Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9–10°N

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Chemical Geology 252 (2008): 214-227, doi:10.1016/j.chemgeo.2008.03.009.In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9-10°N to better constrain processes affecting Fe- isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) is there significant Fe isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S- isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between –0.11 to –0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (-0.6±0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42- followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower temperature, Fe-depleted vents.Support for W. Bach and K. Edwards was provided by NSF grant OCE-0241791 and support for O. Rouxel was provided by funding from the WHOI Deep Ocean Exploration Institute and NSF grant OCE-0622982 and OCE-0647948

Multiple sulphur and iron isotope composition of detrital pyrite in Archaean sedimentary rocks : a new tool for provenance analysis

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 286 (2009): 436-445, doi:10.1016/j.epsl.2009.07.008.Multiple S (δ34S and δ33S) and Fe (δ56Fe) isotope analyses of rounded pyrite grains from 3.1 to 2.6 Ga conglomerates of southern Africa indicate their detrital origin, which supports anoxic surface conditions in the Archaean. Rounded pyrites from Meso- to Neoarchaean gold and uranium-bearing strata of South Africa are derived from both crustal and sedimentary sources, the latter being characterised by non-mass dependent fractionation of S isotopes (Δ33S as negative as -1.35‰) and large range of Fe isotope values (δ56Fe between -1.1 and 1.2‰). Most sediment-sourced pyrite grains are likely derived from sulphide nodules in marine organic matter-rich shales, sedimentary exhalites and volcanogenic massive sulphide deposits. Some sedimentary pyrite grains may have been derived from in situ sulphidised Fe-oxides, prior to their incorporation into the conglomerates, as indicated by unusually high positive δ56Fe values. Sedimentary sulphides without significant non-mass dependent fractionation of S isotopes were also present in the source of some conglomerates. The abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high pO2 as the cause for the absence of significant non-mass dependent fractionation processes in the 3.2 – 2.7 Ga atmosphere. Rounded pyrites from the ca. 2.6 Ga conglomerates of the Belingwe greenstone belt in Zimbabwe have strongly fractionated δ34S, Δ33S and δ56Fe values, the source of which can be traced back to black shale-hosted massive sulphides in the underlying strata. The study demonstrates the utility of combined multiple S and Fe isotope analysis for provenance reconstruction of Archaean sedimentary successions.AH acknowledges support by NAI International Collaboration Grant and NRF grant FA2005040400027. AB participation was supported by NSF grant EAR-937 05-45484, NAI award No. NNA04CC09A, and NSERC 938 Discovery grant. Rouxel's contribution was supported by NSF OCE-0622982

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

This paper is not subject to U.S. copyright. The definitive version was published in Geophysical Research Letters 38 (2011): L16605, doi:10.1029/2011GL048367.Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.We appreciate support from the USGS CMGP, NCCWSC, and the Mendenhall Postdoctoral Program

Time-series analysis of two hydrothermal plumes at 9°50′N East Pacific Rise reveals distinct, heterogeneous bacterial populations

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 10 (2012): 178-192, doi:10.1111/j.1472-4669.2011.00315.xWe deployed sediment traps adjacent to two active hydrothermal vents at 9°50’N on the East Pacific Rise (EPR) to assess variability in bacterial community structure associated with plume particles on the time scale of weeks to months, to determine if an endemic population of plume microbes exists, and to establish ecological relationships between bacterial populations and vent chemistry. Automated rRNA intergenic spacer analysis (ARISA) indicated there are separate communities at the two different vents and temporal community variations between each vent. Correlation analysis between chemistry and microbiology indicated that shifts in the coarse particulate (>1 mm) Fe/(Fe+Mn+Al), Cu, V, Ca, Al, 232Th, and Ti as well as fine-grained particulate (<1 mm) Fe/(Fe+Mn+Al), Fe, Ca and Co are reflected in shifts in microbial populations. 16S rRNA clone libraries from each trap at three time points revealed a high percentage of Epsilonproteobacteria clones and hyperthermophilic Aquificae. There is a shift towards the end of the experiment to more Gammaproteobacteria and Alphaproteobacteria, many of whom likely participate in Fe and S cycling. The particle attached plume environment is genetically distinct from the surrounding seawater. While work to date in hydrothermal environments has focused on determining the microbial communities on hydrothermal chimneys and the basaltic lavas that form the surrounding seafloor, little comparable data exists on the plume environment that physically and chemically connects them. By employing sediment traps for a time series approach to sampling, we show that bacterial community composition on plume particles changes on time scales much shorter than previously known.This work was supported by the NSF Marine Geology and Geophysics program, the Science and Technology program, and the Gordon and Betty Moore Foundation

Triple iron isotope constraints on the role of ocean iron sinks in early atmospheric oxygenation

International audienceThe role that iron played in the oxygenation of Earth’s surface is equivocal. Iron could have consumed molecular oxygen when Fe3+-oxyhydroxides formed in the oceans, or it could have promoted atmospheric oxidation by means of pyrite burial. Through high-precision iron isotopic measurements of Archean-Paleoproterozoic sediments and laboratory grown pyrites, we show that the triple iron isotopic composition of Neoarchean-Paleoproterozoic pyrites requires both extensive marine iron oxidation and sulfide-limited pyritization. Using an isotopic fractionation model informed by these data, we constrain the relative sizes of sedimentary Fe3+-oxyhydroxide and pyrite sinks for Neoarchean marine iron. We show that pyrite burial could have resulted in molecular oxygen export exceeding local Fe2+ oxidation sinks, thereby contributing to early episodes of transient oxygenation of Archean surface environments

