Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H₂S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS⁻ production.     

Contributions from glacially derived sediment to the global iron (oxyhydr)oxide cycle: Implications for iron delivery to the oceans

Estimates of glacial sediment delivery to the oceans have been derived from fluxes of meltwater runoff and iceberg calving, and their sediment loads. The combined total (2900 Tg yr⁻¹) of the suspended sediment load in meltwaters (1400 Tg yr⁻¹) and the sediment delivered by icebergs (1500 Tg yr⁻¹) are within the range of earlier estimates. High-resolution microscopic observations show that suspended sediments from glacial meltwaters, supraglacial, and proglacial sediments, and sediments in basal ice, from Arctic, Alpine, and Antarctic locations all contain iron (oxyhydr)oxide nanoparticles, which are poorly crystalline, typically ∼5 nm in diameter, and which occur as single grains or aggregates that may be isolated or attached to sediment grains. Nanoparticles with these characteristics are potentially bioavailable. A global model comparing the sources and sinks of iron present as (oxyhydr)oxides indicates that sediment delivered by icebergs is a significant source of iron to the open oceans, beyond the continental shelf. Iceberg delivery of sediment containing iron as (oxyhydr)oxides during the Last Glacial Maximum may have been sufficient to fertilise the increase in oceanic productivity required to drawdown atmospheric CO₂ to the levels observed in ice cores.     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.     

Provenance and accumulation rates of opaline silica,Al, Ti,Fe, Mn,Cu, Ni and Co in Pacific pelagic sediments

Accumulation rates and chemical compositions have been obtained for pelagic sediments for 73 locations in the Pacific and for 11 in the Indian Ocean. The data for the Pacific show that many elements accumulate rapidly close to the continents and slowly in the central part of the ocean. This pattern is interrupted by two major zones of relatively high accumulation rates, one along the Equator and one along the East Pacific Rise. Deposition of opaline silica is almost completely restricted to areas of known high biological productivities at the Equator and at very high latitudes. Cu and Ni show stronger tendencies than Fe and Mn to precipitate with opaline silica. The highest accumulation rates of Fe and Mn in the open Pacific occur along the East Pacific Rise, to some extent also Cu and Ni are enriched there due to volcanic processes. Al and Ti show high accumulation rates only close to the continents; these elements appear to be almost completely terrigenous.Provenance studies of minerogen fractions, using the relations between Fe, Ti, Al and Mn, show that significant quantities of basaltic matter (oceanic crust) are incorporated into the sediments only in areas of very low total sedimentation rates in the vicinity of oceanic island groups such as Polynesia and Hawaii, whereas hydrothermal processes act as a major sediment source only on the East Pacific Rise. Sediments in the north as well as in the southernmost part of the Pacific are nearly entirely terrigenous. A balance estimate of the minerogen fraction of the deep-sea sediments from the open Pacific suggests that between 75 and 95% of all sediments in the Pacific are terrigenous and that submarine weathering (and release of basaltic debris in general) and submarine exhalations each account for only a small fraction of the sediments.     

Iron and manganese diagenesis in deep sea volcanogenic sediments and the origins of pore water colloids

