Search

The super-chondritic Mo isotopic composition of the continental crust has been attributed to contributions from subducted oceanic slabs and/or sediments, which introduce isotopically light Mo to the mantle. It has been hypothesized that dehydrated oceanic slabs subduct into the deep mantle and contribute to the genesis of ocean island basalts (OIBs). However, OIBs have similar average δ98/95Mo values (−0.22‰± 0.04‰; 2SE; n = 87) to the depleted mantle. Subducted oceanic sediments may create a light-δ98/95Mo reservoir in the subcontinental lithospheric mantle, but this has not been investigated in detail. Understanding the Mo isotopic systematics of the continental crust and mantle requires an understanding of the Mo isotopic composition of lithospheric mantle-derived volcanic rocks. The lithosphere in the Tibetan region has experienced multiple stages of oceanic subduction and is thus ideal for studying magmas derived from sediment-modified lithospheric mantle. Mafic ultrapotassic volcanic rocks (UPVRs) from the Sailipu area on the southern Tibetan Plateau have high Mg# values (67.1–72.5) and enriched Sr–Nd isotopic compositions and are primitive magmas derived from the lithospheric mantle. These rocks have higher Ce/Mo ratios (225–422) and lighter δ98/95Mo values (−0.45‰ to −0.13‰) than the depleted mantle, mid-ocean ridge basalts (MORBs), and OIBs, as well as high ε Hf (t) values at given ε Nd (t) values compared with the terrestrial array (Δε Hf = 4.59–5.73). The involvement of Ca-poor pelagic sediments rather than the lower continental crust and hydrated oceanic slab best accounts for the high Ce/Mo ratios and light δ98/95Mo values of the studied rocks. The Sailipu UPVRs also have higher Nb/Ta (18.9–20.8) and Th/La (2.6–3.4) ratios than arc-related igneous rocks and MORBs, suggesting that their source was phlogopite-bearing lithospheric mantle with a metasomatic vein component (rutile + monazite ± lawsonite). We propose a two-stage geodynamic process to explain the formation of the Sailipu UPVRs: (1) a metasomatic vein component with high Th/La and Ce/Mo ratios formed in the lithospheric mantle during multiple stages of oceanic subduction; (2) high mantle temperatures related to convective thinning of the lithosphere resulted in melting of the vein component and the ambient mantle, which produced hybrid melts of various mantle domains during the post-orogenic stage. The Sailipu UPVRs have enriched Sr–Nd isotopic compositions and high Th/La and Ce/Mo ratios, similar to lamproites that are widespread in the Tethyan orogenic realm from the Mediterranean to the southern Tibetan Plateau. Given that UPVRs with light δ98/95Mo values have also been identified in the Western Alps, we propose that the isotopically light Mo component is widespread in Tethyan lithospheric mantle. This isotopically light Mo in the lithospheric mantle may be a complementary end-member to the isotopically heavier continental crust. The recycling of subducted oceanic sediments has a key role in the deep recycling of Mo. [ABSTRACT FROM AUTHOR]

The concentration and isotopic composition of sedimentary molybdenum (Mo) has been used to distinguish different redox environments in modern marine settings and in the geological record. We report Mo concentrations and δ98Mo from porewaters and sediments in three anoxic East Anglian salt marsh pond environments: (1) 'iron-rich' sediments containing high concentrations of dissolved ferrous iron (up to 2 mM), (2) 'sulfide-rich' sediments containing very high concentrations of aqueous sulfide (up to 10 mM) and, (3) sediments that we consider to be intermediate between 'iron-rich' and 'sulfide-rich' conditions. In iron-rich sediments, we suggest that iron speciation and mineralogy controls the concentration and isotopic composition of Mo. Despite similar aqueous sulfide profiles, the intermediate and sulfide-rich pond sediment have different porewater Mo concentrations and δ98Mo. In the sulfide-rich pond sediment, we suggest that the concentration and isotopic composition of Mo is controlled by solubility equilibrium with an Fe-Mo-S mineral species (e.g. FeMoS 4) due to similarities in sediment and porewater δ98Mo throughout the sediment column. In the intermediate pond sediment, we conclude that active breakdown of iron oxides redistributes porewater Mo, observable as a peak of dissolved Mo (>100 ppb), which diffuses within the sedimentary porewaters. The sedimentary δ98Mo is higher in sulfide-rich and intermediate pond sediment (mean = 1.66‰, range = 0.98–1.92‰) than in iron-rich pond sediment (mean = 1.10‰, range = 0.28–1.65‰) with all ponds having sedimentary δ98Mo that is lower than seawater. The maximum sedimentary δ98Mo observed in these anoxic sediments, which is 0.5–0.7‰ lower than seawater, appears to be set by Fe-Mo-S equilibration with ambient thiomolybdate species. We suggest diagenetic overprinting can cause more efficient capture of pond water Mo and causes sediment δ98Mo of originally iron-rich pond sediment to evolve to higher values at progressively higher aqueous sulfide concentrations. [ABSTRACT FROM AUTHOR]

