Glacial controls on redox-sensitive trace element cycling in Arctic fjord sediments (Spitsbergen, Svalbard)

Glacial meltwater is an important source of bioessential trace elements to high latitude oceans. Upon delivery to coastal waters, glacially sourced particulate trace elements are processed during early diagenesis in sediments and may be sequestered or recycled back to the water column depending on local biogeochemical conditions. In the glaciated fjords of Svalbard, large amounts of reactive Fe and Mn (oxyhydr)oxides are delivered to the sediment by glacial discharge, resulting in pronounced Fe and Mn cycling concurrent with microbial sulfate reduction. In order to investigate the diagenetic cycling of selected trace elements (As, Co, Cu, Mo, Ni, and U) in this system, we collected sediment cores from two Svalbard fjords, Van Keulenfjorden and Van Mijenfjorden, in a transect along the head-to-mouth fjord axis and analyzed aqueous and solid phase geochemistry with respect to trace elements, sulfur, and carbon along with sulfate reduction rates. We found that Co and Ni associate with Fe and Mn (oxyhydr)oxides and enter the pore water upon reductive metal oxide dissolution. Copper is enriched in the solid phase where sulfate reduction rates are high, likely due to reactions with H2S and the formation of sulfide minerals. Uranium accumulates in the solid phase likely following reduction by both Fe- and sulfate-reducing bacteria, while Mo adsorbs to Fe and Mn (oxyhydr)oxides in the surface sediment and is removed from the pore water at depth where sulfidization makes it particle-reactive. Arsenic is tightly coupled to Fe redox cycling and its partitioning between solid and dissolved phases is influenced by competition with FeS for adsorption sites on crystalline Fe oxides. Differences in trace element cycling between the two fjords suggest delivery of varying amount and composition of tidewater glacier (Van Keulenfjorden) and meltwater stream (Van Mijenfjorden) material, likely related to oxidative processes occurring in meltwater streams. This processing produces a partially weathered, more reactive sediment that is subject to stronger redox cycling of Fe, Mn, S, and associated trace elements upon delivery to Van Mijenfjorden. With climate warming, the patterns of trace element cycling observed in Van Mijenfjorden may also become more prevalent in other Svalbard fjords as tidewater glaciers retreat into meltwater stream valleys

Sulfur cycling in an iron oxide-dominated, dynamic marine depositional system: The Argentine continental margin

The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS). Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths

Seasonal iron fluxes and iron cycling in sandy bioirrigated sediments

Permeable sediments, which represent more than 50% of the continental shelves, have been largely neglected as a potential source of Fe in current global estimates of benthic dissolved iron (Fed) fluxes. There are open questions regarding the effects of a range of factors on Fed fluxes from these deposits, including seasonal dynamics and the role of bioirrigation. To address these gaps, we performed laboratory-based sediment incubation experiments with muddy sands during summer (21 °C) and winter (7 °C). We used bioirrigation mimics to inject overlying water into the permeable sediment with patterns resembling the bioirrigation activity of the prolific bioturbating polychaete, Clymenella torquata. Newly developed in-line Fe accumulators were used to estimate Fe fluxes with a recirculating set-up. We found high Fed fluxes from sandy sediments, especially in benthic chambers with simulated bioirrigation. In the winter fluxes reached >200 µmol Fed m-2 d-1 at the onset of irrigation and then decreased over the course of a 13-day experiment while in the summer fluxes from irrigated sediments reached >100 µmol Fed m-2 d-1 and remained high throughout a 7-day experiment. Despite different geochemical expressions of Fe-S cycling and resulting porewater Fed concentrations in winter and summer, large Fed fluxes were sustained during both seasons. Solid-phase and porewater concentration profiles showed that maximum concentrations of key constituents, including total solid-phase reactive Fe, and porewater Fed and ammonium, were located closer to the sediment water interface (SWI) in irrigated cores than in non-irrigated cores due to the upward advective transport of dissolved porewater constituents. This upward transport also facilitated Fed fluxes out of the sediments, especially during times of active pumping. Our study demonstrates the potential for large Fed fluxes from sandy sediments in both summer and winter, despite relatively low standing stocks of labile organic matter and porewater Fed. The primary driver of these high fluxes was advective porewater transport, in our study induced by the activity of infaunal organisms. These results suggest that permeable sediments, which dominate shelf regions, must be explicitly considered in global estimates of benthic Fed fluxes, and cannot be simply extrapolated from estimates based on muddy sediments

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO₂ storage site before CO₂ arrival

Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2

The evolution of early diagenetic signals in Bering Sea subseafloor sediments in response to varying organic carbon deposition over the last 4.3 Ma

