Description: 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.

Description: 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.

Description: 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.

Description: Arctic fjord sediments of Svalbard receive terrestrial material from glacial runoff and organic matter from marine primary productivity. Organic carbon mineralization proceeds primarily through sulfate and iron reduction in the fjord sediment. The ongoing retreat of glaciers in the high Arctic is altering the input of glacial material to the fjords, with unknown consequences for the iron and sulfur cycles in the fjord sediments. We measured sulfate reduction rates in sediment cores and analyzed porewater geochemistry, then compared these results to long-term sediment incubations to determine the rates of iron reduction and sulfide oxidation in three glacially influenced fjords on the west coast of Spitsbergen, Svalbard. Despite an abundance of glacially-sourced Fe(III)-oxide minerals, active sulfate reduction took place throughout the sediment. Analyses of the sulfur and oxygen isotopic composition of porewater sulfate and sulfate concentrations suggest that sulfide produced from biological sulfate reduction is reoxidized to sulfate. Long-term sediment incubations indicated sulfide oxidation at all three stations. The rate of sulfide oxidation was controlled by both the rate of sulfate reduction and the quantity and reactivity of Fe(III)-oxides. In our experimental incubations, we detected a decrease in Fe(III) content of the 0.5 M HCl and ascorbate-extractable fractions, but not in the 6 M HCl fraction, indicating that the highly reactive Fe(III) fraction is utilized by microorganisms and serves as the oxidant for sulfide oxidation. Our results show that sulfide oxidation in glacially-influenced fjord sediments is a wide-spread geochemical process. Further warming will drive glacial retreat onto land, where sediment-laden glacial meltwater will be altered during flow through proglacial streams and lakes before entering the marine environment. Fjord sediments will likely become more sulfidic, as glaciers deliver less particulate, highly-reactive metal oxides to the marine environment.

Description: Benthic iron (Fe) fluxes from continental shelf sediments are an important source of Fe to the global ocean, yet the magnitude of these fluxes is not well constrained. Processing of Fe in sediments is of particular importance in the Arctic Ocean, which has a large shelf area and Fe limitation of primary productivity. In the Arctic fjords of Svalbard, glacial weathering delivers high volumes of Fe-rich sediment to the fjord benthos. Benthic redox cycling of Fe proceeds through multiple pathways of reduction (i.e., dissimilatory iron reduction and reduction by hydrogen sulfide) and re-oxidation. There are few estimates of the magnitude and controlling factors of the benthic Fe flux in Arctic fjords. We collected cores from two Svalbard fjords (Kongsfjorden and Lilliehöökfjorden), measured dissolved Fe2+ concentrations using a two-dimensional sensor, and analyzed iron, manganese, carbon, and sulfur species to study benthic Fe fluxes. Benthic fluxes of Fe2+ vary throughout the fjords, with a “sweet spot” mid-fjord controlled by the availability of organic carbon linked to sedimentation rates. The flux is also impacted by fjord circulation and sea ice cover, which influence overall mineralization rates in the sediment. Due to ongoing Arctic warming, we predict an increase in the benthic Fe2+ flux with reduced sea ice cover in some fjords and a decrease in the Fe2+ flux with the retreat of tidewater glaciers in other regions. Decreasing benthic Fe2+ fluxes in fjords may exacerbate Fe limitation of primary productivity in the Arctic Ocean.

