Description: Estimating the amount of methane in the seafloor globally as well as the flux of methane from sediments toward the ocean–atmosphere system are important considerations in both geological and climate sciences. Nevertheless, global estimates of methane inventories and rates of methane production and consumption through anaerobic oxidation in marine sediments are very poorly constrained. Tools for regionally assessing methane formation and consumption rates would greatly increase our understanding of the spatial heterogeneity of the methane cycle as well as help constrain the global methane budget. In this article, an algorithm for calculating methane consumption rates in the inner shelf is applied to the gas-rich sediments of the Belt Seas and The Sound (North Sea–Baltic Sea transition). It is based on the depth of free gas determined by hydroacoustic techniques and the local methane solubility concentration. Due to the continuous nature of shipboard hydroacoustic measurements, this algorithm captures spatial heterogeneities in methane fluxes better than geochemical analyses of point sources such as observational/sampling stations. The sensibility of the algorithm with respect to the resolution of the free gas depth measurements (2 m vs. 50 cm) is proven of minor importance (a discrepancy of 〈10%) for a small part of the study area. The algorithm-derived anaerobic methane oxidation rates compare well with previous measured and modeling studies. Finally, regional results reveal that contemporary anaerobic methane oxidation in worldwide inner-shelf sediments may be an order of magnitude lower (ca. 0.24 Tmol year–1) than previous estimates (4.6 Tmol year–1). These algorithms ultimately help improve regional estimates of anaerobic oxidation of methane rates.

Description: The fluids emanating from active submarine hydrothermal vent chimneys provide a window into subseafloor processes and, through mixing with seawater, are responsible for steep thermal and compositional gradients that provide the energetic basis for diverse biological communities. Although several models have been developed to better understand the dynamic interplay of seawater, hydrothermal fluid, minerals and microorganisms inside chimney walls, none provide a fully integrated approach to quantifying the biogeochemistry of these hydrothermal systems. In an effort to remedy this, a fully coupled biogeochemical reaction-transport model of a hydrothermal vent chimney has been developed that explicitly quantifies the rates of microbial catalysis while taking into account geochemical processes such as fluid flow, solute transport and oxidation–reduction reactions associated with fluid mixing as a function of temperature. The metabolisms included in the reaction network are methanogenesis, aerobic oxidation of hydrogen, sulfide and methane and sulfate reduction by hydrogen and methane. Model results indicate that microbial catalysis is generally fastest in the hottest habitable portion of the vent chimney (77–102 °C), and methane and sulfide oxidation peak near the seawater-side of the chimney. The fastest metabolisms are aerobic oxidation of H2 and sulfide and reduction of sulfate by H2 with maximum rates of 140, 900 and 800 pmol cm−3 d−1, respectively. The maximum rate of hydrogenotrophic methanogenesis is just under 0.03 pmol cm−3 d−1, the slowest of the metabolisms considered. Due to thermodynamic inhibition, there is no anaerobic oxidation of methane by sulfate (AOM). These simulations are consistent with vent chimney metabolic activity inferred from phylogenetic data reported in the literature. The model developed here provides a quantitative approach to describing the rates of biogeochemical transformations in hydrothermal systems and can be used to constrain the role of microbial activity in the deep subsurface.

Description: Geochemical data (CH4, SO42−, I−, Cl−, particulate organic carbon (POC), δ13C-CH4, and δ13C-CO2) are presented from the upper 30 m of marine sediment on a tectonic submarine accretionary wedge offshore southwest Taiwan. The sampling stations covered three ridges (Tai-Nan, Yung-An, and Good Weather), each characterized by bottom simulating reflectors, acoustic turbidity, and different types of faulting and anticlines. Sulfate and iodide concentrations varied little from seawater-like values in the upper 1–3 m of sediment at all stations; a feature that is consistent with irrigation of seawater by gas bubbles rising through the soft surface sediments. Below this depth, sulfate was rapidly consumed within 5–10 m by anaerobic oxidation of methane (AOM) at the sulfate-methane transition. Carbon isotopic data imply a mainly biogenic methane source. A numerical transport-reaction model was used to identify the supply pathways of methane and estimate depth-integrated turnover rates at the three ridges. Methane gas ascending from deep layers, facilitated by thrusts and faults, was by far the dominant term in the methane budget at all sites. Differences in the proximity of the sampling sites to the faults and anticlines mainly accounted for the variability in gas fluxes and depth-integrated AOM rates. By comparison, methane produced in situ by POC degradation within the modeled sediment column was unimportant. This study demonstrates that the geochemical trends in the continental margins offshore SW Taiwan are closely related to the different geological settings.

