Iron Geochemistry Research Articles

Geochemistry of iron and trace metals in seep carbonates of the middle Okinawa Trough impacted by hydrothermal plumes

Geochemistry of iron and trace metals in seep carbonates and its dependence on anaerobic oxidation of methane (AOM)-driven diagenesis in cold seeps are not well documented. Here we characterize geochemistry of Fe and trace metals in carbonate nodules collected at an active cold seep in the middle Okinawa Trough (OT) impacted by hydrothermal plumes. The carbonate nodules in the studied core are dominated by aragonite even at sulfate-low core bottom. Most aragonite at the core bottom may have formed much earlier close to the seafloor under high sulfate concentration. Additionally, porewater at the depth may not be developed to a condition for the formation of calcite dominating over aragonite due to constant downward replenishment of sulfate across through shallow SMTZ (40 cm below sediment surface). As indicated by δ13C and δ18O of the carbonates, anaerobic oxidation of thermogenic methane from gas hydrate dissociation is the dominant fluid source for carbonate precipitation. It can be inferred from the existence of vivianite that Fe reduction coupled to AOM (Fe-AOM) may have ever been prevalent at the hydrothermal Fe-impacted seep site. Enhanced inputs of Mo, Co, Cu, Ni, and Zn associated with hydrothermal Fe-oxyhydroxides-organic colloids is the main source for their high enrichment in the carbonate nodules, and clay minerals and AOM-related microbial organics may have played an important role in their partitioning in the nodules. Uranium enrichment in the carbonate nodules is mainly through enhanced U delivery associated with Fe-oxyhydroxides-scavenged organic colloids and additional U enrichment induced by U(VI) reduction. U(IV) incorporation into carbonate lattices dominates U partitioning in the carbonate nodules over the upper 60 cm of the seep sediments, but the incorporation is substantially dampened at depth due to an increase in concentration of dissolved inorganic carbon, which consequently may have rendered U(IV) adsorption on clay minerals as the important U sink in the nodules. Our results suggest that the exceptional enrichments of Co, Cu, Ni, Zn, Mo, and U in seep carbonates may be used as a paleo-proxy to differentiate cold-seep carbonates whose formation has been co-impacted by hydrothermal plumes.

Iron geochemistry in surface sediments of the subtropical northern South China Sea and a comparison with the temperate East China Sea

Iron geochemistry in surface sediments of the subtropical northern South China Sea and a comparison with the temperate East China Sea

Diagenetic Geochemistry of Iron, Sulfur, and Molybdenum in Sediments of the Middle Okinawa Trough Impacted by Hydrothermal Plumes and/or Cold Seeps

AbstractIron (Fe), sulfur (S), and molybdenum (Mo) geochemistry in marine sediments impacted by hydrothermal plumes and/or cold seeps is complex and has not been systematically documented. Here we characterize Fe, S, and Mo diagenesis in sediments between the Minami‐Ensei Knoll hydrothermal field and a cold‐seep site of the middle Okinawa Trough. Results show that distances away from the hydrothermal field and the steep trough slope may significantly affect the transport of hydrothermal Fe. The transformation of hydrothermal reactive Fe to poorly reactive or unreactive Fe‐bearing phyllosilicates decreased the relative fractions of highly reactive Fe (FeHR) in total Fe (FeHR/FeT). Despite this, the standing stocks of Fe oxides in the methane‐free sediments have not been dampened, indicating no net impacts of hydrothermal Fe inputs on the size of Fe oxides. In the methane‐free sediments, low ratios of total reduced inorganic sulfide (TRIS) to total organic carbon (TOC) (TRIS/TOC), highly 34S‐depleted pyrite, and low Mo contents suggest that organoclastic sulfate reduction is at low rates and plays a limited role in carbon cycle. In the cold‐seep sediments, however, intense sulfate reduction coupled to anaerobic methane oxidation significantly elevate TRIS/TOC ratios, Mo enrichment, and isotope compositions of Mo and pyrite‐S. This pathway is expected to be important in carbon cycle in the basin due to the wide occurrence of cold seeps. Our results highlight the important controls of the local extreme depositional/diagenetic conditions on sedimentary S and Mo records, with implications for the reconstruction of paleoredox states of the past earth's surface.

