Salt marsh pond biogeochemistry changes hourly-to-yearly but does not scale with dimensions or geospatial position

Author Posting. © American Geophysical Union, 2020. 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 125(10), (2020): e2020JG005664, doi:10.1029/2020JG005664.Shallow ponds are expanding in many salt marshes with potential impacts on ecosystem functioning. Determining how pond characteristics change over time and scale with physical dimensions and other spatial predictors could facilitate incorporation of ponds into projections of ecosystem change. We evaluated scaling relationships across six differently sized ponds in three regions of the high marshes within the Plum Island Ecosystems‐Long Term Ecological Research site (MA, USA). We further characterized diel fluctuations in surface water chemistry in two ponds to understand short‐term processes that affect emergent properties (e.g., habitat suitability). Primary producers drove oxygen levels to supersaturation during the day, while nighttime respiration resulted in hypoxic to anoxic conditions. Diel swings in oxygen were mirrored by pH and resulted in successive shifts in redox‐sensitive metabolisms, as indicated by nitrate consumption at dusk followed by peaks in ammonium and then sulfide overnight. Abundances of macroalgae and Ruppia maritima correlated with whole‐pond oxygen metabolism rates, but not with surface area (SA), volume (V), or SA:V. Moreover, there were no clear patterns in primary producer abundances, surface water chemistry, or pond metabolism rates across marsh regions supplied by different tidal creeks or that differed in distance to upland borders or creekbanks. Comparisons with data from 2 years prior demonstrate that plant communities and biogeochemical processes are not in steady state. Factors contributing to variability between ponds and years are unclear but likely include infrequent tidal exchange. Temporal and spatial variability and the absence of scaling relationships complicate the integration of high marsh ponds into ecosystem biogeochemical models.Thanks to S. McNichol, S. Jayne, E. Neel, and PIE‐LTER (NSF‐OCE1238212) for field assistance; I. Forbrich for meteorological data (Giblin & Forbrich, 2018); J. Jennings for dissolved nutrient analyses; J. Seewald for ion chromatograph access; and G. Mariotti for elevation data. C. Wilson and an anonymous reviewer provided comments that greatly improved our manuscript. A. C. S. was supported by NSF (OCE1233678), NOAA (NA14NOS4190145), and Sea Grant (NA14OAR4170104) awards, and A. D. by the MIT Undergraduate Research Opportunities Program.2021-03-1

Isotopic exchange of carbon-bound hydrogen over geologic timescales

The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50–100°C) exchange likely occurs on timescales of 10^4 to 10^8 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D_2O indicate that the number of D atoms incorporated during structural rearrangements can be far less than the number of C-H bonds that are broken. Sample calculations indicate that, for steranes in immature sediments, the D/H ratio imparted by biosynthesis may be largely preserved in spite of significant structural changes

Dissolved organic carbon compounds in deep-sea hydrothermal vent fluids from the East Pacific Rise at 9°50′N

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 125 (2018): 41-49, doi:10.1016/j.orggeochem.2018.08.004.Deep-sea hydrothermal vents are unique ecosystems that may release chemically distinct dissolved organic matter to the deep ocean. Here, we describe the composition and concentrations of polar dissolved organic compounds observed in low and high temperature hydrothermal vent fluids at 9°50’N on the East Pacific Rise. The concentration of dissolved organic carbon was 46 μM in the low temperature hydrothermal fluids and 14 μM in the high temperature hydrothermal fluids. In the low temperature vent fluids, quantifiable dissolved organic compounds were dominated by water-soluble vitamins and amino acids. Derivatives of benzoic acid and the organic sulfur compound 2,3-dihydroxypropane-1-sulfonate (DHPS) were also present in low and high temperature hydrothermal fluids. The low temperature vent fluids contain organic compounds that are central to biological processes, suggesting that they are a by-product of biological activity in the subseafloor. These compounds may fuel heterotrophic and other metabolic processes at deep-sea hydrothermal vents and beyond.This project was funded by a grant from WHOI’s Deep Ocean Exploration Institute and WHOI’s Ocean Ridge Initiative (to EBK and SMS) and by NSF OCE-1154320 (to EBK and KL), OCE- 1136727 (to SMS and JSS), and OCE 1131095 (to SMS)

Abiotic redox reactions in hydrothermal mixing zones: decreased energy availability for the subsurface biosphere