Glacial meltwater is an important source of bioessential trace elements to high latitude oceans. Upon delivery to coastal waters, glacially sourced particulate trace elements are processed during early diagenesis in sediments and may be sequestered or recycled back to the water column depending on local biogeochemical conditions. In the glaciated fjords of Svalbard, large amounts of reactive Fe and Mn (oxyhydr)oxides are delivered to the sediment by glacial discharge, resulting in pronounced Fe and Mn cycling concurrent with microbial sulfate reduction. In order to investigate the diagenetic cycling of selected trace elements (As, Co, Cu, Mo, Ni, and U) in this system, we collected sediment cores from two Svalbard fjords, Van Keulenfjorden and Van Mijenfjorden, in a transect along the head-to-mouth fjord axis and analyzed aqueous and solid phase geochemistry with respect to trace elements, sulfur, and carbon along with sulfate reduction rates. We found that Co and Ni associate with Fe and Mn (oxyhydr)oxides and enter the pore water upon reductive metal oxide dissolution. Copper is enriched in the solid phase where sulfate reduction rates are high, likely due to reactions with H 2 S and the formation of sulfide minerals. Uranium accumulates in the solid phase likely following reduction by both Fe- and sulfate-reducing bacteria, while Mo adsorbs to Fe and Mn (oxyhydr)oxides in the surface sediment and is removed from the pore water at depth where sulfidization makes it particle-reactive. Arsenic is tightly coupled to Fe redox cycling and its partitioning between solid and dissolved phases is influenced by competition with FeS for adsorption sites on crystalline Fe oxides. Differences in trace element cycling between the two fjords suggest delivery of varying amount and composition of tidewater glacier (Van Keulenfjorden) and meltwater stream (Van Mijenfjorden) material, likely related to oxidative processes occurring in meltwater streams. This processing produces a partially weathered, more reactive sediment that is subject to stronger redox cycling of Fe, Mn, S, and associated trace elements upon delivery to Van Mijenfjorden. With climate warming, the patterns of trace element cycling observed in Van Mijenfjorden may also become more prevalent in other Svalbard fjords as tidewater glaciers retreat into meltwater stream valleys. [ABSTRACT FROM AUTHOR]

Bulk organic stable carbon isotope (δ 13 C) and element geochemistry (total organic carbon (TOC) and organic carbon to total nitrogen (C/N)) analysis is a developing technique in Holocene relative sea-level (RSL) research. The uptake of this technique in Northern Europe is limited compared to North America, where the common existence of coastal marshes with isotopically distinctive C 3 and C 4 vegetation associated with well-defined inundation tolerance permits the reconstruction of RSL in the sediment record. In Northern Europe, the reduced range in δ 13 C values between organic matter sources in C 3 estuaries can make the identification of elevation-dependent environments in the Holocene sediment record challenging and this is compounded by the potential for post-depositional alteration in bulk δ 13 C values. The use of contemporary regional δ 13 C, C/N and TOC datasets representing the range of physiographic conditions commonly encountered in coastal wetland sediment sequences opens up the potential of using absolute values of sediment geochemistry to infer depositional environments and associated reference water levels. In this paper, the application of contemporary bulk organic δ 13 C, C/N and TOC to reconstruct Holocene RSL is further explored. An extended contemporary regional geochemical dataset of published δ 13 C, C/N and TOC observations ( n = 142) from tidal-dominated C 3 wetland deposits (representing tidal flat, saltmarsh, reedswamp and fen carr environments) in temperate NW Europe is compiled, and procedures implemented to correct for the 13 C Suess effect on contemporary δ 13 C are detailed. Partitioning around medoids analysis identifies two distinctive geochemical groups in the NW European dataset, with tidal flat/saltmarsh and reedswamp/fen carr environments exhibiting characteristically different sediment δ 13 C, C/N and TOC values. A logistic regression model is developed from the NW European dataset in order to objectively identify in the sediment record geochemical groups and, more importantly, group transitions, thus allowing the altitude of reference water levels to be determined. The application of this method in RSL research is demonstrated using the Holocene sediments of the Mersey Estuary (UK), in which δ 13 C, C/N and TOC variability is typical of that encountered in Holocene sediments from C 3 coastal wetlands in NW Europe. Group membership was predicted with high probability in the depositional contexts studied and the accuracy of group prediction is verified by microfossil evidence. The method presented facilitates the application of δ 13 C, C/N and TOC analysis in RSL reconstruction studies in C 3 vegetated wetlands throughout temperate NW Europe. [ABSTRACT FROM AUTHOR]

Information about diagenetic processes and temperatures during burial of sediments entering the subduction zone is important for understanding changes in physical properties and seismic behavior during deformation. The geochemistry of authigenic carbonates from accretionary prisms can serve as proxies for conditions during carbonate cementation and resultant lithification. We report results from the Nankai accretionary prism recovered from Integrated Ocean Drilling Program (IODP) sites C0011 and C0012 and we document continued cementation of deep sediment sections prior to subduction. Elemental and isotope data provide evidence for complex mixing of different isotopic reservoirs in pore waters contributing to carbonate chemical signatures. Carbon stable isotope values exhibit a broad range (δ 13 C V-PDB = +0.1‰ to −22.5‰) that corresponds to different stages of cement formation during burial. Carbonate formation temperatures from carbonate-clumped isotope geochemistry range from 16 °C to 63 °C at Site C0011 and 8.7 °C to 68 °C at Site C0012. The correspondence between the clumped-isotope temperatures and extrapolations of measured in situ temperatures indicate the carbonate is continuing to form at present. Calculated water isotopic compositions are in some cases enriched in 18 O relative to measured interstitial waters suggesting a component of inherited seawater or input from clay-bound water. Low oxygen isotope values and the observed Ba/Ca ratios are also consistent with carbonate cementation at depth. Strontium isotopes of interstitial waters ( 87 Sr/ 86 Sr of 0.7059–0.7069) and carbonates ( 87 Sr/ 86 Sr of 0.70715–0.70891) support formation of carbonates from a mixture of strontium reservoirs including current interstitial waters and relic seawater contemporaneous with deposition. Collectively our data reflect mixed sources of dissolved inorganic carbon and cations that include authigenic phases driven by organic carbon and volcanic alteration reactions. Physical properties of input sediments continue to undergo modification by carbonate cementation at present. Due to ongoing recrystallization, temperatures from carbonate-clumped isotopes reflect the modern geothermal gradient and may serve as useful measures of geothermal gradients in other siliciclastic basins where carbonate cementation occurs. We conclude that clumped-isotope signatures in authigenic carbonates from accretionary prisms are important proxies for the timing and conditions of cementation in active margins. Our results highlight the importance of using multi-proxy approaches to elucidate the history of carbonate cementation, particularly to establish carbonate precipitation at depth and its potential impact on the physical and mechanical properties of the sediment prior to subduction. [ABSTRACT FROM AUTHOR]