Interfacial geochemistry of iron applied to atmospheric and oceanic environments

Realizing the United Nations Sustainable Development Goals on water and climate through research in chemistry demands innovative and integrated approaches to studying environmental systems from the macro to the molecular scales. Due to the ubiquity of iron (Fe)-containing materials in the natural and built environments, they find their way to air, water, and soil with natural weathering and human activities. These materials are redox and (photo)chemically active with relatively high affinity to complexing inorganic and organic species of relevance to geochemical and atmospheric systems that include outdoor and indoor air. The current state of knowledge of the environmental chemistry of Fe shows that Fe-containing materials influence pollutant transport and transformation, micronutrient availability, and the climate. However, the extent of these influences is affected by the solvation effects of bulk and interfacial water. In this perspectives article, we highlight advances in experimental and theoretical approaches focused on studying the interfacial reactivity of Fe-containing materials in geochemical and atmospheric environments. Specifically, the surface chemistry of Fe-(oxyhydr)oxides and its role in changing the chemical composition of the natural and built environments is presented to connect fundamental concepts to implications. This paper also provides an outlook for future studies in this interdisciplinary area.

Magnetic properties of gas hydrate-bearing sediments and their association with iron geochemistry in the Sea of Marmara, Turkey

The anaerobic oxidation of methane, a key geochemical process that is involved in the cycling of sulfate and iron (oxyhydr)oxides in marine sediments, results in the formation of iron sulfides. Although ferrimagnetic iron sulfides have been identified in seepage systems, the link between iron migration and sediment magnetic properties remains poorly understood. Here, we investigate two cores from the Sea of Marmara to evaluate biogeochemical iron cycling and iron sulfide mineralogy in gas hydrate-bearing sediments. Magnetic analyses indicate the presence of greigite and pyrrhotite in a core from a hydrate-rich site with a high hydrocarbon flux, which contrasts with a lack of these minerals in a core characterized by only mild seepage. This is supported by the results of rock magnetic and scanning electron microscope analyses of the sediments. The presence of authigenic greigite is critical for assessing local redox records and together with the occurrence of monoclinic pyrrhotite may suggest specific diagenetic processes in gas hydrate environments. Our analysis demonstrates the usefulness of these ferrimagnetic minerals, with a high saturation isothermal remanent magnetization to magnetic susceptibility ratio (SIRM/χ > 15 kAm−1) and a high index of hysteresis parameters (DJH > 0.2) indicative of magnetic mineralogy changes, for evaluating variability in the intensity of seepage fluxes and for estimating gas hydrate distributions.

Dynamic coupling of ferrihydrite transformation and associated arsenic desorption/redistribution mediated by sulfate-reducing bacteria

Sulfate-reducing bacteria play an important role in the geochemistry of iron (oxyhydr)oxide and arsenic (As) in natural environments; however, the associated reaction processes are yet to be fully understood. In this study, batch experiments coupled with geochemical, spectroscopic, microscopic, and thermodynamic analyses were conducted to investigate the dynamic coupling of ferrihydrite transformation and the associated As desorption/redistribution mediated by Desulfovibrio vulgaris (D. vulgaris). The results indicated that D. vulgaris could induce ferrihydrite transformation via S2−-driven and direct reduction processes. In the absence of SO42−, D. vulgaris directly reduced ferrihydrite, and As desorption and re-sorption occurred simultaneously during the partial transformation of ferrihydrite to magnetite. The increase in SO42− loading promoted the S2−-driven reduction of ferrihydrite and accelerated the subsequent mineralogical transformation. In the low and medium SO42− treatments, ferrihydrite was completely transformed to a mixture of magnetite and mackinawite, which increased the fraction of As in the residual phase and stabilized As. In the high SO42− treatment, although the replacement of ferrihydrite by only mackinawite also increased the fraction of As in the residual phase, 22.1% of the total As was released into the solution due to the poor adsorption affinity of As to mackinawite and the conversion of As5+ to As3+. The mechanisms of ferrihydrite reduction, mineralogy transformation, and As mobilization and redistribution mediated by sulfate-reducing bacteria are closely related to the surrounding SO42− loadings. These results advance our understanding of the biogeochemical behavior of Fe, S, and As, and are helpful for the risk assessment and remediation of As contamination.

