Description: The carbon regeneration in the water column of the Cariaco Basin (Venezuela) was investigated using a regression model of total alkalinity (TA) and the concentration of total inorganic carbon (TCO2). Primary productivity (PP) was determined from the inorganic carbon fraction assimilated by phytoplankton and the variation of the 22 and 23ºC isotherm was used as an indicator of coastal upwelling. The results indicate that CO2 levels were lowest (1962 µmol/kg) at the surface and increased to 2451 µmol/kg below the oxic-anoxic redox interface. The vertical regeneration distribution of carbon was dominated (82%) by organic carbon originating from the soft tissue of photosynthetic organisms, whereas 18% originated from the dissolution of biogenic calcite. The regeneration of organic carbon was highest in the surface layer in agreement with the primary productivity values. However, at the oxic-anoxic interface a second more intense maximum was detected (70-80%), generated by chemotrophic respiration of organic material by microorganisms. The percentages in the anoxic layers were lower than in the oxic zone because aerobic decomposition occurs more rapidly than anaerobic respiration of organic material because more labile fractions of organic carbon have already been mineralized in the upper layers.

Description: A kinetic-bioenergetic reaction model for the anaerobic oxidation of methane (AOM) in coastal marine sediments is presented. The model considers a fixed depth interval of sediments below the zone of bioturbation (the window-of-observation), subject to seasonal variations of temperature and inputs of organic substrates and sulfate. It includes (1) nine microbially-mediated reaction pathways involved in CH4 production/consumption; (2) an explicit representation of five functional microbial groups; and (3) bioenergetic limitations of the microbial metabolic pathways. Fermentation of organic substrates is assumed to produce hydrogen (H2) and acetate (Ac) as key reactive intermediates. Competition among the metabolic pathways is controlled by the relative kinetic efficiencies of the various microbial processes and by bioenergetic constraints. Model results imply that the functional microbial biomasses within the window-of-observation undergo little variation over the year, as a result of kinetic and thermodynamic buffering of the seasonal forcings. Furthermore, the microbial processes proceed at only small fractions of their maximum potential rates. These findings provide a theoretical justification for the approximation of steady-state microbial biomasses, which is frequently used in diagenetic modeling. In contrast, AOM rates show a strong seasonal evolution: AOM only becomes spontaneous in winter, when hydrogenotrophic sulfate reduction (hySR) sufficiently reduces the local H2 concentration. The bioenergetic limitation of AOM is thus a critical factor modulating this process in seasonally-forced nearshore marine sediments. A global sensitivity analysis based on a 2-level factorial design reveals that AOM rates are most sensitive to the kinetic parameters describing hySR and acetotrophic methanogenesis (acME). The growth and substrate uptake kinetics of AOM are unimportant, whereas the threshold value of ATP energy conservation for AOM is the most sensitive thermodynamic parameter. These results confirm that anaerobic methane oxidizing microorganisms are metabolizing close to their thermodynamic limit, with the energetic balance being controlled by the relative rates of hySR and acME. The removal of Ac by acME primarily allows more sulfate (SO42−) to be utilized for H2 oxidation, thereby promoting AOM.

Description: Bacterial sulfate reduction (SR) is often determined by radiotracer techniques using 35S‐labeled sulfate. In environments featuring simultaneous sulfide oxidation, SR can be underestimated due to re‐oxidation of 35S‐sulfide. Recycling of 35S‐tracer is expected to be high in sediment with low concentrations of pore‐water sulfide and high abundance of giant filamentous sulfur‐oxidizing bacteria (GFSOB). Here, we applied a sulfide‐spiking method, originally developed for water samples, to sediments along a shelf‐slope transect (72, 128, 243, 752 m water depth) traversing the Peruvian oxygen minimum zone. Sediment spiked with unlabeled sulfide prior to 35S‐sulfate injection to prevent radiotracer recycling was compared to unspiked sediment. At stations characterized by low natural sulfide and abundant GFSOB (128 and 243 m), the method revealed 1–3 times higher SR rates in spiked sediment. Spiking had no effect on SR in sediment with high natural sulfide despite presence of GFSOB (72 m). Bioturbated sediment devoid of GFSOB (752 m) showed elevated SR in spiked samples, likely from artificial introduction of sulfidic conditions. Sulfide oxidation rates at the 128 and 243 m station, derived from the difference in SR between spiked and unspiked sediment, approximated rates of dissimilatory nitrate reduction to ammonium by GFSOB. Gross SR contributed considerably to benthic dissolved inorganic carbon fluxes at the three shallowest station, confirming that SR is an important process for benthic carbon respirations within the oxygen minimum zone. We recommend to further explore the spiking method to capture SR in sediment featuring low sulfide concentrations and high sulfur cycling by GFSOB.