Recent geochemical work shows that subduction-zone serpentinites are repositories for fluid-mobile elements absorbed during interaction with sediment-derived fluids. Unraveling the geochemical fingerprint of these rocks helps to define timing of tectonic accretion of sediments along the subduction interface and the role of serpentinite in element recycling to volcanic arcs. Here we present the trace element and isotopic composition (B–O–H, Sr, Pb) of high-pressure serpentinites from the Voltri Massif (Ligurian Western Alps, Italy), to discuss their role as incompatible element carriers and their contribution to recycling of sediment-derived components in subduction zones. The serpentinites presented here record metamorphic olivine growth during eclogite-facies metamorphism and show undeformed and mylonitic textures. Field relations show that undeformed rocks are enclosed in deformed ones and that no metasedimentary rocks are present nearby. Undeformed serpentinite has very high δ 11 B SRM951 (from +26‰ to +30‰), low Sr and Pb isotope ratios ( 87 Sr/ 86 Sr = 0.7053–0.7069; 206 Pb/ 204 Pb = 18.131–18.205) and low As and Sb contents (0.1 and 0.01 μg/g, respectively). Oxygen and hydrogen isotope compositions are +4.5‰ and −67‰, respectively. In contrast, mylonitic serpentinite shows lower δ 11 B (from +22‰ to +17‰), significant enrichment in radiogenic Sr and Pb isotopes ( 87 Sr/ 86 Sr up to 0.7105; 206 Pb/ 204 Pb up to 18.725), and enrichment in As and Sb (1.3 and 0.39 μg/g, respectively). δ 18 O of the mylonitic serpentinites reaches values of +5.9‰, whereas δD is comparable with that of undeformed rocks (approximately −70‰). In mylonitic serpentinites, the B and Sr isotopic values and the fluid-mobile element (FME) concentrations are near those for the Voltri metasedimentary rocks (calc- and mica-schists). Pb systematics also reveal influx of a crust-derived component. Our dataset shows that undeformed serpentinite still preserves an oceanic geochemical fingerprint, whereas mylonitic serpentinite is reset in its concentrations of FME and its B, Sr and Pb isotope compositions, due to interaction with sediment- and crust-derived fluids. The environment of this interaction is either compatible with (i) an outer-rise zone setting, with percolation of seawater-derived fluids enriched in sedimentary components into bending-related fault structures, or with (ii) subduction channel domains, where ascending sediment-derived slab fluids infiltrate slices of former oceanic serpentinite accreted to the plate interface domain. Influx of sediment-derived subduction fluids along major deformation zones in serpentinite modifies the element budget of the rocks, with important implications for element recycling and the tectonic history of serpentinite. The B, Sr and Pb isotopic systematics, coupled with FME concentration in serpentinites are particularly helpful geochemical tracers of interaction between different reservoirs in subduction-interface environments, and are more sensitive than the traditionally applied stable oxygen and hydrogen isotope compositions. [ABSTRACT FROM AUTHOR]

Dark brown sediment layers are a potential stratigraphic tool in Quaternary Arctic Ocean sediments. They are rich in Mn, Fe, and trace metals scavenged from the water column and were most likely deposited during interglacial intervals. In this study, we combine sediment and pore water data from sediment cores taken in different parts of the Arctic Ocean to investigate the influence of early diagenetic processes on sediment geochemistry. In most studied cores, Mn, Co, and Mo are released into the pore waters from Mn oxide dissolution in deeper (>1.5 m) sediment layers. The relationship between sedimentary Mn, Co, and Mo contents in excess of the lithogenic background (element xs ) shows that Co xs /Mo xs values are a diagnostic tool to distinguish between layers with diagenetic metal addition from the pore waters (Co xs /Mo xs < 1), layers affected by Mn oxide dissolution and metal release (Co xs /Mo xs > 10), and unaffected layers (Co xs /Mo xs from 1 to 10). Steady-state calculations based on current pore water profiles reveal that in the studied cores, the diagenetic addition of these metals from the pore water pool alone is not sufficient to produce the sedimentary metal enrichments. However, it seems evident that dissolution of Mn oxides in the Mn reduction zone can permanently alter the primary geochemical signature of the dark brown layers. Therefore, pore water data and Co xs /Mo xs values should be considered before core correlation when this correlation is solely based on Mn contents and dark sediment color. In contrast to the mostly non-lithogenic origin of Mn in the dark brown layers, sedimentary Fe consists of a large lithogenic (80%) and a small non-lithogenic fraction (20%). Our pore water data show that diagenetic Fe remobilization is not currently occurring in the sediment. The dominant Fe sources are coastal erosion and river input. Budget calculations show that Fe seems to be trapped in the modern Arctic Ocean and accumulates in shelf and basin sediments. The Fe isotopic signal δ 56 Fe of the solid phase is positive (∼0.2–0.3‰) in samples defined as the lithogenic background without significant Fe enrichments. With increasing non-lithogenic Fe contents in the sediment, δ 56 Fe becomes more negative, which indicates a shelf-to-basin export of an isotopically lighter Fe fraction. We assume that the same transport process is true for Mn. [ABSTRACT FROM AUTHOR]