Description: This study investigates the controls on organic carbon and molybdenum (Mo) accumulation in sediments deposited within the Western Interior Seaway across the Cenomanian–Turonian boundary interval (94.34–93.04 Ma) including Oceanic Anoxic Event 2 (OAE2). Carbon fluxes to the sediment–water interface (reflecting changes in primary productivity) and bottom-water oxygen concentrations (reflecting preservation effects) are reconstructed from field data and used to constrain a benthic model that simulates the geochemistry of unconsolidated sediments as they were deposited. The results show that increased availability of reactive iron prevents Mo sequestration as thiomolybdate (MoS42 −) during OAE2 (O2 ~ 105 μM) by (i) inhibiting sulfate reduction, and (ii) buffering any free sulfide that becomes available. In the post-OAE2 period (O2 ~ 50 μM), Mo accumulation is favored by a large reduction in iron flux. Importantly, this occurs in parallel with oxygenated bottom waters and high rates of aerobic carbon degradation in the surface sediments, implying that elevated Mo burial fluxes in ancient marine facies do not necessarily reflect euxinic or even anoxic conditions within the water column. Our findings suggest that both an increase in production and preservation lead to enrichment in organic carbon in the Western Interior Seaway. More generally, the results demonstrate that a careful consideration of the coupling between iron, carbon and oxygen cycles during the early stages of diagenesis is critical for interpreting geochemical proxies in modern and ancient settings.

Description: This study presents benthic data from 12 samplings from February to December 2010 in a 28 m deep channel in the southwest Baltic Sea. In winter, the distribution of solutes in the porewater was strongly modulated by bioirrigation which efficiently flushed the upper 10 cm of sediment, leading to concentrations which varied little from bottom water values. Solute pumping by bioirrigation fell sharply in the summer as the bottom waters became severely hypoxic (〈 2 μM O2). At this point the giant sulfide-oxidizing bacteria Beggiatoa was visible on surface sediments. Despite an increase in O2 following mixing of the water column in November, macrofauna remained absent until the end of the sampling. Contrary to expectations, metabolites such as dissolved inorganic carbon, ammonium and hydrogen sulfide did not accumulate in the upper 10 cm during the hypoxic period when bioirrigation was absent, but instead tended toward bottom water values. This was taken as evidence for episodic bubbling of methane gas out of the sediment acting as an abiogenic irrigation process. Porewater–seawater mixing by escaping bubbles provides a pathway for enhanced nutrient release to the bottom water and may exacerbate the feedback with hypoxia. Subsurface dissolved phosphate (TPO4) peaks in excess of 400 μM developed in autumn, resulting in a very large diffusive TPO4 flux to the water column of 0.7 ± 0.2 mmol m−2 d−1. The model was not able to simulate this TPO4 source as release of iron-bound P (Fe–P) or organic P. As an alternative hypothesis, the TPO4 peak was reproduced using new kinetic expressions that allow Beggiatoa to take up porewater TPO4 and accumulate an intracellular P pool during periods with oxic bottom waters. TPO4 is then released during hypoxia, as previous published results with sulfide-oxidizing bacteria indicate. The TPO4 added to the porewater over the year by organic P and Fe–P is recycled through Beggiatoa, meaning that no additional source of TPO4 is needed to explain the TPO4 peak. Further experimental studies are needed to strengthen this conclusion and rule out Fe–P and organic P as candidate sources of ephemeral TPO4 release. A measured C/P ratio of 〈 20 for the diffusive flux to the water column during hypoxia directly demonstrates preferential release of P relative to C under oxygen-deficient bottom waters. This coincides with a strong decrease in dissolved inorganic N/P ratios in the water column to ~ 1. Our results suggest that sulfide oxidizing bacteria could act as phosphorus capacitors in systems with oscillating redox conditions, releasing massive amounts of TPO4 in a short space of time and dramatically increasing the internal loading of TPO4 to the overlying water.