Geology, mineralogy, geochemistry and deposit model of iron and manganese in Bouarfa mine, Eastern High Atlas, Morocco

The Bouarfa Iron and Manganese Deposits are contained in the Sinemurian carbonate formations in the eastern High Atlas. It is a large deposit which has allowed the exploitation of more than 1.5 million tons of manganese and which still contains millions of tons of reserves. The mapping carried out shows the extension of the mineralization with oxides and hydroxides of Mn and Fe. The definition of types of mineralization shows that they are essentially stratiform deposits with some bodies and veins in the fault zones. The result of the mineralogical identification and geochemical analyses shows that it is a sedimentary deposit resulting from at least two mineralizing events with a high Fe-Mn content during the installation of the Sinemurian shallow carbonate platform. This is an environment of rapid oxidation and relatively sufficient sulphide inputs under redox conditions.

Constraints on Early Paleozoic Deep‐Ocean Oxygen Concentrations From the Iron Geochemistry of the Bay of Islands Ophiolite

The deep ocean is generally considered to have changed from anoxic in the Precambrian to oxygenated by the Late Paleozoic (∼420–400 Ma) due to changes in atmospheric oxygen concentrations. When the transition occurred, that is, in the Early Paleozoic or not until the Late Paleozoic, is less well constrained. To address this, we measured Fe3+/ΣFe of volcanic rocks, sheeted dykes, gabbros, and ultramafic rocks from the Early Paleozoic (∼485 Ma) Bay of Islands (BOI) ophiolite as a proxy for hydrothermal alteration in the presence or absence of O2 derived from deep marine fluids. Combining this data with previously published data from the BOI indicates that volcanic rocks are oxidized relative to intrusive crustal rocks (0.35 ± 0.02 vs. 0.19 ± 0.01, 1 standard error), which we interpret to indicate that the volcanic section was altered by marine-derived fluids that contained some dissolved O2. We compare our results directly to the Macquarie Island and Troodos ophiolites, drilled oceanic crust, previously compiled data for ophiolitic volcanic rocks, and newly compiled data for ophiolitic intrusive rocks. These comparisons show that the BOI volcanic (but not intrusive) rocks are oxidized relative to Precambrian equivalents, but are less oxidized relative to Late Paleozoic to modern equivalents. We interpret these results to indicate that the Early Paleozoic ocean contained dissolved O2, but at concentrations ∼2.4× lower than for the Late Paleozoic to today.

Crab bioturbation drives coupled iron-phosphate-sulfide cycling in mangrove and salt marsh soils

Coastal wetlands sequestering abundant blue carbon in soils are biogeochemical hotspots and critical habitats for benthic animals like invertebrate fiddler crabs. Here, we reveal how crab bioturbation (i.e., burrowing activity) drives the redox geochemistry of ferrous iron (Fe(II)), phosphate (PO43-), and sulfide (S(-II)) under contrasting vegetation types and hydrological conditions. We used in-situ approaches of diffusive gradients in thin films to perform detailed mm-scale burrow observations in two subtropical wetlands with a vegetation gradient of mudflat-salt marsh-mangrove. Burrow flushing caused a top-down hydrologic connectivity through the crab burrows and thus created a deep depth for the occurrence of Fe(III) reduction and sulfate reduction which were accompanied by P mobilization. The burrow oxidation zone, indicated by lower concentrations of Fe(II), PO43- and S(-II), were shallower in mudflats and salt marshes than in mangroves due to the unique respiratory roots of mangrove plants. The redox of Fe(II), PO43- and S(-II) in crab burrow was insensitive to the convection flow-induced input of dissolved oxygen through the surrounding soil matrix, indicating the burrow soil is an independent microenvironment. Crab burrowing activities favored Fe-S coupling which is conductive the formation of pyrite and alkalinity generation. Overall, our in-situ high-resolution observations and porewater hydraulic dynamics revealed spatially variable soil geochemistry, active coupled cycling of Fe-P-S in crab burrows, and mm-scale hotspots of redox cycling within burrows.