Volcanogenic sediments are typically rich in Fe and Mn-bearing minerals that undergo substantial alteration during early marine diagenesis, however their impact on the global biogeochemical cycling of Fe and Mn has not been widely addressed. This study compares the near surface (0-20 cm below sea floor [cmbsf]) aqueous (<0.02 μm) and aqueous + colloidal here in after ‘dissolved’ (<0.2 μm) pore water Fe and Mn distributions, and ancillary O_2(aq), and solid-phase reactive Fe distributions, between two volcanogenic sediment settings: [1] a deep sea tephra-rich deposit neighbouring the volcanically active island of Montserrat and [2] mixed biosiliceous-volcanogenic sediments from abyssal depths near the volcanically inactive Crozet Islands archipelago. Shallow penetration of O_2(aq) into Montserrat sediments was observed (<1 cmbsf), and inferred to partially reflect oxidation of fine grained Fe(II) minerals, whereas penetration of O_2(aq) into abyssal Crozet sediments was >5 cmbsf and largely controlled by the oxidation of organic matter. Dissolved Fe and Mn distributions in Montserrat pore waters were lowest in the surface oxic-layer (0.3 μM Fe; 32 μM Mn), with maxima (20 μM Fe; 200 μM Mn) in the upper 1-15 cmbsf. Unlike Montserrat, Fe and Mn in Crozet pore waters were ubiquitously partitioned between 0.2 μm and 0.02 μm filtrations, indicating that the pore water distributions of Fe and Mn in the (traditionally termed) ‘dissolved’ size fraction are dominated by colloids, with respective mean abundances of 80% and 61%. Plausible mechanisms for the origin and composition of pore water colloids are discussed, and include prolonged exposure of Crozet surface sediments to early diagenesis compared to Montserrat, favouring nano-particulate goethite formation, and the elevated dissolved Si concentrations, which are shown to encourage fine-grained smectite formation. In addition, organic matter may stabilise authigenic Fe and Mn in the Crozet pore waters. We conclude that volcanogenic sediment diagenesis leads to a flux of colloidal material to the overlying bottom water, which may impact significantly on deep ocean biogeochemistry. Diffusive flux estimates from Montserrat suggest that diagenesis within tephra deposits of active island volcanism may also be an important source of dissolved Mn to the bottom waters, and therefore a source for the widespread hydrogenous MnO_x deposits found in the Caribbean region.     

Chemical evolution of mid-ocean ridge hot springs

Chemical analyses yielding elemental concentrations of major and minor elements of four hot springs on the East Pacific Rise at 21°N and 10 hot springs from the southern trough of the Guaymas Basin, Gulf of California provide a basis for thermodynamic modeling of conductive cooling of the hydrothermal endmembers, mixing of the hydrothermal endmember with seawater, and reaction of an EPR-type fluid with sediment of bulk chemical composition corresponding to unaltered sediment from DSDP hole 477 in the Guaymas Basin. Results of the calculations indicate that conductive cooling of endmember fluids within closed chimneys and conduits accounts for the solution composition of one vent on the East Pacific Rise and several vents in Guaymas Basin. Mixing of the hydrothermal fluids with seawater yields a prediction of mineral assemblages closely approximating those observed in samples of chimneys from the East Pacific Rise and drill cores in Guaymas Basin. The hypothesis that Guaymas Basin hydrothermal fluids result from interaction of an EPR-type fluid with sediment cover in Guaymas Basin is supported by calculations which predict an increase in pH to a value similar to Guaymas Basin fluids, an order-of-magnitude decrease in metal concentrations, and an excellent agreement between predicted mineral assemblages as a function of extent of interaction with sediment, and observed mineral assemblage distribution with depth.     

Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.     

Zinc mobility and speciation in soil covered by contaminated dredged sediment using micrometer-scale and bulk-averaging X-ray fluorescence, absorption and diffraction techniques

