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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]