Effects of manganese, iron and sulfur geochemistry on arsenic migration in the estuarine sediment of a small river in Xiamen, Southeast China

The geochemistry of iron (Fe), manganese (Mn) and sulfur (S) and their effects on arsenic (As) mobility in the mudflats of small river estuaries remain unclear. Here, diffusive gradient in thin films (DGT) and high-resolution dialysis (HR-Peeper) techniques combined with a sequential extraction procedure (BCR) were employed to investigate As, Fe, Mn and S geochemistry in the mudflat of the Jiuxi River estuary, Southeast China. Grain size analysis indicated that fine-grained particles were likely to be deposited in the estuarine intertidal zone and coastal area. DGT and HR-Peeper results revealed that in the estuary and coastal area, the dissolved As in sediment in summer was controlled by Mn geochemistry, which includes not only the release of As through Mn/Fe reduction but also the stabilization of dissolved As in pore water. This stabilization of dissolved As may due to the formation of As–Mn-OM complexes. In winter, the significant positive correlations between DGT-Fe, DGT-Mn, DGT-As and DGT-S indicated that sulfate reduction was the start of As mobilization in sediment in winter. In both the estuary and the coastal area, the easily reducible Fe, Mn and As contents in intertidal sediment were higher than those in the subtidal zone. Combined with the As flux across the sediment-overlying water interface (SWI), these phenomena suggested that As in subtidal sediment diffused into overlying water and that As in overlying water tended to accumulate in the intertidal sediment. The total organic carbon content (TOC) and DGT results in the lower reach, estuary and coastal areas indicated that organic matter is the controlling factor of Fe/Mn reduction, sulfate reduction and As mobilization. The BCR test results showed higher reactive fraction contents of Fe, Mn and As in winter sediment, which threaten the overlying water quality.

Mineralogy and geochemistry of native iron

Basite magmatism has been manifested repeatedly for a long time in various geodynamic structures within the eastern part of the Siberian platform. In the Middle Paleozoic, it was related to rifting processes, and in the Late Paleozoic-Early Mesozoic – to the initiation and development of trap syneclises. Differences of the geodynamic regime of magma formation are displayed in the material composition of rocks. This report presents a generalizing study of the petro-geochemical features of the tholeiitic basaltic melts formed in different geodynamic settings. The initial magmas composition changes significantly at different stages of the magmatic system development. Using multicomponent analysis, we reviewed the impact of the fractionation processes of the basal melt, which occurred under various PT conditions, on its material composition. Among the trapp bodies there are powerful differentiated intrusions. A significant change of the composition occurs during the intra-chamber differentiation of the melt in a sequence of rock strata varied from the basic magnesian to felsic alkaline rocks. In the resulting series of rocks, the content of rare elements included in the lattice of the early femic phases decreases, as well as the accumulation of almost all incompatible elements. The evolution of melts of normal alkalinity occurs with an increase of REE content and their insignificant separation. Intrusions that have undergone the stage of high-pressure fractionation in the deep transitional chamber are of particular importance. As a result of such differentiation, a peculiar group of rocks is formed in the cross section of the Middle Paleozoic bodies, such as monzonite-porphyries in one case and anorthosite gabbro-dolerites - in the other. It is established that the monzoitoid type of differentiation is characterized by accumulation of LREE, LILE and elements of the zirconium group Nb, Ta, Hf and Y. Isolation of anorthosite gabbro-dolerites in the cross-section of bodies, as well as an increase in the content of aluminum, calcium, and strontium in them, is an indication of the anorthositic tendency of magmatic melt differentiation/When the basite-tholeiite melt interacts with the mantle reducing fluid in the deep core, its metallization occurs with the release of drop-liquid separations of native iron up to the formation of its large segregations. Intrusions with a large-scale content of native iron are found among the trap formations of Siberia. All this leads to a decrease in the total concentration and activity of iron in the partially metallized silicate matrix, there is a significant increase in the content of MgO and trace elements-Ni, Co, Cr. The Fe-phase-containing intrusives are characterized by minimal LILE, HFSE, and REE contents. Start your abstract here… 250 to 500 words concise and factual abstract is required. The abstract should include the purpose of research, principal results and major conclusions. References should be avoided, if it is essential, only cite the author(s) and year(s) without giving reference list. Prepare your abstract in this file and upload it into the registration web field.