The mobility and solid-state speciation of zinc in a pseudogley soil (pH = 8.2-8.3) before and after contamination by land-disposition of a dredged sediment ([Zn] = 6600 mg kg⁻¹) affected by smelter operations were studied in a 50 m² pilot-scale test site and the laboratory using state-of-the-art synchrotron-based techniques. Sediment disposition on land caused the migration of micrometer-sized, smelter-related, sphalerite (ZnS) and franklinite (ZnFe₂O₄) grains and dissolved Zn from the sediment downwards to a soil depth of 20 cm over a period of 18 months. Gravitational movement of fine-grained metal contaminants probably occurred continuously, while peaks of Zn leaching were observed in the summer when the oxidative dissolution of ZnS was favored by non-flooding conditions. The Zn concentration in the <50 μm soil fraction increased from ∼61 ppm to ∼94 ppm in the first 12 months at 0-10 cm depth, and to ∼269 ppm in the first 15 months following the sediment deposition. Higher Zn concentrations and enrichments were observed in the fine (<2 μm) and very fine (<0.2 μm) fractions after 15 months (480 mg kg⁻¹ and 1000 mg kg⁻¹, respectively), compared to 200 mg kg⁻¹ in the <2 μm fraction of the initial soil. In total, 1.2% of the Zn initially present in the sediment was released to the environment after 15 months, representing an integrated quantity of ∼4 kg Zn over an area of 50 m². Microfocused X-ray fluorescence (XRF), diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques were used to image chemical associations of Zn with Fe and Mn, and to identify mineral and Zn species in selected points-of-interest in the uncontaminated and contaminated soil. Bulk average powder EXAFS spectroscopy was used to quantify the proportion of each Zn species in the soil. In the uncontaminated soil, Zn is largely speciated as Zn-containing phyllosilicate, and to a minor extent as zincochromite (ZnCr₂O₄), ^IVZn-sorbed turbostratic birnessite (δ-MnO₂), and Zn-substituted goethite. In the upper 0-10 cm of the contaminated soil, ∼60 ± 10% of total Zn is present as ZnS inherited from the overlying sediment. Poorly-crystalline Zn-sorbed Fe (oxyhydr)oxides and zinciferous phyllosilicate amount to ∼20-30 ± 10% each and, therefore, make up most of the remaining Zn. Smaller amounts of franklinite (ZnFe₂O₄), Zn-birnessite and Zn-goethite were also detected. Further solubilization of the Zn inventory in the sediment, and also remobilization of Zn from the poorly-crystalline neoformed Fe (oxyhydr)oxide precipitates, are expected over time. This study shows that land deposition of contaminated dredged sediments is a source of Zn for the covered soil and, consequently, presents environmental hazards. Remediation technologies should be devised to either sequester Zn into sparingly soluble crystalline phases, or remove Zn by collecting leachates beneath the sediment.     

Trace metal enrichments in Lake Tanganyika sediments: Controls on trace metal burial in lacustrine systems

We investigate the distributions of several key diagenetic reactants (C, S, Fe) and redox-sensitive trace metals (Mo, Cd, Re, U) in sediments from Lake Tanganyika, East Africa. This study includes modern sediments from a chemocline transect, which spans oxygenated shallow waters to sulfidic conditions at depth, as well as ancient sediments from a longer core (∼2 m) taken at ∼900 m water depth. Modern sediments from depths spanning ∼70-335 m are generally characterized by increasing enrichments of C, S, Mo, Cd, and U with increasing water depth but static Fe distributions. It appears that the sedimentary enrichments of these elements are, to varying degrees, influenced by a combination of organic carbon cycling and sulfur cycling. These modern lake characteristics contrast with a period of high total organic carbon (C_org), total sulfur (S_Tot), and trace metal concentrations observed in the 900 m core, a period which follows the most recent deglaciation (∼18-11 ky). This interval is followed abruptly by an interval (∼11-6 ky) that is characterized by lower C, S, U, and Mo. Consistent with other work we suspect that the low concentrations of S, Mo, and U may indicate a period of intense lake mixing, during which time the lake may have been less productive and less reducing as compared to the present. An alternative, but not mutually exclusive, hypothesis is that changes in the lake’s chemical inventory, driven by significant hydrological changes, could be influencing the distribution of sedimentary trace elements through time.     