© The Author(s), 202. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in McDermott, J. M., Sylva, S. P., Ono, S., German, C. R., & Seewald, J. S. Abiotic redox reactions in hydrothermal mixing zones: decreased energy availability for the subsurface biosphere. Proceedings of the National Academy of Sciences of the United States of America, 117(34), (2020): 20453-20461, doi:10.1073/pnas.2003108117.Subseafloor mixing of high-temperature hot-spring fluids with cold seawater creates intermediate-temperature diffuse fluids that are replete with potential chemical energy. This energy can be harnessed by a chemosynthetic biosphere that permeates hydrothermal regions on Earth. Shifts in the abundance of redox-reactive species in diffuse fluids are often interpreted to reflect the direct influence of subseafloor microbial activity on fluid geochemical budgets. Here, we examine hydrothermal fluids venting at 44 to 149 °C at the Piccard hydrothermal field that span the canonical 122 °C limit to life, and thus provide a rare opportunity to study the transition between habitable and uninhabitable environments. In contrast with previous studies, we show that hydrocarbons are contributed by biomass pyrolysis, while abiotic sulfate (SO42−) reduction produces large depletions in H2. The latter process consumes energy that could otherwise support key metabolic strategies employed by the subseafloor biosphere. Available Gibbs free energy is reduced by 71 to 86% across the habitable temperature range for both hydrogenotrophic SO42− reduction to hydrogen sulfide (H2S) and carbon dioxide (CO2) reduction to methane (CH4). The abiotic H2 sink we identify has implications for the productivity of subseafloor microbial ecosystems and is an important process to consider within models of H2 production and consumption in young oceanic crust.Financial support was provided by the National Aeronautics and Space Administration (NASA) Astrobiology program (Awards NNX09AB75G and 80NSSC19K1427 to C.R.G. and J.S.S.) and the NSF (Award OCE-1061863 to C.R.G. and J.S.S.). Ship and vehicle time for cruise FK008 was provided by the Schmidt Ocean Institute. We thank the ROV Jason II and HROV Nereus groups, and the captain, officers, and crew of R/V Atlantis (AT18-16) and R/V Falkor (FK008) for their dedication to skillful operations at sea. We thank our scientific colleagues from both cruises, as well as Meg Tivey, Frieder Klein, and Scott Wankel for insightful discussions. We are grateful to the editor and two anonymous reviewers for providing helpful comments and suggestions

Genus-specific carbon fixation activity measurements reveal distinct responses to oxygen among hydrothermal vent campylobacteria

Author Posting. © American Society for Microbiology, 2022. This article is posted here by permission of American Society for Microbiology for personal use, not for redistribution. The definitive version was published in Applied and Environmental Microbiology 88(2),(2022): e02083-21, https://doi.org/10.1128/AEM.02083-21.Molecular surveys of low temperature deep-sea hydrothermal vent fluids have shown that Campylobacteria (previously Epsilonproteobacteria) often dominate the microbial community and that three genera, Arcobacter, Sulfurimonas, and Sulfurovum, frequently coexist. In this study, we used replicated radiocarbon incubations of deep-sea hydrothermal fluids to investigate activity of each genus under three experimental conditions. To quantify genus-specific radiocarbon incorporation, we used newly designed oligonucleotide probes for Arcobacter, Sulfurimonas, and Sulfurovum to quantify their activity using catalyzed-reporter deposition fluorescence in situ hybridization (CARD-FISH) combined with fluorescence-activated cell sorting. All three genera actively fixed CO2 in short-term (∼ 20 h) incubations, but responded differently to the additions of nitrate and oxygen. Oxygen additions had the largest effect on community composition, and caused a pronounced shift in community composition at the amplicon sequence variant (ASV) level after only 20 h of incubation. The effect of oxygen on carbon fixation rates appeared to depend on the initial starting community. The presented results support the hypothesis that these chemoautotrophic genera possess functionally redundant core metabolic capabilities, but also reveal finer-scale differences in growth likely reflecting adaptation of physiologically-distinct phylotypes to varying oxygen concentrations in situ. Overall, our study provides new insights into how oxygen controls community composition and total chemoautotrophic activity, and underscores how quickly deep-sea vent microbial communities respond to disturbances.This research was funded by the U.S. National Science Foundation grants OCE-1131095 (S.M.S.) and OCE-1136727 (S.M.S., J.S.S.). Further support was provided by the WHOI Investment in Science Fund (S.M.S.). Funding for J.M. was further provided by doctoral fellowships from the Natural Sciences and Engineering Research Council of Canada (PGSD3-430487-2013, PGSM-405117-2011) and the National Aeronautics and Space Administration Earth Systems Science Fellowship (PLANET14F-0075), an award from the Canadian Meteorological and Oceanographic Society, and the WHOI Academic Programs Office