The Neoproterozoic–Cambrian transition was a key time interval in the history of the Earth, especially for variations in oceanic and atmospheric chemical composition. However, two conflicting views exist concerning the nature of ocean chemistry across the Precambrian–Cambrian boundary. Abundant geochemical evidence suggests that oceanic basins were fully oxygenated by the late Ediacaran, while other studies provide seemingly conflicting evidence for anoxic deep waters, with ferruginous conditions [Fe(II)-enriched] persisting into the Cambrian. Here, two early Cambrian sedimentary platform and shelf-slope sections in South China were investigated to trace early Cambrian ocean chemistry from Mo isotopes. The results reveal that early Cambrian sediments deposited under oxic to anoxic/euxinic conditions have δ 98/95 Mo values ranging from −0.28‰ to 2.29‰, which suggests that early Cambrian seawater may have had δ 98/95 Mo values of at least 2.29‰, similar to modern oceans. The heaviest and relatively homogeneous δ 98/95 Mo values were recorded in siltstone samples formed under completely oxic conditions, which is considered that Mn oxide-free shuttling was responsible for such heavy δ 98/95 Mo value. Further, combined with Fe species data and the accumulation extent of Mo and U, the variation of δ 98/95 Mo values in the two studied sections demonstrate a redox-stratified ocean with completely oxic shallow water and predominantly anoxic (even euxinic) deeper water having developed early on, which eventually became completely oxygenated. This suggests that oceanic circulation at the time became reorganized, and such changes in oceanic chemistry may have been responsible for triggering the “Cambrian Explosion” of biological diversity. [ABSTRACT FROM AUTHOR]

Understanding the extreme carbon isotope excursions found in carbonate rocks of the Ediacaran Period (635–541 Ma), where δ 13 C of marine carbonates ( δ 13 C carb ) reach their minimum ( - 12 ‰ ) for Earth history, is one of the most vexing problems in Precambrian geology. Known colloquially as the ‘Shuram’ excursion, the event has been interpreted by many as a product of a profoundly different Ediacaran carbon cycle. More recently, diagenetic processes have been invoked, with the very negative δ 13 C values of Ediacaran carbonates explained via meteoric alteration, late-stage burial diagenesis or growth of authigenic carbonates in the sediment column, thus challenging models which rely upon a dramatically changing redox state of the Ediacaran oceans. Here we present 257 δ 44 / 40 Ca and 131 δ 26 Mg measurements, along with [Mg], [Mn] and [Sr] data, from carbonates of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia to bring new isotope systems to bear on understanding the ‘Shuram’ excursion. Data from four measured sections spanning the basin reveal stratigraphically coherent trends, with variability of ∼1.5‰ in δ 26 Mg and ∼1.2‰ in δ 44 / 40 Ca. This Ca isotope variability dwarfs the 0.2–0.3 ‰ change seen coeval with the Permian–Triassic mass extinction, the largest recorded in the rock record, and is on par with putative changes in the δ 44 / 40 Ca value of seawater seen over the Phanerozoic Eon. Changes in both isotopic systems are too large to explain with changes in the isotopic composition of Ca and Mg in global seawater given modern budgets and residence times, and thus must be products of alternative processes. Relationships between δ 44 / 40 Ca and [Sr] and δ 26 Mg and [Mg] are consistent with mineralogical control ( e.g. , aragonite vs. calcite, limestone vs. dolostone) on calcium and magnesium isotope variability. The most pristine samples in the Wonoka dataset, preserving Sr concentrations (in the 1000s of ppm range) and δ 44 / 40 Ca values inherited from an originally aragonitic polymorph, have δ 13 C carb of - 8 ‰ to - 7 ‰ , thereby providing strong geochemical evidence that extremely negative δ 13 C carb values are primary products of the Ediacaran surface environment. [ABSTRACT FROM AUTHOR]