The Association of Cobalt with Iron and Manganese (Oxyhydr)oxides in Marine Sediment

Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments. We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment, we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulphides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Plankton: Its chemical composition and its significance as a source of pelagic sediments

The absolute concentrations of minor and trace elements vary considerably in plankton. However, normalization of elemental abundances versus the minor elements Fe, Al and Zn (instead of the commonly used normalization versus seawater concentrations) demonstrates that these elements show remarkably constant proportions vis à vis each other. Thus, Ti, Fe, Al, Mn, V, and Zr occur in marine lower organisms in the same proportions as in the average shale, whereas Ba, Cr, Cu, Ni, Cd, Pb, Zn and B are enriched relative to the shale abundances, as are also Ca, Mg, Na, K, and Sr. These patterns appear to suggest that marine plankton are rich in lithogenic matter, but this is probably not the normal case.Contrary to the uniformity of plankton, sediments from the Pacific vary considerably in composition. Under the Equatorial high-productivity region the sediments show striking similarities with a mixture of average shale and average plankton mass, as could be expected, whereas sediments from the East Pacific Rise differ considerably from such mixtures. An iron—manganese phase (of deep-seated origin?), mixed with biological matter, on the other hand, yields model sediments with remarkable similarities to the East Pacific Rise deposits. It is therefore likely that biological processes account for a considerable fraction of some elements such as Cu, Ni, Zn and Ba also in the East Pacific Rise metalliferous sediments.     

Arsenic incorporation into authigenic pyrite, Bengal Basin sediment, Bangladesh

Sediment from two deep boreholes (∼400 m) approximately 90 km apart in southern Bangladesh was analyzed by X-ray absorption spectroscopy (XAS), total chemical analyses, chemical extractions, and electron probe microanalysis to establish the importance of authigenic pyrite as a sink for arsenic in the Bengal Basin. Authigenic framboidal and massive pyrite (median values 1500 and 3200 ppm As, respectively), is the principal arsenic residence in sediment from both boreholes. Although pyrite is dominant, ferric oxyhydroxides and secondary iron phases contain a large fraction of the sediment-bound arsenic between approximately 20 and 100 m, which is the depth range of wells containing the greatest amount of dissolved arsenic. The lack of pyrite in this interval is attributed to rapid sediment deposition and a low sulfur flux from riverine and atmospheric sources. The ability of deeper aquifers (>150 m) to produce ground water with low dissolved arsenic in southern Bangladesh reflects adequate sulfur supplies and sufficient time to redistribute the arsenic into pyrite during diagenesis.     

Paleoenvironmental implications of concentration and C/C ratios of Fe(CO3)OH in goethite from a mid-latitude Cenomanian laterite in southwestern Minnesota

A mid-Cretaceous (∼95 Ma) laterite in southwestern Minnesota contains pisolites that consist primarily of gibbsite, quartz, and kaolinite with smaller amounts of goethite (α-FeOOH) and hematite. The presence of minor berthierine (an Fe(II) sheet silicate) suggests that this Cenomanian laterite experienced some degree of low temperature reductive diagenesis during its burial history. The prospects for extracting useful paleoenvironmental information from the pisolitic goethite were explored by studying measured mole fraction (X_m) and δ¹³C_m values of the Fe(CO₃)OH component in solid solution in the goethite using the method of incremental vacuum dehydration-decarbonation.Data arrays that occupy distinctly different domains in plots of δ¹³C_m vs. 1/X_m suggest the existence of two generations of goethite in the pisolites. The apparently younger generation of goethite (“generation 2”) evolves CO₂ at 170 °C, while the older generation (“generation 1”) evolves CO₂ at 220 °C. The distribution of the data suggests that generation 2 goethite is a proxy for mixing of CO₂ from three distinct CO₂ sources in an oxidative environment which post-dated the reductive diagenesis. The small amount of generation 1 goethite seems to have persisted through the reductive diagenesis, and nine of the generation 1 goethite data appear to define a proxy, two-endmember, soil CO₂ mixing line. Such two-component mixing is consistent with expectations for a highly evolved, carbonate-free laterite (i.e., the pre-diagenetic Cenomanian weathering system). The δ¹³C_m values of these nine data points range from −23.1‰ to −13.7‰, whereas X_m values range from 0.0007 to 0.0222. Linear regression of these nine data yields a slope of 0.0064, which corresponds to an ancient tropospheric CO₂ concentration of about 1900 ppmV.Isotopic data from pisolitic kaolinite indicate a paleotemperature of about 24 °C at a paleolatitude of ∼40°N. This is substantially warmer than modern continental temperatures at such latitudes and is consistent with published indications of a generally warmer mid-Cretaceous climate. Moreover, the correspondence of a warmer mid-Cretaceous climate with the inferred, relatively high concentration of Cenomanian tropospheric CO₂ (∼1900 ppmV) is consistent with the idea that variations of atmospheric CO₂ have a relation to climate change. The results of this study emphasize the importance of careful evaluation of incremental dehydration-decarbonation data from natural goethites to assess the possibility that more than one generation of goethite is present in a sample. However, the results also indicate that the carbon isotope information recorded in admixed goethite generations may be sorted out and used in paleoenvironmental interpretations.     