Transient pore-water and solid-phase signatures in deep subseafloor marine sediments, resulting from changes in both the amount and the quality of the organic matter input, are common but often difficult to interpret. We combined high-resolution pore-water and solid-phase data from Integrated Ocean Drilling Program (IODP) Expedition 323 Site U1341 (Bowers Ridge, Bering Sea) with inverse reaction-transport modeling to examine the evolution and potential preservation of diagenetic signals in these deep subseafloor sediments. We explore how these signals reflect major changes in the deposition and reactivity of organic matter to the seafloor at Bowers Ridge. Results of the inverse model approach reveal that 2.51-2.58 Ma ago a high deposition flux of extremely labile organic matter, probably linked to increased surface water primary productivity, affected this site. Associated elevated organoclastic sulfate reduction rates facilitated low sulfate concentrations, the onset of methanogenesis, and consequently sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Sulfate depletion caused the dissolution of biogenic barite reflected by a sedimentary interval with low Ba/Al ratios. Two sulfate-methane transition zones (SMTZs) evolved where high rates of AOM controlled sulfate consumption which was sustained by the influx of sulfate from seawater above and a deep source below. The positions of both SMTZs shifted non-synchronously over the sub-sequent similar to 130,000 yrs, until methanogenesis and AOM declined. The present-day sulfate concentration and sulfur isotope profiles still reflect the impact of the reactive organic matter pulse. They also record a period of very low reactive organic matter deposition during the middle to late Pleistocene, probably linked to very low primary productivity, resulting in little microbial carbon turnover in the sediment. Our study shows that combining biogeochemical signatures recorded in the solid-phase of deep subseafloor sediments with the analysis of transient pore-water signals by inverse reaction-transport modeling yields new insights into past deep biosphere processes and the paleoproductivity of marine basins. (C) 2013 Elsevier Ltd. All rights reserved

Challenges and risks of the future : biofuels as inductors of sustainable development

The present study evaluates the potential of biofuel production to promote social inclusion, assuring protection of environmental assets, food production and sustainable regional development, in the most arid and poor areas of Brazil. Reasons and consequences of low contribution of family agriculture to biofuel production are identified. Statistical analysis is based on recent official data, confirmed by several publications carried out by social organizations. Analysis is also based on technical literature published by the biofuel sector. The study shows that family agriculture may participate and benefit from biofuel production

Iron and manganese speciation and cycling in glacially influenced high-latitude fjord sediments (West Spitsbergen, Svalbard): Evidence for a benthic recycling-transport mechanism

Glacial environments may provide an important but poorly constrained source of potentially bioavailable iron and manganese phases to the coastal ocean in high-latitude regions. Little is known about the fate and biogeochemical cycling of glacially derived iron and manganese in the coastal marine realm. Sediment and porewater samples were collected along transects from the fjord mouths to the tidewater glaciers at the fjord heads in Smeerenburgfjorden, Kongsfjorden, and Van Keulenfjorden along Western Svalbard. Solid-phase iron and manganese speciation, determined by sequential chemical extraction, could be linked to the compositions of the local bedrock and hydrological/weathering conditions below the local glaciers. The concentration and sulfur isotope composition of chromium reducible sulfur (CRS) in Kongs- and Van Keulenfjorden sediments largely reflect the delivery rate and isotope composition of detrital pyrite originating from adjacent glaciers. The varying input of reducible iron and manganese oxide phases and the input of organic matter of varying reactivity control the pathways of organic carbon mineralization in the sediments of the three fjords. High reducible iron and manganese oxide concentrations and elevated metal accumulation rates coupled to low input of “fresh” organic matter lead to a strong expression of dissimilatory metal oxide reduction evidenced in very high porewater iron (up to 800 lM) and manganese (up to 210 lM) concentrations in Kongsfjorden and Van Keulenfjorden. Sediment reworking by the benthic macrofauna and physical sediment resuspension via iceberg calving may be additional factors that promote extensive benthic iron and manganese cycling in these fjords. On-going benthic recycling of glacially derived dissolved iron into overlying seawater, where partial reoxidation and deposition occurs, facilitates the transport of iron across the fjords and potentially into adjacent continental shelf waters. Such iron-dominated fjord sediments are likely to provide significant fluxes of potentially bioavailable iron to coastal waters and beyond. By contrast, low delivery of reducible iron (oxyhydr)oxide phases and elevated organic carbon mineralization rates driven by elevated input of “fresh” marine organic matter allow organoclastic sulfate reduction to dominate carbon remineralization at the outer Smeerenburgfjorden sites, which may limit iron fluxes to the water column

An engineered PQQ-dependent alcohol dehydrogenase for the oxidation of 5-(hydroxymethyl)furoic acid

Furan-2,5-dicarboxylic acid (FDCA) is a bio-based platform chemical with the potential to replace terephthalic acid in the production of polymers. A critical step for enzymatic and whole-cell production of FDCA from 5-(hydroxymethyl)furfural (HMF) is the transformation of 5-(hydroxymethyl)furoic acid (HMFA) into 5-formylfuroic acid (FFA). Here, we establish periplasmic pyrroloquinoline quinone (PQQ)-dependent alcohol dehydrogenases (ADHs) as biocatalytic tools for the oxidation of HMFA, HMF, and 5-formylfurfural (FFF). Further, we identify several amino acid residues including the “lid loop” of the substrate channel as promising targets for future engineering steps toward a fully periplasmic oxidation pathway to FDCA