Mine tailings in a redox-active environment: Iron geochemistry and potential environmental consequences

Iron (Fe) oxyhydroxides provide many functions in soils, mainly owing to their large surface area and high surface charge density. The reactivity of Fe oxyhydroxides is function of their mineralogical characteristics (e.g., crystallinity degree and crystal size). Detailed studies of these features are essential for predicting the stability and reactivity of these minerals within soil and sediments. The present study aimed to evaluate geochemical changes in Fe-rich tailings after the world's largest mining disaster in SE Brazil (in 2015) and to predict the potential environmental implications for the estuary. The mineralogical characteristics of the tailings were studied at three different times (2015, 2107, and 2019) to assess how an active redox environment affects Fe oxyhydroxides and to estimate the time frame within which significant changes occur. The study findings indicate a large decrease in the Fe oxyhydroxides crystallinity, which were initially composed (93%) of highly crystalline Fe oxyhydroxides (i.e., goethite and hematite) and 6.7% of poorly crystalline Fe oxyhydroxides (i.e., lepidocrocite and ferrihydrite). Within 4 years the mineralogical features of Fe oxyhydroxides had shifted, and in 2019 poorly crystalline Fe oxyhydroxides represented 47% of the Fe forms. Scanning electron microscope micrographs and the mean crystal size evidenced a decrease in particle size from 109 nm to 49 nm for goethite in the d111 direction. The changes in mean crystal size increased the reactivity of Fe oxyhydroxides, resulting in a greater number of interactions with cationic and anionic species. The decreased crystallinity and increased reactivity led to the compounds being more susceptible to reductive dissolution. Overall, the findings show that the decrease in crystallinity along with higher susceptibility to reductive dissolution of Fe oxyhydroxides can affect the fate of environmentally detrimental elements (e.g., phosphorus and trace metals) thereby increasing the concentration of these pollutants in estuarine soils and waters.

Sedimentary pyrite sulfur isotope compositions preserve signatures of the surface microbial mat environment in sediments underlying low-oxygen cyanobacterial mats.

The sedimentary pyrite sulfur isotope (δ34 S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ34 S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ34 S geochemistry. Pyrite δ34 S values often capture δ34 S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ34 S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ34 S trends and δ34 S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment-water interface of this sinkhole hosts a low-oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ34 S signatures in early Earth environments. Porewater sulfide δ34 S values vary by up to ~25‰ throughout the day due to light-driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5cm in the sediment. Progressive consumption of the sulfate reservoir drives δ34 S variability, instead of variations in average cell-specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ34 S values of pyrite are similar to porewater sulfide δ34 S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ34 S signatures of pyrite deposited in organic-rich, iron-poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis.

Geochemistry of iron and sulfur in the Holocene marine sediments under contrasting depositional settings, with caveats for applications of paleoredox proxies

Cycling and fates of iron (Fe) and sulfur (S) in marine sediments are influenced by depositional settings to differential extents. The information is crucial for addressing the responses of their benthic diagenesis to changing climates and environments and also for reconstructing paleo-depositional conditions, but has not been well constrained. Detailed chemical speciation was utilized to characterize geochemistry of Fe and S, and then to reveal the impacts of depositional settings on their diagenesis at three locations, representing contrasting depositional environments: (i) highly dynamic Yangtze River estuary (YRE), (ii) the depocenter of South Yellow Sea (SYS), which is only remotely impacted by large river, and (iii) the middle Okinawa trough (OT), a back-arc deep basin along the outer edge of the East China Sea (ECS) slope. Results show that the YRE sediments favor accumulation of total highly reactive Fe (FeHR), while the SYS sediments are poor in FeHR due to low FeHR in their source material and/or preferential trapping of FeHR during sediment transport through the semi-enclosed Bohai Sea. Ferruginous sediment regimes in the highly dynamic YRE system facilitate Fe(III) reduction and burial of unsulfidized Fe(II), while the SYS and OT sediments favor sulfate reduction and pyritization of Fe(II). Pyrite is always the main sink of reduced S that escapes reoxidation in the entire continental margin, regardless of depositional environments. Abundant reactive Fe(III) but low total reduced inorganic sulfide (TRIS) contents in the three sites suggest that TRIS burial is largely controlled by the availability of degradable OC and/or dynamic regimes of sediments. The applicability of two widely used Fe- and S-based proxies to distinguish bottom-water conditions, that is, OC/TRIS ratio and FeHR to total Fe (FeHR/FeT) ratio, were examined in the three contrasting environments, and caveats were given for future applications of the two proxies.

