Sources and mechanisms for the enrichment of highly reactive iron in euxinic Black Sea sediments

The deep basinal euxinic sediments of the Black Sea are enriched in iron that is highly susceptible to sulfidization compared to oxic/suboxic continental margin sediments in the Black Sea and oxic/dysoxic continental margin and deep-sea sediments worldwide. A mass balance treatment of iron speciation data from three deep basin sediment cores shows that this enrichment is due to a combination of (1)highly reactive iron-bearing phases (sulfides and oxides) whose ultimate source was by diagenetic mobilization from the shelf (Wijsman and others, 2001) and (2) enhanced iron reactivity in the lithogenous component of deep basinal sediments. The cause of the enhanced reactivity of lithogenous iron is problematical. Possible mechanisms include microbial oxidation of non-reactive iron silicates and the preferential deposition of a fine-grained, reactive iron-enriched lithogenous component in the deep basin by the fractionation of the lithogenous flux during transport across the shelf. The application of paleoredox indicators based on iron reactivity (Degree of Pyritization, Indicator of Anoxicity) should take into account that the availability of highly reactive iron, and hence the concentration of reactive iron phases in the sediment, is controlled by a variety of chemical, physical and biological factors, some of which are not related directly to redox conditions in the water column

Rates of carbonate cementation associated with sulphate reduction in DSDP/ODP sediments: implications for the formation of concretions

DSDP/ODP porewater profiles in organic carbon-bearing (<5% org. C) sediments commonly show decreases in Ca2+ concentrations and increases in alkalinity over depths where sulphate is being removed by microbial reduction. These Ca2+ depletion profiles represent the combined effect of diffusion, advection and reaction (addition by ion exchange and removal by precipitation mainly as CaCO3 and/or dolomite). A diagenetic model has been used to estimate the rate constant (k) for Ca2+ removal by precipitation during sulphate depletion over depths of 15-150 m, assuming first order kinetics. The rate constants for Ca2+ removal range from 10(-14) to 10(-11) s(-1) in 19 DSDP/ODP sediments, which span a range of bottom water temperatures (0-10 degreesC), lithologies (calcareous to clastic) and sedimentation rates (0.001-0.4 cm year(-1)). Values of k correlate with sedimentation rate (omega) such that log k=1.16 log omega-10.3, indicating that faster rates of Ca2+ removal occur at higher sedimentation rates where there are also higher degrees of saturation with respect to CaCO3 and dolomite. Depth-integrated masses of Ca2+ removed (<100 mumol cm(-2)) during sulphate depletion over these depth ranges are equivalent to a dispersed phase of approximately 1.5 wt.% CaCO3 or 3 wt.% dolomite in a compacted sediment. The complete occlusion of sediment porosity observed in concretions with isotopic signatures suggesting carbonate sourced from sulphate reduction therefore requires more time (a depositional hiatus), more rapid sulphate reduction (possibly by anaerobic methane oxidation) and/or the continued transport of isotopically light carbonate to the concretion site after sulphate reduction has ceased

The low-temperature geochemical cycle of iron: From continental fluxes to marine sediment deposition

Suspended sediments from 34 major rivers (geographically widespread)and 36 glacial meltwater streams have been examined for their variations in different operationally-defined iron fractions; FeHR (iron oxides soluble in dithionite), FePR (iron soluble in boiling HCl but not in dithionite) and FeU (total iron less that soluble in boiling HCl). River particulates show a close association between FeHR and total iron (FeT), reflecting the effects of chemical weathering which derive oxide iron from, and retain it in close association with, total iron. Consistent with this, continentalscale average FeHR/FeT ratios vary with runoff ratios (average river runoff per unit area/average precipitation per unit area). By contrast, the diminished effects of chemical weathering produce no recognizable association of FeHR with FeT in glacial particulates, and instead both FePR and FeU are closely correlated with FeT, reflecting essentially pristine mineralogy. A comparison of the globally-averaged compositions of riverine particulates and marine sediments reveals that the latter are depleted in FeHR, FePR and FeT but enriched in FeU. The river and glacial particulate data are combined with estimates of authigenic, hydrothermal, atmospheric and coastal erosive iron fluxes from the literature to produce a global budget for FeHR, FePR, FeU and FeT. This budget suggests that the differences between riverine particulates and marine sediments can be explained by; (i) preferentially removing FeHR from the riverine particulate flux by deposition into inner shore reservoirs such as floodplains, salt marshes and estuaries; and (ii) mixing the resulting riverine particulates with FeHRdepleted glacial particulates. Preliminary measurements of inner shore sediments are consistent with (i) above. Phanerozoic and modern normal marine sediments have similar iron speciation characteristics, which implies the existence of a long-term steady state for the iron cycle. This steady state could be maintained by a glacioeustatic feedback, where FeHR-enriched riverine particulates are either more effectively trapped when sealevel is high (small ice masses, diminished glacial erosion), or are mixed with greater masses of FeHR-depleted glacial particulates when sealevel is low (large ice masses, enhanced glacial erosion). Further important controls on the steady state for FeHR operate through the formation of euxinic sediments and ironstones, which also provide sealevel-dependent sinks for FeHR-enriched sediment