Primary productivity below the seafloor at deep-sea hot springs

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Proceedings of the National Academy of Sciences.of the United States of America 115 (2018): 6756–6761, doi:10.1073/pnas.1804351115.The existence of a chemosynthetic subseafloor biosphere was immediately recognized when deep-sea hot springs were discovered in 1977. However, quantifying how much new carbon is fixed in this environment has remained elusive. In this study, we incubated natural subseafloor communities under in situ pressure/temperature and measured their chemosynthetic growth efficiency and metabolic rates. Combining these data with fluid flux and in situ chemical measurements, we derived empirical constraints on chemosynthetic activity in the natural environment. Our study shows subseafloor microorganisms are highly productive (up to 1.4 Tg C produced yearly), fast-growing (turning over every 17–41 hours), and physiologically diverse. These estimates place deep-sea hot springs in a quantitative framework and allow us to assess their importance for global biogeochemical cycles.This research was funded by a grant of the Dimensions of Biodiversity program of the US National Science Foundation (NSF-OCE-1136727 to S.M.S. and J.S.S.). Funding for J.M. was further provided by doctoral fellowships from the Natural Sciences and Engineering Research Council of Canada (PGSD3-430487-2013, PGSM-405117-2011) and the National Aeronautics and Space Administration Earth Systems Science Fellowship (PLANET14F-0075), an award from the Canadian Meteorological and Oceanographic Society, and the WHOI Academic Programs Office

Shallow ponds are heterogeneous habitats within a temperate salt marsh ecosystem

Author Posting. © American Geophysical Union, 2017. 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 122 (2017): 1371–1384, doi:10.1002/2017JG003780.Integrating spatial heterogeneity into assessments of salt marsh biogeochemistry is becoming increasingly important because disturbances that reduce plant productivity and soil drainage may contribute to an expansion of shallow ponds. These permanently inundated and sometimes prominent landscape features can exist for decades, yet little is known about pond biogeochemistry or their role in marsh ecosystem functioning. We characterized three ponds in a temperate salt marsh (MA, USA) over alternating periods of tidal isolation and flushing, during summer and fall, by evaluating the composition of plant communities and organic matter pools and measuring surface water oxygen, temperature, and conductivity. The ponds were located in the high marsh and had similar depths, temperatures, and salinities. Despite this, they had different levels of suspended particulate, dissolved, and sediment organic matter and abundances of phytoplankton, macroalgae, and Ruppia maritima. Differences in plant communities were reflected in pond metabolism rates, which ranged from autotrophic to heterotrophic. Integrating ponds into landcover-based estimates of marsh metabolism resulted in slower rates of net production (−8.1 ± 0.3 to −15.7 ± 0.9%) and respiration (−2.9 ± 0.5 to −10.0 ± 0.4%), compared to rates based on emergent grasses alone. Seasonality had a greater effect on pond water chemistry, organic matter pools, and algal abundances than tidal connectivity. Alternating stretches of tidal isolation and flushing did not affect pond salinities or algal communities, suggesting that exchange between ponds and nearby creeks was limited. Overall, we found that ponds are heterogeneous habitats and future expansion could reduce landscape connectivity and the ability of marshes to capture and store carbon.National Science Foundation Grant Number: OCE1233678; PIE-LTER Grant Number: OCE1238212; TIDE Grant Number: OCE13544942017-12-1

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

Geochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea

Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic–hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273–285 °C) and major element compositions, low dissolved CO2 concentrations (4.4 mmol/kg) and high measured pH (4.2–4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative δDH2O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6–2.7), high endmember CO2 (up to 274 mmol/kg) and negative δ34SH2S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO2 at PACMANUS is more enriched in 13C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (⩽80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water–rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones

Subseafloor microbial communities in hydrogen-rich vent fluids from hydrothermal systems along the Mid-Cayman Rise

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Environmental Microbiology 18 (2016): 1970–1987, doi:10.1111/1462-2920.13173.Warm fluids emanating from hydrothermal vents can be used as windows into the rocky subseafloor habitat and its resident microbial community. Two new vent systems on the Mid-Cayman Rise each exhibits novel geologic settings and distinctively hydrogen-rich vent fluid compositions. We have determined and compared the chemistry, potential energy yielding reactions, abundance, community composition, diversity, and function of microbes in venting fluids from both sites: Piccard, the world's deepest vent site, hosted in mafic rocks; and Von Damm, an adjacent, ultramafic-influenced system. Von Damm hosted a wider diversity of lineages and metabolisms in comparison to Piccard, consistent with thermodynamic models that predict more numerous energy sources at ultramafic systems. There was little overlap in the phylotypes found at each site, although similar and dominant hydrogen-utilizing genera were present at both. Despite the differences in community structure, depth, geology, and fluid chemistry, energetic modelling and metagenomic analysis indicate near functional equivalence between Von Damm and Piccard, likely driven by the high hydrogen concentrations and elevated temperatures at both sites. Results are compared with hydrothermal sites worldwide to provide a global perspective on the distinctiveness of these newly discovered sites and the interplay among rocks, fluid composition and life in the subseafloor.National Aeronautics and Space Administration Grant Number: NNX09AB756; Alfred P. Sloan Foundation; NSF Grant Number: OCE10618