History of metalliferous sedimentation at deep sea drilling site 319 in the South Eastern Pacific

Marked variations in the chemical and mineralogical composition of sediments at Site 319 have occurred during the 15 M.y. history of sedimentation at this site. The change in composition through time parallels the variability observed in surface sediments from various parts of the Nazca Plate and can be related to variations in the proportion of hydrothermal, hydrogenous, detrital and biogenous phases reaching this site at different times. Metal accumulation rates at Site 319 reach a maximum near the basement for most elements, suggesting a strong hydrothermal contribution during the early history of this site. The hydrothermal contribution decreased rapidly as Site 319 moved away from the spreading center, although a subtle increase in this source is detectable about the time spreading began on the East Pacific Rise. The most recent sedimentation exhibits a strong detritalhydrogenous influence. Post-depositional diagenesis of amorphous phases has converted them to ironrich smectite and well-crystallized goethite without significantly altering the bulk composition of the sediment.     

The role of grain dissolution and diagenetic mineral precipitation in the cycling of metals and phosphorus: A study of a contaminated urban freshwater sediment

This paper describes the detrital mineralogy, early diagenetic reactions and authigenic mineral precipitates for freshwater contaminated sediments deposited in an urban water body (the Salford Quays of the Manchester Ship Canal, Greater Manchester, UK). These sediments contain a mix of natural and anthropogenic detrital grains. Detrital grains are dominated by quartz and clay grains, whilst anthropogenic grains are dominated by metal-rich glass grains, concentrated at a depth of 12–17 cm in the sediment as a result of historical inputs. Sediment porewaters contain significant concentrations of Fe, Mn, Zn and phosphate. Bacterial Fe(III) and Mn(IV) reduction are hypothesised to supply Fe²⁺ and Mn²⁺ to porewaters, with phosphate released from Fe oxide reduction or organic matter oxidation. Petrographic observations indicate that the metal-rich glass grains are undergoing chemical dissolution during early diagenesis, supplying Fe and Zn to porewaters.     

A new Fe/Mn geothermometer for hydrothermal systems: Implications for high-salinity fluids at 13°N on the East Pacific Rise

Field and experimental investigations demonstrate the chemistry of mid-ocean ridge hydrothermal vent fluids reflects fluid-mineral reaction at higher temperatures than those typically measured at the seafloor. To account for this and, in turn, be able to better constrain sub-seafloor hydrothermal processes, we have developed an empirical geothermometer based on the dissolved Fe/Mn ratio in high-temperature fluids. Using data from basalt alteration experiments, the relationship; T (°C) = 331.24 + 112.41*log[Fe/Mn] has been calibrated between 350 and 450 °C. The apparent Fe-Mn equilibrium demonstrated by the experimental data is in good agreement with natural vent fluids, suggesting broad applicability. When used in conjunction with constraints imposed by quartz solubility, associated sub-seafloor pressures can be estimated for basalt-hosted systems. As an example, this methodology is used to interpret new data from 13°N on the East Pacific Rise, where high-temperature fluids both enriched and depleted in chloride (339-646 mmol/kg), relative to seawater, are actively venting within a close proximity. Accounting for these variable salinities, active phase separation is clearly taking place at 13°N, yet the fluid Fe/Mn ratios and the silica concentrations suggest equilibration at temperatures less than those coinciding with the two-phase region. These data show the chloride-enriched fluid reflects the highest temperature and pressure (∼432 °C, 400 bars) of equilibration, consistent with circulation near the top of the inferred magma chamber. This is in agreement with the elevated CO₂ concentration relative to the chloride-depleted fluids. The noted temperature derived from the Fe/Mn geothermometer is higher than the critical temperature for a fluid of equivalent salinity. This carries the important implication that, despite being chloride-enriched relative to seawater, these fluids evolved as the vapor component of even higher salinity brine.     