Siderite concretions from nonmarine shales (Westphalian A) of the Pennines, England: Controls on their growth and composition

Back-scattered electron microscopy has been used to examine the microstructure of nonmarine-shale-hosted siderite concretions. The concretions are composed of 50-100 mu m, zoned crystallites, which exhibit no noticeable center-to-edge variation within any individual concretion. This indicates that siderite crystallites nucleated at virtually the same time across the entire concretion and that the concretions did not grow by radial addition of siderite layers around a central nucleus. Further siderite precipitation took place by crystal growth onto the nuclei. The total proportion of siderite in any part of the concretion bears no simple relationship to the porosity of the enclosing shale at the time of precipitation, and growth by passive precipitation in pore space is unlikely. Integration of microprobe data with bulk mineral-chemical and stable-isotope data suggests that the siderite crystallites are composed of an Fe-Mn-rich end member with a delta(13)C value of similar to +10 parts per thousand and a Mg-Ca-rich end member with a delta(13)C value of similar to 0 parts per thousand to -5 parts per thousand. The mineral-chemical and stable-isotope compositions of these concretions resulted from microbially mediated processes operating close (< 10 m) to the sediment-water interface, during methanogenesis. Methanogenesis can generate low-delta(13)C as well as high-delta(13)C carbonate cements, hence deep-burial diagenetic reactions, such as decarboxylation of organic matter, need not be invoked to generate solutes for siderite precipitation

Ice sheets as a significant source of highly reactive nanoparticulate iron to the oceans

The Greenland and Antarctic Ice Sheets cover ~\n10% of global land surface, but are rarely considered as active components of the global iron cycle. The ocean waters around both ice sheets harbour highly productive coastal ecosystems, many of which are iron limited. Measurements of iron concentrations in subglacial runoff from a large Greenland Ice Sheet catchment reveal the potential for globally significant export of labile iron fractions to the near-coastal euphotic zone. We estimate that the flux of bioavailable iron associated with glacial runoff is 0.40–2.54?Tg per year in Greenland and 0.06–0.17?Tg per year in Antarctica. Iron fluxes are dominated by a highly reactive and potentially bioavailable nanoparticulate suspended sediment fraction, similar to that identified in Antarctic icebergs. Estimates of labile iron fluxes in meltwater are comparable with aeolian dust fluxes to the oceans surrounding Greenland and Antarctica, and are similarly expected to increase in a warming climate with enhanced melting

Glacial and periglacial floodplain sediments regulate hydrologic transfer of reactive iron to a high arctic fjord

The transport of reactive iron (i.e. colloidal and dissolved) by a glacier-fed stream system draining a high relief periglacial landscape in the high Arctic archipelago of Svalbard is described. A negative, non-linear relationship between discharge and iron concentration is found, indicative of increased iron acquisition along baseflow pathways. Because the glaciers are cold-based and there are no intra- or sub-permafrost groundwater springs, baseflow is principally supplied by the active layer and the colluvial and alluvial sediments in the lower valley. Collectively, these environments increase the flux of iron in the stream by 40% over a floodplain length of just 8km, resulting in 6kg Fe km-2a-1 of reactive iron export for a 20% glacierized watershed. We show that pyrite oxidation in shallow-groundwater flowpaths of the floodplain is the most important source of reactive iron, although it is far less influential in the upper parts of the catchment where other sources are significant (including ironstone and secondary oxide coatings). Microbial catalysis of the pyrite oxidation occurs in the floodplain, enabling rapid, hyporheic water exchange to enhance the iron fluxes at high discharge and cause the non-linear relationship between discharge and reactive iron concentrations. Furthermore, because the pyrite oxidation is tightly coupled to carbonate and silicate mineral weathering, other nutrients such as base cations and silica are also released to the stream system. Our work therefore shows that high Arctic floodplains should be regarded as critically important regulators of terrestrial nutrient fluxes to coastal ecosystems from glacial and periglacial sources

A revised scheme for the reactivity of iron (oxyhydr)oxide minerals towards dissolved sulfide

The reaction between dissolved sulfide and synthetic iron (oxyhydr)oxide minerals was studied in artificial seawater and 0.1 M NaCl at pH 7.5 and 25°C. Electron transfer between surface-complexed sulfide and solid phase Fe(III) results in the oxidation of dissolved sulfide to elemental sulfur, and the subsequent dissolution of the surface-reduced Fe. Sulfide oxidation and Fe(II) dissolution kinetics were evaluated for freshly precipitated hydrous ferric oxide (HFO), lepidocrocite, goethite, magnetite, hematite, and Al-substituted lepidocrocite. Reaction kinetics were expressed in terms of an empirical rate equation of the form: R-i = k(i)(H2S)(t=0)(0.5)A where Ri is the rate of Fe(II) dissolution (RFe) or the rate of sulfide oxidation (RS), ki is the appropriate rate constant (kFe or kS), (H2S)t=0 is the initial dissolved sulfide concentration, and A is the initial mineral surface area. The rate constants derived from the above equation suggest that the reactivity of Fe (oxyhydr)oxide minerals varies over two orders of magnitude, with increasing reactivity in the order, goethite < hematite < magnetite << lepidocrocite ≈ HFO. Competitive adsorption of major seawater solutes has little effect on reaction kinetics for the most reactive minerals, but results in rates which are reduced by 65-80% for goethite, magnetite, and hematite. This decrease in reaction rates likely arises from the blocking of surface sites for sulfide complexation by the adsorption of seawater solutes during the later, slower stages of adsorption (possibly attributable to diffusion into micropores or aggregates). The derivation of half lives for the sulfide-promoted reductive dissolution of Fe (oxyhydr)oxides in seawater, suggests that mineral reactivity can broadly be considered in terms of two mineral groups. Minerals with a lower degree of crystal order (hydrous ferric oxides and lepidocrocite) are reactive on a time-scale of minutes to hours. The more ordered minerals (goethite, magnetite, and hematite) are reactive on a time-scale of tens of days. Substitution of impurities within the mineral structure (as is likely in nature) has an effect on mineral reactivity. However, these effects are unlikely to have a significant impact on the relative reactivities of the two mineral groups