Small-Scale Geochemical Heterogeneities and Seasonal Variation of Iron and Sulfide in Salt Marshes Revealed by Two-Dimensional Sensors

Loss of tidal wetlands is a world-wide phenomenon. Many factors may contribute to such loss, but among them are geochemical stressors such as exposure of the marsh plants to elevated levels on hydrogen sulfide in the pore water of the marsh peat. Here we report the results of a study of the geochemistry of iron and sulfide at different seasons in unrestored (JoCo) and partially restored (Big Egg) salt marshes in Jamaica Bay, a highly urbanized estuary in New York City where the loss of salt marsh area has accelerated in recent years. The spatial and temporal 2-dimensional distribution patterns of dissolved Fe2+ and H2S in salt marshes were in situ mapped with high resolution planar sensors for the first time. The vertical profiles of Fe2+ and hydrogen sulfide, as well as related solutes and redox potentials in marsh were also evaluated by sampling the pore water at discrete depths. Sediment cores were collected at various seasons and the solid phase Fe, S, N, C, and chromium reducible sulfide in marsh peat at discrete depths were further investigated in order to study Fe and S cycles, and their relationship to the organic matter cycling at different seasons. Our results revealed that the redox sensitive elements Fe2+ and S2– showed significantly heterogeneous and complex three dimensional distribution patterns in salt marsh, over mm to cm scales, directly associated with the plant roots due to the oxygen leakage from roots and redox diagenetic reactions. We hypothesize that the oxic layers with low/undetected H2S and Fe2+ formed around roots help marsh plants to survive in the high levels of H2S by reducing sulfide absorption. The overall concentrations of Fe2+ and H2S and distribution patterns also seasonally varied with temperature change. H2S level in JoCo sampling site could change from <0.02 mM in spring to >5 mM in fall season, reflecting significantly seasonal variation in the rates of bacterial oxidation of organic matter at this marsh site. Solid phase Fe and S showed that very high fractions of the diagenetically reactive iron at JoCo and Big Egg were associated with pyrite that can persist for long periods in anoxic sediments. This implies that there is insufficient diagenetically reactive iron to buffer the pore water hydrogen sulfide through formation of iron sulfides at JoCo and Big Egg.

Characterizing geochemistry of organic carbon, sulfur, and iron in sediments of the middle Okinawa Trough since the last glacial maximum

The diagenetic interplays of organic carbon (OC), sulfur (S), and iron (Fe) in marine sediments and their responses to changes in depositional and climatic conditions are poorly characterized. In this study, chemical speciation and isotopes were combined to characterize diagenesis of OC, S and Fe in sediments of the middle Okinawa Trough (OT), a back-arc deep basin along the edge of the East China Sea outer shelf, since the Last Glacial Maximum (LGM). Two key geochemical proxies, i.e., OC/pyrite-S ratios and the degrees of pyritization, indicate anoxic bottom-water conditions during the last Glacial/Deglacial, which promoted burial of OC and pyrite. However, a shift to oxic conditions during the Deglacial-Holocene transition facilitated aerobic respiration, resulting in lower burial of OC and pyrite. In contrast to previous studies, the environmental changes induced by large sea-level rises since the LGM have not triggered significant variations in pyrite-S isotopic compositions, probably due to persistently low sedimentation rates. Variable extents of Fe enrichment are identified in the sediments since the LGM, with lower enrichment during the Holocene probably due to increased distance of Fe shuttling and concomitant Fe ageing. Anoxic bottom water during the Glacial/Deglacial did not induce an expected intensification of OC sulfurization, probably because sedimentary Fe enrichment favored pyrite formation but competitively dampened OC sulfurization. Lines of geochemical evidence hint at a discontinuous deposition at ~200 cm depth probably caused by mass wasting.

Mud, Microbes, and Macrofauna: Seasonal Dynamics of the Iron Biogeochemical Cycle in an Intertidal Mudflat