Description: Highlights • Investigation of seasonal Fe-S-C cycling in Arctic fjord sediments and water column. • Results show benthic respiration and increased benthic Fe2+ flux over winter. • Findings suggest that fjord sediments respond rapidly to water column changes. • With glacial retreat, fjords may produce less benthic Fe and sequester less carbon. Glaciated fjords are dynamic systems dominated by seasonal events such as spring phytoplankton blooms and pulses of glacial sediment-bearing meltwater delivery. These fjords are also characterized by strong spatial gradients in environmental factors such as sedimentation rate and primary productivity from the glacier-influenced head to the marine-influenced mouth. Such seasonal variations and spatial gradients, combined with the ongoing influence of climate change, generate non-steady state conditions, which have a strong impact on the mineralization of organic carbon in the fjord sediments and the flux of nutrients from the seabed. In order to investigate the role of fjord seasonal events and variability on diagenetic cycling of iron (Fe) and sulfur (S), we sampled Kongsfjorden (Svalbard, 79°N) in the spring, mid-summer, and late summer. We investigated sediment structure and biogeochemistry, conducted laboratory experiments to determine reaction rates, and compared these findings to water column productivity and turbidity. We found that rapid sedimentation near the glacial input buried algal matter-rich layers that fueled sub-surface peaks in mineralization rates over multi-year timescales. Sulfate reduction rates were limited by organic carbon availability and competition with Fe-reducers, while Fe reduction was controlled by the availability of reactive Fe(III) oxides. Pore water Fe2+ concentrations were influenced by sulfur cycling pathways and abiotic reactions such as carbonate precipitation and potentially reverse weathering. Seasonal changes in sedimentation and organic carbon supply caused lower sulfate reduction and sulfide production rates in spring, driving generally higher spring fluxes of Fe2+ from the sediment. The results of this study reveal the potential for an increased benthic source of nutrients such as Fe with continued benthic remineralization over winter in Kongsfjorden. Interannual changes in primary productivity, which are likely to intensify with global warming, and shifts in glacial sediment delivery have immediate impacts on the benthic cycling of Fe and S in this tightly coupled system, with a long term trend likely toward decreased benthic Fe fluxes. With the glacial retreat and changes in productivity predicted due to climate change, glaciated fjords such as Kongsfjorden may become a less efficient carbon sink by burying less terrestrial and marine-sourced organic matter in the deep sediments.

Description: Fjord ecosystems of the high Arctic are distinct from fjords of temperate latitudes due to the influence of glaciers, icebergs, sea ice, and the permanently low temperatures. The sediment microbiology and biogeochemical processes were analyzed during an international research program with multiple field studies in Svalbard, situated between the Barents Sea and the Arctic Ocean. We here describe the physical and geochemical setting and the predominant microbiological processes in several fjords. Physiological studies of sediments and pure cultures show how the predominantly psychrophilic bacteria are adapted to the near-zero temperature. The microbial communities include bacteria responsible for organic matter hydrolytic degradation, fermentation, and terminal oxidation to CO2. These processes drive the cycling of carbon, sulfur, iron, and manganese. The balance between the dominant sediment microbial processes changes along transects out through the fjords, reflecting the varying impact of the glacier-derived rock flour, rich in metal oxides at the head, and the plankton-derived, labile, marine organic matter at the mouth. Due to accelerated warming of Arctic ecosystems, glaciers are retreating with impacts on the physical, chemical, and biological functioning of the fjord sediment ecosystems.

Description: testTEST Glaciated fjords are dynamic systems dominated by seasonal events such as spring phytoplankton blooms and pulses of glacial sediment-bearing meltwater delivery. These fjords are also characterized by strong spatial gradients in environmental factors such as sedimentation rate and primary productivity from the glacier-influenced head to the marine-influenced mouth. Such seasonal variations and spatial gradients, combined with the ongoing influence of climate change, generate non-steady state conditions, which have a strong impact on the mineralization of organic carbon in the fjord sediments and the flux of nutrients from the seabed. In order to investigate the role of fjord seasonal events and variability on diagenetic cycling of iron (Fe) and sulfur (S), we sampled Kongsfjorden (Svalbard, 79°N) in the spring, mid-summer, and late summer. We investigated sediment structure and biogeochemistry, conducted laboratory experiments to determine reaction rates, and compared these findings to water column productivity and turbidity. We found that rapid sedimentation near the glacial input buried algal matter-rich layers that fueled sub-surface peaks in mineralization rates over multi-year timescales. Sulfate reduction rates were limited by organic carbon availability and competition with Fe-reducers, while Fe reduction was controlled by the availability of reactive Fe(III) oxides. Pore water Fe2+ concentrations were influenced by sulfur cycling pathways and abiotic reactions such as carbonate precipitation and potentially reverse weathering. Seasonal changes in sedimentation and organic carbon supply caused lower sulfate reduction and sulfide production rates in spring, driving generally higher spring fluxes of Fe2+ from the sediment. The results of this study reveal the potential for an increased benthic source of nutrients such as Fe with continued benthic remineralization over winter in Kongsfjorden. Interannual changes in primary productivity, which are likely to intensify with global warming, and shifts in glacial sediment delivery have immediate impacts on the benthic cycling of Fe and S in this tightly coupled system, with a long term trend likely toward decreased benthic Fe fluxes. With the glacial retreat and changes in productivity predicted due to climate change, glaciated fjords such as Kongsfjorden may become a less efficient carbon sink by burying less terrestrial and marine-sourced organic matter in the deep sediments.