Abstract: Despite the importance of diatoms in regulating climate and the existence of large opal-containing sediments in key air-ocean exchange areas, most geochemical proxy records are based on carbonates. Among them, Boron (B) content and isotopic composition have been widely used to reconstruct pH from foraminifera and coral fossils. We assessed the possibility of a pH/CO2 seawater concentration control on B content in diatom opal to determine whether or not frustule B concentrations could be used as a pH proxy or to clarify algae physiological responses to acidifying pH. We cultured two well-studied diatom species, Thalassiosira pseudonana and Thalassiosira weissflogii at varying pH conditions and determined Si and C quotas. Frustule B content was measured by both laser-ablation inductively coupled mass spectrometry (LA-ICPMS) and secondary ion mass spectrometry (SIMS/ion probe). For both species, frustules grown at higher pH have higher B contents and higher Si requirements per fixed C. If this trend is representative of diatom silicification in a future more acidic ocean, it could contribute to changes in the efficiency of diatom ballasting and C export, as well as changes in the contribution of diatoms relative to other phytoplankton groups in Si-limited regions. If B enters the cell through the same transporter employed for HCO3 − uptake, an increased HCO3 − requirement with decreasing CO2 concentrations (higher pH), and higher B(OH)4/HCO3 − ratios would explain the observed increase in frustule B content with increasing pH. The mechanism of B transport from the site of uptake to the site of silica deposition is unknown, but may occur via silicon transport vesicles, in which B(OH)4 − may be imported for B detoxification and/or as part of a pH regulation strategy either though Na-dependent B(OH)4 −/Cl− antiport or B(OH)4 −/H+ antiport. B deposition in the silica matrix may occur via substitution of a B(OH)4 − for a negatively charged SiO− formed during silicification. With the current analytical precision, B content of frustules is unlikely to resolve ocean pH with a precision of paleoceanographic interest. However, if frustule B content was controlled mainly by HCO3 − uptake for photosynthesis, which appears to show a threshold behavior, then measurements of B content might reveal the varying importance of active HCO3 − acquisition mechanisms of diatoms in the past. [Copyright &y& Elsevier]

Abstract: We present a new integrated multi-site chronology for Lake Lisan, which occupied the Dead Sea basin and Jordan Valley during the last glacial period (70–14kka, Marine Isotope Stages 4,3,2). The Dead Sea basin lacustrine deposits are unique among closed basin sediments in that they formed in a deep, hypersaline water body that precipitated primary aragonite which is amenable to radiometric dating by U-series, providing a solid basis for studies of the relationship of Middle East climate to other changes in the high latitudes or the tropics. The application of U–Th dating for lacustrine carbonates requires corrections for detrital U and Th and hydrogenous (“initial”) 230Th. Here we followed an iterative approach, in which we evaluate the composition of the detrital contamination independently for every set of coeval samples to determine the corrected ages. These were further filtered and combined with lithological–limnological considerations, which were used to construct age–height models for all studied stratigraphic sections. Finally, the ages of stratigraphic tie-points were used to integrate the individual age–height models into a unified chronology. The resulting chronological framework indicates that the ages of several primary gypsum units associated with catastrophic lake level drops correspond with the timing of Heinrich events in the North Atlantic. Thus, a final iterative step involves refining the ages of “Lisan-gypsum events” based on the ages of Heinrich events 6, 5, 5a, 4, and 1. This approach yields an unprecedented basin-wide, unified, event-anchored chronology for the Lisan Formation, with typical age uncertainties ca. 1000–2000years (95% confidence limit) across the entire last glacial, well below those typically related to individual U–Th and radiocarbon dating of “dirty” carbonates from similar time intervals. The results can be further extrapolated to new sites and serve as a geochronometric reference for the reconstruction of the limnological history of Lake Lisan. [Copyright &y& Elsevier]

Abstract: Manganese enrichment is common in various sedimentary environments, e.g. deep ocean floor, shallow sedimentary environments where the overlying water column is oxic and phreatic aquifers, in which the Mn aquatic geochemistry is controlled by redox conditions. In many cases, aquifers recharged by organic-rich waters contain high amounts of dissolved Mn2+ that was mobilized from sedimentary Mn-oxides during microbial oxidation of the organic matter under low-oxygen conditions. Thus, the identification and quantification of the processes controlling Mn mobilization and speciation is of great practical importance as a geochemical tool for sustainable management of aquifers. This study uses column experiments to quantify the role of adsorption and precipitation in retarding Mn2+ mobilization in sandy aquifers under low-oxygen conditions. Flow-through columns were packed with pristine sandy sediment and were recharged by low-oxygen artificial solutions containing different Mn2+ concentrations. Outflow solutions from the column experiments were analyzed and simulated using a Mn2+ transport-reaction model. The results were used to demonstrate the importance of adsorption on Mn mobilization in three different aquifers. The experimental data showed that adsorption of Mn2+ on the column solids was the main control on the Mn2+ breakthrough behavior. Nevertheless, up to 20% of the Mn that entered the experimental columns was precipitated as MnCO3. The rate of MnCO3 precipitation (k p =0.04h−1) was found to be ∼3 orders of magnitude slower than the rate of Mn2+ adsorption (k a =10–200h−1). Given the slow mineral-precipitation kinetics, the water flow rate is critical in determining the potential of MnCO3 precipitation in immobilizing Mn within an aquifer. A scale-up of the Mn retardation time found in the column experiments to natural aquifer conditions, suggests that adsorption is responsible for the prolonged retardation of Mn2+ observed in three different sandy aquifers. An important practical conclusion of this study is that the environmental response to perturbation in the hydro-geochemical regime of an aquifer might be delayed for several decades. [Copyright &y& Elsevier]

Abstract: Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938m water depth indicate that only ∼20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment–water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment–water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes. [Copyright &y& Elsevier]

Abstract: The Antique and Byzantine sediments of the northern harbor of Tyre (Lebanon) store high amounts of metals and metalloids as the result of a millennial anthropogenic contamination as well as of efficient trapping and immobilization processes. Geochemical and mineralogical analyses reveal the contrasted patterns for the accumulation of trace metal(loid)s in the sedimentary sequence recovered by coring the inner part, now emerged, of the ancient harbor. Lead, Sn, Cu and Ag concentrations can be as high as 3000, 150, 1000, and 1.2μg/g, respectively. Enrichment factors were calculated with respect to (1) Th and (2) the chemistry of the substratum and appear to be driven by anthropogenic inputs. Indeed, a drastic change in both excess concentrations and concentration ratios is observed through Roman and Byzantine times, pointing to major intensification of the trade and use of metals in Tyre, coherent with historical data. Good preservation of the archeological signal, despite (1) sediment disturbances that have caused age depth inversions, and (2) the large time lapse since the time of deposition of anthropogenic trace metal(loid)s is probably due to the reducing character of the sediments. Tyre’s sedimentary sequence provides an interesting analog for modern carbonate-rich harbor environments, in which a millenary accumulation of trace metal(loid)s has been overall well preserved and suggests a restricted mobility of anthropogenic contamination for a period of time in excess of 1500years. [Copyright &y& Elsevier]

