No abstract

Bioavailable iron is an important micro-nutrient for marine phytoplankton and therefore critical to global biogeochemical cycles. Anoxic marine sediment is a significant source of Fe(II) to the ocean. Here, we investigate how the fluxes of Fe(II), both towards the sedimentary oxic layer and across the sediment-water interface, are impacted by the high concentration and flux of porewater sulfide in cold seep environments. We present new porewater data from four recently documented cold 15 seeps around Svalbard as well as from continental shelves and fjords in northern Norway. We quantitatively investigated porewater data first by calculating the Fe(II) fluxes towards oxidized surface sediments and bottom water and, second, applied a transport-reaction model to estimate the mass balance of several key chemical species. Sedimentary sulfur speciation data from two of the sites were used to constrain Fe(II) consumption in the shallow sediments. We showed that the iron reduction zone is usually confined to the top 10 cm of the sediments from our studied sites due to high sulfate 20 turnover and therefore high sulfide flux. Such a thin iron reduction zone allows proportionally more Fe(II) to reach the bottom water. Rapid precipitation of pyrite occurs at the base of the iron reduction zone, where the downward diffusing Fe(II) meets upward migrating hydrogen sulfide. Dissolved H 2 released during pyrite formation stimulates a small but significant rate of sulfate reduction in the same horizon, which results in faster production of hydrogen sulfide and a positive feedback for iron reduction in the shallow sediment. Deeper in the sediment, where sulfate is actively consumed due to 25 anaerobic methane oxidation, no apparent formation of pyrite is observed from the available measurements and our modeling results. This is mostly due to the relatively low availability of Fe(II) as a result of slower turnover of the less active iron mineral phases. Such an observation may contradict the use of pyrite abundance to deduce the sulfate-methanetransition-zone in past sedimentary records. A series of model sensitivity tests were performed to systematically investigate how the Fe(II) dynamics is impacted by higher deposition rate of iron (oxyhydr)oxides minerals on the seafloor and 30 intensifying methane supply. We showed that the increases in iron reduction rate, pyrite formation rate, and Fe(II) flux are expected with higher seafloor iron (oxyhydr)oxides deposition initially. However, complicated feedbacks between Fe(II) Biogeosciences Discuss., https://doi.2 production and sulfate reduction pose negative feedbacks to pyrite formation in the sediments. With a larger supply of methane, Fe(II) flux towards the oxic surface sediments is initially intensified by the higher production of hydrogen sulfide until such an interplay is too fast that essentially all reactive iron minerals settled on the seafloor dissolve immediately and dissolved iron is fixed through pyrite precipitation. Such an interplay between Fe(II) and sulfide determi...

Anoxic marine sediments contribute a significant amount of dissolved iron (Fe 2+) to the ocean which is crucial for the global carbon cycle. Here, we investigate iron cycling in four Arctic cold seeps where sediments are anoxic and sulfidic due to the high rates of methane-fueled sulfate reduction. We estimated Fe 2+ diffusive fluxes towards the oxic sediment layer to be in the range of 0.8 to 138.7 μmole/m 2 /day and Fe 2+ fluxes across the sediment-water interface to be in the range of 0.3 to 102.2 μmole/m 2 /day. Such variable fluxes cannot be explained by Fe 2+ production from organic matter-coupled dissimilatory reduction alone. We propose that the reduction of dissolved and complexed Fe 3+ as well as the rapid formation of iron sulfide minerals are the most important reactions regulating the fluxes of Fe 2+ in these cold seeps. By comparing seafloor visual observations with subsurface pore fluid composition, we demonstrate how the joint cycling of iron and sulfur determines the distribution of chemosynthesisbased biota.