Plutonium, 241Am and 137Cs ratios,inventories and vertical profiles in Washington and Oregon continental shelf sediments

Continental shelf sediments from nine locations off Washington and Oregon have ^239,240Pu inventories which average 8.0 ± 2.6 mCi/km². The Columbia River and seawaters advecting over the shelf supply Pu which is removed to underlying sediments, principally through scavenging by inorganic paniculate matter. Mass balance calculations argue that less than 20 percent of the advected Pu need be scavenged from the water column to balance river input and total shelf sediment inventories. The percentage of the Pu removed through scavenging is consistent with observed participate concentrations in shelf waters and published sediment/water distribution coefficients.No marked separation of Pu from ¹³⁷Cs is observed with depth in Pacific shelf sediments as has been reported in Atlantic coastal sediments. This interocean distinctness can be explained by differences in particle mixing and downward diffusion of Cs in sediments of varying porosities. The transuranic inventories and Pu/Cs ratios in the Pacific sediments do not support the hypothesis of Livingston and Bowen that Pu is remobilized within the sediment column by ‘complexone’ formation with (principally) organic substances.Excess ²¹⁰Pb/^239,240Pu inventory ratios in eight representative cores from the Washington shelf average 100 ± 19, even though absolute values of both inventories vary by much larger factors. This reasonably constant ratio, for a given water depth, permits estimation of total Pu inventories and prediction of sites of unusual Pu accumulation from data on the more easily measured natural radionuclide.     

Tungsten isotopes as tracers of core-mantle interactions: The influence of subducted sediments

The postulated difference in W isotopic composition of the Earth’s core of ∼2 ε_W units, compared to the bulk silicate earth (BSE) has previously been used to search for evidence of core-mantle interaction (CMI) in ocean island basalts (OIB). The absence of W isotope anomalies has thus been taken as evidence that CMI does not occur. However, the addition of subducted sediment with high W to the sources of OIB could obscure a core signature. This possibility brings into question the utility of W isotopes as tracers for CMI. To accurately consider the effects of sediment addition to mantle sources of OIB with respect to W requires improved constraints on the abundances of W in subducting sediment. Here, we present high-precision W abundance data (and other HFSE) for a suite of sediments from the Banda subduction regime in East Indonesia. Subducting East Indonesian sediments have trace element concentrations that resemble those of average upper continental crust (UCC), making these sediments valuable to consider as typical of subducted sediments. Average W abundances of 2.1 ppm, corrected for carbon content coupled with current models of 0.5% core addition and 1% sediment addition to EM1 or HIMU plume, suggest that a model hybrid source should exhibit values of ε_W = −0.24 with ∼25 ppb W. Prior studies have not reported such low W isotopic compositions or high estimated W concentrations present in the sources of either Hawaiian or French Polynesian lavas, so such large additions of core material to these plume sources seems unlikely. Given these constraints, core contributions to these source, if present, can be no more than ∼0.1%.     

Pyrite oxidation during sample storage determines phosphorus fractionation in carbonate-poor anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (∼94 Ma) and the Paleocene-Eocene thermal maximum (∼55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO₃ contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO₃ can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.