Sources of iron for pyrite formation in marine sediments

More than two hundred aerobic continental margin, aerobic deep sea, dysaerobic, and anaerobic / euxinic sediments have been examined for their variations in different operationally defined iron fractions, each of which represents a different reactivity towards dissolved sulfide. Aerobic continental margin, deep sea, and dysaerobic sediments contain similar contents of highly reactive iron (dithionite-soluble iron plus pyrite iron), poorly reactive iron (iron soluble in HCl less that soluble in dithionite), and unreactive iron (total iron less that soluble in HCl). By contrast non-turbidite euxinic samples from the Black Sea, as well as euxinic samples from the Cariaco Basin and Framvaren are enriched in highly reactive iron. These sediments contain a small lithogenous fraction and a large biogenous, organic C-rich fraction, which decays by sulphate reduction in an iron-rich water column to form pyrite-rich sediment. Other anaerobic / euxinic samples from the Black Sea, Orca Basin, and Kau Bay contain lower concentrations of biogenous sediment and are not therefore enriched in highly reactive iron. Degrees of Pyritization (DOP) for all the aerobic, dysaerobic, and anaerobic/euxinix samples (except those low in biogenous material) are consistent with analogous ancient sediments and indicate that most pyrite formation occurs form the highly reactive iron fraction

Biolabile ferrous iron bearing nanoparticles in glacial sediments

Glaciers and ice sheets are a significant source of nanoparticulate Fe, which is potentially important in sustaining the high productivity observed in the near-coastal regions proximal to terrestrial ice cover. However, the bioavailability of particulate iron is poorly understood, despite its importance in the ocean Fe inventory. We combined high-resolution imaging and spectroscopy to investigate the abundance, morphology and valence state of particulate iron in glacial sediments. Our results document the widespread occurrence of amorphous and Fe(II)-rich and Fe(II)-bearing nanoparticles in Arctic glacial meltwaters and iceberg debris, compared to Fe(III)-rich dominated particulates in an aeolian dust sample. Fe(II) is thought to be highly biolabile in marine environments. Our work shows that glacially derived Fe is more labile than previously assumed, and consequently that glaciers and ice sheets are therefore able to export potentially bioavailable Fe(II)-containing nanoparticulate material to downstream ecosystems, including those in a marine setting. Our findings provide further evidence that Greenland Ice Sheet meltwaters may provide biolabile particulate Fe that may fuel the large summer phytoplankton bloom in the Labrador Sea, and that Fe(II)-rich particulates from a region of very high productivity downstream of a polar ice sheet may be glacial in origin

Antarctic ice sheet fertilises the Southern Ocean

Open access journalSouthern Ocean (SO) marine primary productivity (PP) is strongly influenced by the availability of iron in surface waters, which is thought to exert a significant control upon atmospheric CO2 concentrations on glacial/interglacial timescales. The zone bordering the Antarctic Ice Sheet exhibits high PP and seasonal plankton blooms in response to light and variations in iron availability. The sources of iron stimulating elevated SO PP are in debate. Established contributors include dust, coastal sediments/upwelling, icebergs and sea ice. Subglacial meltwater exported at the ice margin is a more recent suggestion, arising from intense iron cycling beneath the ice sheet. Icebergs and subglacial meltwater may supply a large amount of bioavailable iron to the SO, estimated in this study at 0.07-0.2 Tg yr-1. Here we apply the MIT global ocean model (Follows et al., 2007) to determine the potential impact of this level of iron export from the ice sheet upon SO PP. The export of iron from the ice sheet raises modelled SO PP by up to 40%, and provides one plausible explanation for seasonally very high in situ measurements of PP in the near-coastal zone. The impact on SO PP is greatest in coastal regions, which are also areas of high measured marine PP. These results suggest that the export of Antarctic runoff and icebergs may have an important impact on SO PP and should be included in future biogeochemical modelling.Philip Leverhulme PrizeLeverhulme Research FellowshipLeverhulme TrustRoyal Society Fellowship7th European Community Framework Programme - Marie Curie Intra European FellowshipNatural Environment Research Council (NERC