Abstract: The Patagonian fjords have a clear potential to provide high-resolution sedimentary and geochemical records of past climate and environmental change in the Southern Andes. To improve our ability to interpret these proxy records, we investigated the processes that control fjord sediment inorganic geochemistry through a geochemical, mineralogical and sedimentological analysis of surface sediment samples from the fjords of Northern Chilean Patagonia. A simple Terrestrial Index based on measurements of salinity and Fraction of Terrestrial Carbon was used to estimate the terrestrial input/river discharge at each site. Our results demonstrate that, under the cold climate conditions of Patagonia, chemical weathering is weak and the inorganic geochemical composition of the fjord sediments is primarily controlled by hydrodynamic mineralogical sorting, i.e., the intensity of river discharge. Our results suggest that the distribution of Fe, Ti and Zr in surface sediments is controlled by their association with heavy and/or coarse minerals, whereas Al is independent of hydrodynamic processes. The elemental ratios Fe/Al, Ti/Al and Zr/Al are therefore well suited for estimating changes in the energy of terrestrial sediment supply into the fjords through time. Zr/Al is particularly sensitive in proximal environments, while Fe/Al is most useful in the outer fjords and on the continental margin. In the most proximal environments, however, Fe/Al is inversely related to hydrodynamic conditions. Caution should therefore be exercised when interpreting Fe/Al ratios in terms of past river discharge. The application of these proxies to long sediment cores from Quitralco fjord and Golfo Elefantes validates our interpretations. Our results also emphasize the need to measure Al-based elemental ratios at high precision, which can be achieved using simultaneous acquisition ICP-AES technology. This study therefore constitutes a strong basis for the interpretation of sedimentary records from the Chilean Fjords. [Copyright &y& Elsevier]

Abstract: The variations of environmental conditions (T°, pH, δ13CDIC, [DIC], δ18O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ13C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ13C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species. [Copyright &y& Elsevier]

Abstract: Microbial methane in sedimentary basins comprises approximately 20% of global natural gas resources, yet little is known about the environmental requirements and metabolic rates of these subsurface microbial communities. The Illinois Basin, located in the midcontinent of the United States, is an ideal location to investigate hydrogeochemical factors controlling methanogenesis as microbial methane accumulations occur: (1) in three organic-rich reservoirs of different geologic ages and organic matter types – Upper Devonian New Albany Shale (up to 900m depth), Pennsylvanian coals (up to 600m depth), and Quaternary glacial sediments (shallow aquifers); (2) across steep salinity gradients; and (3) with variable concentrations of . For all three organic-rich reservoirs aqueous geochemical conditions are favorable for microbial methanogenesis, with near neutral pH, concentrations <2mM, and Cl− concentrations <3M. Also, carbon isotopic fractionation of CH4, CO2, and DIC is consistent with microbial methanogenesis, and increased carbon isotopic fractionation with average reservoir depth corresponds to a decrease of groundwater flushing rates with average depth of reservoir. Plots of stable isotopes of water and Cl− show mixing between a brine endmember and freshwater, suggesting that meteoric groundwater recharge has affected all microbial methanogenic systems. Additionally, similar methanogenic communities are present in all three reservoirs with comparable cell counts (8.69E3–2.58E6cells/mL). TRFLP results show low numbers of archaea species with only two dominant groups of base pairs in coals, shale, and limestone aquifers. These results compare favorably with other methanogen-containing deep subsurface environments. Individual hydrogeochemical parameters that have a Spearman correlation coefficient greater than 0.3 to variations in methanogenic species include stable isotopes of water (δ18O and δD), type of substrate (i.e. coals versus shale), pH, and Cl− concentration. The matching of variations between methanogenic TRFLP data and conservative tracers suggests that deep circulation of meteoric waters influenced archaeal communities in the Illinois Basin. In addition, coalification and burial estimates suggest that in the study area, coals and shale reservoirs were previously sterilized (>80°C in nutrient poor environments), necessitating the re-introduction of microbes into the subsurface via groundwater transport. [Copyright &y& Elsevier]

Abstract: Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment–seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34–180cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4cmyr−1 at the apex of the MV but they rapidly decrease to 0.4cmyr−1 at the periphery. The associated fluxes of boron, lithium and methane vary between 7–301, 0.5–6 and 0–806mmolm−2 yr−1, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy. [ABSTRACT FROM AUTHOR]

Abstract: Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900±70years to 4400±170years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers. [Copyright &y& Elsevier]