A First Look at Dissolved Ge Isotopes in Marine Sediments

The removal of chemical species from seawater during the precipitation of authigenic minerals is difficult to constrain but may play a major role in the global biogeochemical cycles of some elements, including silicon (Si) and germanium (Ge). Here, we present Ge/Si, δ^(74)Ge, and supporting chemical data of pore waters and core incubations at three continental margin sites in California and the Gulf of Mexico. We used these data to partition Ge release and uptake by the various allogenic (delivered via sedimentation) and authigenic (formed in situ) phases in these sediments. About half of the pore water Ge (δ^(74)Ge_(pw) = 1.3–2.4‰) is supplied by biogenic silica dissolution (δ^(74)Ge ~ 3‰), with the other half contributed by lithogenic particulates (δ^(74)Ge ~ 0.6‰). The highest Ge/Si (~3μmol/mol) and lowest δ^(74)Ge (1.3–1.9‰) are observed at the Fe redox horizon, suggesting a supply from detrital Ge-rich Fe oxides. The precipitation of authigenic phases (most likely aluminosilicate clays) in deeper sediments preferentially incorporates Ge over Si, resulting in low pore water Ge/Si (~0.3μmol/mol). The lack of corresponding δ^(74)Ge_(pw) trend indicates negligible Ge isotope fractionation during this process. Ge fluxes measured via core incubations were variable and appeared strongly controlled by Fe redox behavior near the sediment-water interface. In some cases, reductive Fe oxide dissolution appeared to enhance the benthic Ge flux by over 100% and released fractionated low δ74Ge of ~−0.7‰, resulting in overall benthic δ^(74)Ge_(inc) between –0.2 and 3.6‰, depending on Fe oxide contribution to Ge flux. We estimate that detrital inputs supply 12–31% of total dissolved Ge to continental margin pore fluids globally, resulting in an average pore water and benthic flux δ^(74)Ge between 2.2 and 2.7‰. Assuming 10-60% of pore water Ge is captured by the authigenic aluminosilicate sink, the dissolved Ge flux to the ocean derived from terrigenous inputs should be roughly 2.5–6.6 Mmol/y, much higher than previously estimated. Our results imply that authigenic Si burial in continental margins should be in the range of 1–8 Tmol/y (best estimate 3.1 Tmol/y), sufficient to close the global marine Si budget

A First Look at Dissolved Ge Isotopes in Marine Sediments

The removal of chemical species from seawater during the precipitation of authigenic minerals is difficult to constrain but may play a major role in the global biogeochemical cycles of some elements, including silicon (Si) and germanium (Ge). Here, we present Ge/Si, δ74Ge, and supporting chemical data of pore waters and core incubations at three continental margin sites in California and the Gulf of Mexico. We used these data to partition Ge release and uptake by the various allogenic (delivered via sedimentation) and authigenic (formed in situ) phases in these sediments. About half of the pore water Ge (δ74Gepw = 1.3–2.4‰) is supplied by biogenic silica dissolution (δ74Ge ~ 3‰), with the other half contributed by lithogenic particulates (δ74Ge ~ 0.6‰). The highest Ge/Si (~3μmol/mol) and lowest δ74Ge (1.3–1.9‰) are observed at the Fe redox horizon, suggesting a supply from detrital Ge-rich Fe oxides. The precipitation of authigenic phases (most likely aluminosilicate clays) in deeper sediments preferentially incorporates Ge over Si, resulting in low pore water Ge/Si (~0.3μmol/mol). The lack of corresponding δ74Gepw trend indicates negligible Ge isotope fractionation during this process. Ge fluxes measured via core incubations were variable and appeared strongly controlled by Fe redox behavior near the sediment-water interface. In some cases, reductive Fe oxide dissolution appeared to enhance the benthic Ge flux by over 100% and released fractionated low δ74Ge of ~−0.7‰, resulting in overall benthic δ74Geinc between –0.2 and 3.6‰, depending on Fe oxide contribution to Ge flux. We estimate that detrital inputs supply 12–31% of total dissolved Ge to continental margin pore fluids globally, resulting in an average pore water and benthic flux δ74Ge between 2.2 and 2.7‰. Assuming 10-60% of pore water Ge is captured by the authigenic aluminosilicate sink, the dissolved Ge flux to the ocean derived from terrigenous inputs should be roughly 2.5–6.6 Mmol/y, much higher than previously estimated. Our results imply that authigenic Si burial in continental margins should be in the range of 1–8 Tmol/y (best estimate 3.1 Tmol/y), sufficient to close the global marine Si budget

Iron isotope systematics in estuaries : the case of North River, Massachusetts (USA)

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 4045-4059, doi:10.1016/j.gca.2009.04.026.Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ56Fe values (with an average of 0.43 ± 0.04 ‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ56Fe values vary from -0.09‰ at no flocculation to ~ 0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ56Fe composition of rivers can also be characterized by more positive δ56Fe values (up to 0.3 per mil) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe isotopes during continental run-off.This study was supported by the National Science Foundation (OCE 0550066) to O. Rouxel and Edward Sholkovitz

Iron isotope fractionation in subterranean estuaries

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 3413-3430, doi:10.1016/j.gca.2008.05.001.Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redoxstratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ56Fe values between 0.3 and –1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ56Fe values down to –5‰. These low δ56Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Feoxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe values between –2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ56Fe values relative to river values.This study was supported by the National Science Foundation (OCE 0550066) to OR and ES , (OCE 0095384) to MC and ES and NASA Astrobiology Institute - Cycle 3 CAN-02-OSS-02 to KJE