Microorganisms and burrowing animals exert a pronounced impact on the cycling of redox sensitive metals in coastal sediments both spatially and temporally. In this study, we monitored the spatiotemporal dynamics of porewater and highly reactive solid phase iron with the corresponding prokaryotic and eukaryotic sedimentary microbial communities over one annual cycle from November 2015 to November 2016 in a bioturbated intertidal mudflat. Continuous and seasonally variable pools of both porewater Fe(II) and highly reactive iron (FeHR) were observed throughout the seasons with significant increases of Fe(II) and FeHR in response to increased sediment temperature in summer months. Maximum concentrations of Fe(II) and FeHR were predominantly confined to the upper 5 cm of sediment throughout the year. Iron-oxidizing and -reducing microorganisms were present and stable temporally, and exhibited a depth-dependent stratification likely due to availability of Fe(II) and FeHR pools, respectively. Zetaproteobacteria, presumptive lithotrophic iron-oxidizing bacteria, were present at abundances around 0.5 – 1% in the top five cm of sediment with decling abundance with depth. As a whole the microbial community was relatively stable across the seasons, and showed strongest separation with depth, probably driven by changes in oxygen availability and organic matter. The Deltaproteobacteria, principally taxa known to be associated with sulfur and iron cycling, were prevalent, especially at >5 cm depth. Gammaproteobacteria and Bacteroidetes were also abundant, with putatively aerobic members especially prevalent in the cm of the sediment. The relative abundance of diatoms, estimated from abundance of 18S rRNA gene counts, showed evidence of a seasonal signal possibly tied to spring and fall blooms. Overall, analysis of phytoplankton found significant abundance at depth, likely due to the feeding and bio-mixing activity of marine worms. Macro-, and meiofauna, consistent with expected taxa, were detected throughout the year via 18S gene counts, and showed some seasonal variations that may influence sedimentary iron transformations by active microbial grazing. In summary, this analysis revealed relatively consistent temporal and spatial trends in iron geochemistry and microbial and macrobial community composition, while also indicating a complex dynamic of microbial and macrobial interactions are responsible for maintaining these processes.

The formation of the physical and chemical condition along the continuum land waters Azov Sea in the context of iron geochemistry studies

The authors studied the formation of the chemical type and class of water, the isotopic composition of sulfur and oxygen of sulfate ions, the content of Fetotal along the continuum land waters Azov Sea, i.e. from the moment of iron resurgence in mine workings before its partial deposition in the bottom sediments of the Sea of Azov.

Distribution of iron in the Western Indian Ocean and the Eastern tropical South pacific: An inter-basin comparison

The Western Indian Ocean (WIO) and Eastern Tropical South Pacific (ETSP) are distinctly different regimes, yet they share several important features. These include a strong upwelling system, a large oxygen minimum zone (OMZ) with active denitrification, a spreading center with extensive hydrothermal activity, and a vast oligotrophic upper water column. Here, we show that the distribution and geochemistry of iron shows remarkable similarities as well. In particular, both basins exhibit large sub-surface plumes of iron derived from sediments underlying the oxygen minimum zones and from hydrothermal sources. Moreover, the behavior of Fe, especially its redox cycling, is remarkably similar in the Arabian Sea and Peruvian oxygen minimum zone, reflecting similar processes associated with the nitrogen cycle in each region. The large Fe plumes under each OMZ are well below the oxygen-free depth, yet they are probably dependent on internal redox cycling and scavenging of Fe within the overlying OMZs. Globally, both the Arabian Sea and Peru margin sediments are hot spots of carbon oxidation, which probably contributes to their importance as Fe sources.The fate of hydrothermally derived Fe in the WIO and ETSP is particularly interesting to compare because their source terms are very different even though their oxidation rates, once they have entered the water column, should be directly comparable. In the ETSP, hydrothermal inputs from along a section of the ultra-fast spreading Southern East Pacific Rise (SEPR) are integrated into a single coherent plume that is exported west across the ocean interior for >4000km. In contrast, hydrothermal inputs to the WIO derive from multiple sources including outflow from the Red Sea via the Gulf of Aden, the Indonesian Throughflow, and from multiple vent-sources along the Carlsbad Ridge, Central Indian Ridge and SW Indian Ridge which are slow, medium and ultra-slow spreading, respectively. As a result, hydrothermally sourced Fe distributions are more complex in the WIO, with several overlapping plumes and distinctly different distributions of two other hydrothermally-derived metals, aluminum and manganese. Here we argue that comparative studies of these basins, with a future emphasis on benthic-water column interactions, will advance knowledge about Fe biogeochemistry and how distributions in the WIO, in particular, are likely to change in the future.

Study of apatite and iron geochemistry and mineralization for identification of the rare earth elements deposit, Gazestan in Bafgh region (Yazd Province)

Study of apatite and iron geochemistry and mineralization for identification of the rare earth elements deposit, Gazestan in Bafgh region (Yazd Province)