., dissolved organic carbon). Analysis of gas and oil samples from the thermogenic gas hydrate site, Barkley Canyon, indicated the thermogenic hydrocarbons were generated from a source rock with a low hydrocarbon producing potential. The pore water and sediment geochemistry from Barkley Canyon and Bullseye vent were evaluated to identify fluid flux regimes and the metabolic pathways that control how methane carbon was cycled by the microbial consortium. Evidence for coupling between anaerobic oxidation of methane (AOM) and methanogenesis was inferred from the stable carbon isotope composition of the dissolved inorganic carbon (DIC) and methane at both locations. Lipid biomarker analysis further indicated sulfate reducing bacteria consumed organic matter sources in addition to methane. This study demonstrated the value of integrating geochemical, chronological and geophysical data to understand the sources and cycling of methane in cold seep systems and provided a more comprehensive model for how the northern Cascadia margin is interconnected and how the gas hydrate system has evolved

Colored dissolved organic matter in shallow estuaries : relationships between carbon sources and light attenuation

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 13 (2016): 583-595, doi:10.5194/bg-13-583-2016.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.Funding was provided by the Woods Hole Oceanographic Institution Summer Student Fellowship Program and the USGS Coastal and Marine Geology Program

Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment.

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Wang, F., Kroeger, K. D., Gonneea, M. E., Pohlman, J. W., & Tang, J. Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment. Ecology and Evolution, 9(4), (2019):1911-1921, doi:10.1002/ece3.4884.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.We acknowledge collaboration and support from Tim Smith of the Cape Cod National Seashore, James Rassman and Tonna‐Marie Surgeon‐Rogers of the Waquoit Bay National Estuarine Research Reserve, Margot McKlveen of the Marine Biological Laboratory, Jennifer O'keefe Suttles, Wally Brooks and Michael Casso of the USGS, and Amanda Spivak of the Woods Hole Oceanographic Institution. This study was funded by the NOAA National Estuarine Research Reserve Science Collaborative (NA09NOS4190153 and NA14NOS4190145) awarded to JT and KK, MIT Sea Grant (2015‐R/RC‐141), and USGS‐Land Carbon and Coastal & Marine Geology projects. F.W. was also supported by funding from Natural Science Foundation of China (31300419, 31670621, 31870463). Any use of trade names is for descriptive purposes and does not imply endorsement by the U.S. government

The use of stable and radiocarbon isotopes as a method for delineating sources of organic material in anchialine systems

A duel isotope (stable and radiocarbon) investigation of anchialine cave systems in the Yucatan Peninsula compares the food web of a coastal and an inland cenote. Isotopic data demonstrates distinct photosynthetic and chemoautotrophic trophic levels, as well as the ability of fauna within the cave to be selective feeders even within these nutrient poor environments

Radiocarbon age-offsets in an arctic lake reveal the long-term response of permafrost carbon to climate change

Author Posting. © American Geophysical Union, 2014. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 119 (2014): 1630–1651, doi:10.1002/2014JG002688.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.National Science Foundation. Grant Number: ARC-09021692015-02-2

Hydrologic controls of methane dynamics in Karst subterranean estuaries

Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 32(12), (2019): 1759-1775, doi:10.1029/2018GB006026.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.Funding for T. M. I. and D. B. was provided by TAMU‐CONACYT (project 2015‐049). D. B. was supported by the Research‐in‐Residence program (NSF award 1137336, Inter‐university Training in Continental‐scale Ecology), the Boost Fellowship (Texas A&M University at Galveston), and the Postdoctoral Scholar Program by Woods Hole Oceanographic Institution and U.S. Geological Survey. We thank Jacob Pohlman and István Brankovits for assistance with field expeditions. Special thanks to the late Bil Phillips (Speleotech) for the support and expertise provided us during field operations. We also thank Pete van Hengstum for productive discussions and guidance during the development of the manuscript. Michael Casso and Adrian Green helped with laboratory analyses. The manuscript was greatly improved by helpful comments from an anonymus reviewer, Jeff Chanton, and Meagan Gonneea. This work is contribution number UMCES 5541. Any use of trade names is for descriptive purposes and does not imply endorsement by the U.S. Government. The authors declare no competing financial interests. Archival data are available through the USGS ScienceBase‐Catalog at https://doi.org/10.5066/P9U0KRVM

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z>75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect. (C) 2011 Elsevier B.V. All rights reserved.Keywords: Cascadia margin, Organic matter, Rare earth elements, Fluid migration, Pore waterKeywords: Cascadia margin, Organic matter, Rare earth elements, Fluid migration, Pore wate

Mass fractionation of noble gases in synthetic methane hydrate : implications for naturally occurring gas hydrate dissociation

This paper is not subject to U.S. copyright. The definitive version was published in Chemical Geology 339 (2013): 242-250, doi:10.1016/j.chemgeo.2012.09.033.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.Partial support for this research was provided by Interagency Agreements DE-FE0002911 and DE-NT0006147 between the U.S. Geological Survey Gas Hydrates Project and the U.S. Department of Energy's Methane Hydrates Research and Development Program