Abstract: Despite its location on sediment-free basalt, vent fluids from the Main Endeavour Field (MEF) contain chemical species that indicate fluids have interacted with sediments during circulation. We report on the distribution and isotopic abundances of organic compounds (C 1–C 3 alkanes and alkenes, benzene and toluene) in fluids collected from the Main Endeavour Field (MEF) in July, 2000, to understand the processes that regulate their abundances and characterize fluid sources. Aqueous organic compounds are derived from the thermal alteration of sedimentary organic matter and subsequently undergo further oxidation reactions during fluid flow. Fluid:sediment mass ratios calculated using ΣNH4 concentrations indicate that the sediments are distal to the MEF, resulting in a common reservoir of fluids for all of the vents. Following the generation from sediment alteration, aqueous organic compounds undergo secondary alteration reactions via a stepwise oxidation reaction mechanism. Alkane distributions and isotopic compositions indicate that organic compounds in MEF fluids have undergone a greater extent of alteration as compared to Middle Valley fluids, either due to differences in subsurface redox conditions or the residence time of fluids at subsurface conditions. The distributions of the aromatic compounds benzene and toluene are qualitatively consistent with the subsurface conditions indicated by equilibration of aqueous alkanes and alkanes. However, benzene and toluene do not achieve chemical equilibrium in the subsurface. Methane and CO2 also do not equilibrate chemically or isotopically at reaction zone temperatures, a likely result of an insufficient reaction time after addition of CO2 from magmatic sources during upflow. The organic geochemistry supports the assumption that the sediments with which MEF fluids interact has the same composition as sediments present in Middle Valley itself, and highlight differences in subsurface reaction zone conditions and fluid flow pathways at these two sites. [Copyright &y& Elsevier]

Abstract: High-pressure, low-temperature (HP–LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500°C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P–T–x paths. Li concentrations (⩽90ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP–LT rocks are significantly higher than MORB (4–6ppm), but similar to HP–LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP–LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP–LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5–10% of the Li in these fluids is derived from sediments. Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ7Li⩽+1±3‰) than the depleted mantle (∼+3.5±0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC–GLOSS composition over the full range of model temperatures (50–600°C) gives an average fluid δ7Li (∼+7±5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50–260°C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ7Li=+4±2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5±3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ7Li alone. [Copyright &y& Elsevier]

Abstract: This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating (3H/3He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe2+ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950–2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO3, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use. [Copyright &y& Elsevier]

Abstract: We present first data on the geochemistry, mineralogy and morphology of near-vent sediments (35 and 200m from active vent) and ridge flank sediments (approximately 3km from the vent field) as well as oxyhydroxide deposits from the Endeavour segment, Juan de Fuca Ridge. The purpose of the study was to understand better the origin and characteristic features of metalliferous sediments associated with base and precious metal massive sulfides in volcanic terrains. Hydrothermal components in sediments are Fe–Si±S-rich and Mn–Fe–Si-rich phases, sulfides and barite, which were exclusively derived from plume fallout. Sulfides are only a minor constituent of near-vent sediments (2–4wt%) and were not detected in ridge flank sediments. The study suggests that the distribution of hydrothermal phases and associated elements in near-vent and ridge flank sediments is affected mainly by processes of agglomeration, dissolution, absorption and settling that take place within a plume and to a lesser extent post-depositional processes. Rapid deposition of sulfides in the vicinity of the vents is reflected in a sharp drop of the Cu concentrations in sediments with increasing distance from the vents. Besides sulfides, important carriers of Pb, Cu, Zn and Co in near-vent sediments are Fe–Mn oxyhydroxides that occur together with silica as aggregates of gel-like material and flaky particles and as coatings on filaments. Away from the vents, trace metals are mostly in Fe–Mn oxyhydroxides and authigenic Fe-rich montmorillonite. Oxyhydroxides at the Main Endeavour field are interpreted to have originated from oxidation of mound sulfides accompanied by precipitation of primary Fe-oxyhydroxide+silica from low-temperature fluids. At the Mothra field, seafloor deposits and chimney crusts composed of Fe-oxyhydroxide±Mn+silica are considered to be direct precipitates from hydrothermal fluids that have been less diluted with seawater. Oxyhydroxide deposits exhibit unique microtextures that resemble mineralized microorganisms and may indicate existence of diverse microbial communities. [Copyright &y& Elsevier]

Abstract: The shift of lava geochemistry between volcanic front to rear-arc volcanoes in active subduction zones is a widespread phenomenon. It is somehow linked to an increase of the slab surface depth of the subducting oceanic lithosphere and increasing thickness of the mantle wedge and new constraints for its causes may improve our understanding of magma generation and element recycling in subduction zones in general. As a case study, this paper focuses on the geochemical composition of lavas from two adjacent volcanic centres from the volcanic front (VF) to rear-arc (RA) transition of the Southern Kamchatkan subduction zone, with the aim to examine whether the shift in lava geochemistry is associated with processes in the mantle wedge or in the subducted oceanic lithosphere or both. The trace element and O–Sr–Nd–Hf–Pb (double-spike)-isotopic composition of the mafic Mutnovsky (VF) and Gorely (RA) lavas in conjunction with geochemical modelling provides constraints for the degree of partial melting in the mantle wedge and the nature of their slab components. Degrees of partial melting are inferred to be significantly higher beneath Mutnovsky (∼18%) than Gorely (∼10%). The Mutnovsky (VF) slab component is dominated by hydrous fluids, derived from subducted sediments and altered oceanic crust, eventually containing minor but variable amounts of sediment melts. The composition of the Gorely slab component strongly points to a hydrous silicate melt, most likely mainly stemming from subducted sediments, although additional fluid-contribution from the underlying altered oceanic crust (AOC) is likely. Moreover, the Hf–Nd-isotope data combined with geochemical modelling suggest progressive break-down of accessory zircon in the melting metasediments. Therefore, the drastic VF to RA shift in basalt chemistry mainly arises from the transition of the nature of the slab component (from hydrous fluid to melt) in conjunction with decreasing degrees of partial melting within ∼15km across-arc. Finally, systematic variations of key inter-element with high-precision Pb-isotope ratios provide geochemical evidence for a pollution of the Mutnovsky mantle source with Gorely melt components but not vice versa, most likely resulting from trench-ward mantle wedge corner flow. We also present a geodynamic model integrating the location of the Mutnovsky and Gorely volcanic centres and their lava geochemistry with the recently proposed thermal structure of the southern Kamchatkan arc and constraints about phase equilibria in subducted sediments and AOC. Herein, the slab surface hosting the subducted sediments suffers a transition from dehydration to melting above a continuously dehydrating layer of AOC. Wider implications of this study are that an onset of (flush-) sediment melting may ultimately be the main trigger for the VF to RA transition of lava geochemistry in subduction zones. [Copyright &y& Elsevier]