Description: Subduction of the oceanic Cocos plate offshore Costa Rica causes strong advection of methane-charged fluids. Presented here are the first direct measurements of microbial anaerobic oxidation of methane (AOM) and sulfate reduction (SR) rates in sediments from the two mounds, applying radiotracer techniques in combination with numerical modeling. In addition, analysis of carbonate δ18O, δ13C, and 87Sr / 86Sr signatures constrain the origin of the carbonate-precipitating fluid. Average rates of microbial activities showed differences with a factor of 4.8 to 6.3 between Mound 11 [AOM 140.71 (±40.84 SD); SR 117.25 (±82.06 SD) mmol m−2 d−1, respectively] and Mound 12 [AOM 22.37 (±0.85 SD); SR 23.99 (±5.79 SD) mmol m−2 d−1, respectively]. Modeling results yielded flow velocities of 50 cm a−1 at Mound 11 and 8–15 cm a−1 at Mound 12. Analysis of oxygen and carbon isotope variations of authigenic carbonates from the two locations revealed higher values for Mound 11 (δ18O: 4.7 to 5.9‰, δ13C: −21.0 to −29.6‰), compared to Mound 12 (δ18O: 4.1 to 4.5‰, δ13C: −45.7 to −48.9‰). Analysis of carbonates 87Sr / 86Sr indicated temporal changes of deep-source fluid admixture at Mound 12. The present study is in accordance with previous work supporting considerable differences of methane flux between the two Mounds. It also strengthens the hypothesis of a predominantly deep fluid source for Mound 11 versus a rather shallow source of biogenic methane for Mound 12. The results demonstrate that methane-driven microbial activity is a valid ground truthing tool for geophysical measurements of fluid advection and constraining of recent methane fluxes in the study area. The study further shows that the combination of microbial rate measurements, numerical modeling, and authigenic carbonate analysis provide a suitable approach to constrain temporal and spatial variations of methane charged fluid flow at the Pacific Costa Rican margin.

Description: We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3−, NO2−, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 μM) and increased to 125 μM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (−10.3 mmol O2 m−2 d−1) and decreased quasi-exponentially with water depth to −3.2 mmol O2 m−2 d−1. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N m−2 d−1. Overall, the sediments acted as net sink for DIN. Observed increases in δ15NNO3 and δ18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0‰ (15εapp) and 14.1‰ (18εapp). Measurements of δ15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2−. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2−. The principal findings were that (i) net benthic 14N/15N fractionation (εDEN) was 12.9 ± 1.7‰, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2− (−22 ± 1.9‰), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported εDEN for fine-grained sediments are much lower (4–8‰). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater–seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.

Description: Animal burrowing and sediment-mixing (bioturbation) began during the run up to the Ediacaran/Cambrian boundary1, 2, 3, initiating a transition4, 5 between the stratified Precambrian6 and more well-mixed Phanerozoic7 sedimentary records, against the backdrop of a variable8, 9 global oxygen reservoir probably smaller in size than present10, 11. Phosphorus is the long-term12 limiting nutrient for oxygen production via burial of organic carbon13, and its retention (relative to carbon) within organic matter in marine sediments is enhanced by bioturbation14, 15, 16, 17, 18. Here we explore the biogeochemical implications of a bioturbation-induced organic phosphorus sink in a simple model. We show that increased bioturbation robustly triggers a net decrease in the size of the global oxygen reservoir—the magnitude of which is contingent upon the prescribed difference in carbon to phosphorus ratios between bioturbated and laminated sediments. Bioturbation also reduces steady-state marine phosphate levels, but this effect is offset by the decline in iron-adsorbed phosphate burial that results from a decrease in oxygen concentrations. The introduction of oxygen-sensitive bioturbation to dynamical model runs is sufficient to trigger a negative feedback loop: the intensity of bioturbation is limited by the oxygen decrease it initially causes. The onset of this feedback is consistent with redox variations observed during the early Cambrian rise of bioturbation, leading us to suggest that bioturbation helped to regulate early oxygen and phosphorus cycles.

Description: Two ∼6 m long sediment cores were collected along the ∼300 m isobath on the Alaskan Beaufort Sea continental margin. Both cores showed distinct sulfate-methane transition zones (SMTZ) at 105 and 120 cm below seafloor (cmbsf). Sulfate was not completely depleted below the SMTZ but remained between 30 and 500 μM. Sulfate reduction and anaerobic oxidation of methane (AOM) determined by radiotracer incubations were active throughout the methanogenic zone. Although a mass balance could not explain the source of sulfate below the SMTZ, geochemical profiles and correlation network analyses of biotic and abiotic data suggest a cryptic sulfur cycle involving iron, manganese and barite. Inhibition experiments with molybdate and 2-bromoethanesulfonate (BES) indicated decoupling of sulfate reduction and AOM and competition between sulfate reducers and methanogens for substrates. While correlation network analyses predicted coupling of AOM to iron reduction, the addition of manganese or iron did not stimulate AOM. Since none of the classical archaeal anaerobic methanotrophs (ANME) were abundant, the involvement of unknown or unconventional phylotypes in AOM is conceivable. The resistance of AOM activity to inhibitors implies deviation from conventional enzymatic pathways. This work suggests that the classical redox cascade of electron acceptor utilization based on Gibbs energy yields does not always hold in diffusion-dominated systems, and instead biotic processes may be more strongly coupled to mineralogy.