We analyzed Al, Ti, Fe, Mn, Cu, Ba, Cd, U, Mo, V, and Re in water column, settling particulate, and sediment (0 to 22 cm) samples from the intense oxygen minimum zone (OMZ) of the eastern tropical North Pacific near Mazatla´n, Mexico. The goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique “suboxic” geochemical signature.The water column was characterized by a Mn maximum, reaching ∼8 nmol kg−1 at 400 m. Concentrations of Cu, Ba, Cd, Mo, Re, U, and V were unaffected by the low O2 conditions and were comparable to those of the open ocean. Sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin. Al, Ti, and Fe were mostly (at least 79%) lithogenic. About 75% of the Mn was nonlithogenic. Significant amounts (at least 58%) of Cu, Ba, Cd, and Mo were nonlithogenic.Sediment geochemistry varied across the continental shelf and slope. Cadmium, U, and Re have prominent maxima centered at 310 m, with 12.3 ppm, 10.9 ppm, and 68.3 ppb, respectively, at the core top. High values of Mo (averaging 6.8 ppm) and V (averaging 90 ppm) are seen in OMZ surface sediment. Additional down-core enrichment occurs for all redox-sensitive elements in the top 10 cm. For U, Mo, V, and Re, surface sediments are a poor indicator of metal enrichment. Comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition, especially for Cd, U, and Mo.We evaluated Re/Mo and Cd/U ratios as tracers for redox environments. Rhenium and Mo concentrations and Re/Mo ratios do not lead to consistent conclusions. Concurrent enrichments of Re and Mo are an indicator of an anoxic depositional environment. In contrast, high Re/Mo ratios are an indicator of suboxic conditions. Cadmium is enriched in surface sediments, while U has considerable down-core enrichment. The concentrations of Cd and U and the Cd/U ratio do not follow patterns predicted from thermodynamics. Though the water column is suboxic, these four redox-sensitive elements indicate that the sediments are anoxic. The implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column. [Copyright &y& Elsevier]

The first and possibly only major rise of atmospheric oxygen, from pO2 ≤ 0.1% PAL (the present atmospheric level) to pO2 ≥ 10% PAL, appears to have occurred sometime before 2 Ga ago, although the exact time of and the cause(s) for the rise have been hotly debated. Equally important questions on the atmospheric oxygen concern its stability, especially the mechanisms regulating the atmospheric pO2 level and the causes and magnitude of pO2 variations since the first major rise of atmospheric oxygen. Previous efforts to model the pO2 variation during the Phanerozoic time have typically relied on secondary information, such as the carbon and sulfur isotopic records of sedimentary rocks, and on simple dynamics of the geochemical cycles of O, C, S, and P based on box-type models. As a result, many kinetic questions about the variation and stability of atmospheric oxygen could not have been answered. Here we quantitatively evaluate the dynamics and stability of atmospheric O2 and CO2, using recent experimental data, field observations, and a new model for the C-O coupled geochemical cycles. We examine the change with time in the fluxes of various compounds (O2, CO2, phosphate, organic C, carbonate C, C-bearing reduced volcanic gases, and C-free reduced volcanic gases) among the various reservoirs (atmosphere, soil, surface ocean, deep ocean, the lower crust and mantle, and upper crust) under a variety of scenarios. Our model does not assume steady-state fluxes for any of the reservoirs. Rather, the model incorporates the kinetic experimental data on oxidation of coal, a proxy for kerogen, the dynamics of soil formation and erosion, the kinetics of decomposition of organic matter in the Oceans by aerobic and anaerobic bacteria, the equilibrium ocean-atmosphere carbonate model, the observed relationships among the organic burial flux, dissolved O2 content of deep ocean, and sedimentation rates, and the three-box model ocean. The important parameters that strongly influence the dynamics of atmospheric O2, are found to be (a) the total area of soil formation on Earth; (b) the average soil depth; (c) the average rate of physical erosion of soils, which is linked to the average rate of accumulation of clastic sediments in the oceans; (d) the composition and flux of volcanic gas; and (e) the level of atmospheric CO2. We develop kinetic equations linking these parameters to the production and consumption fluxes of atmospheric oxygen and also to stable pO2 values. Considering the likely ranges of variations in these parameters in geologic history, we suggest that the atmospheric pO2 level is likely to have stayed within a very narrow range of 0.6–2 PAL and that the entire ocean, except for local euxinic basins, is likely to have been basically oxygenated since the first major rise of atmospheric oxygen more than 2 Ga ago. [Copyright &y& Elsevier]