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We present a suite of major element stable isotope (δ13C, δ18O, δ44/40Ca, δ26Mg), and selected trace element (Sr/Ca and Mg/Ca) data from Pleistocene sediments from the Great Barrier Reef (IODP Expedition 325), as well as Holocene surface sediments from the Bahamas (Triple Goose Creek, Andros Island) to identify geochemical fingerprints associated with early marine and meteoric diagenesis. Sediments from both sites exhibit co-variation in δ13C and δ18O values, depletion in trace elements, and distinct geochemical trends in δ26Mg and δ44/40Ca values that reflect differences between diagenetic alteration in marine and meteoric fluids. While marine diagenesis results in lower Sr/Ca ratios, higher δ44/40Ca values, and little effect on bulk sediment δ26Mg values, meteoric diagenesis leads to lower Sr/Ca ratios, lower δ44/40Ca values, and lower δ26Mg values. Using a numerical model of diagenesis, we show how diagenetic alteration by meteoric fluids must occur after an initial period of diagenetic alteration by marine fluids, a two-stepped diagenetic history that complicates the interpretation of geochemical data in meteorically altered marine carbonate sediments. Finally, we discuss how paired metal isotopes may serve as a robust indicator of meteoric alteration in ancient shallow-water marine carbonate sediments. [ABSTRACT FROM AUTHOR]

The global carbon and iron cycles are intimately linked as redox-sensitive iron oxides readily bind organic carbon in a variety of environmental settings, including marine and lacustrine sediments. While these iron-organic carbon complexes sequester vast quantities of organic carbon, the composition of the organic matter within them remains unknown for lacustrine environments. Here we present C K 1s and Fe L 3,2 edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of surface sediments and authigenic iron complexes from adjacent basins of a pristine boreal lake located in Québec, Canada, with contrasting oxygen exposure regimes. We demonstrate differences in organic carbon speciation in sediments from both basins, as well as co-localization of organic carbon and iron on a sub-micron scale in 100 nm thick samples. Differences in redox cycling across these two basins allow for a direct comparison of the effect of oscillating redox conditions on the composition of organic carbon sequestered by iron. Our results suggest that reactive organic molecules, which may be polysaccharides, were found preferentially associated with iron in the perennially oxic sediments compared to more phenol rich organics in the seasonally anoxic sediments, highlighting the importance of iron oxides in the protection and preservation of labile organic compounds. Traces of aliphatic carbon were observed in sediments from the anoxic basin, alongside carboxyl and aromatic functionalities. This carboxyl-rich aliphatic material could possibly interact with the sediment mineral matrix either through a ligand exchange mechanism between the mineral phases and the carboxyl functionalities, or via non-specific hydrophobic interactions involving the aliphatic moieties. Finally, our work also shows that OC:Fe ratios should be used with caution when inferring a binding mechanism between OC and iron oxides. [ABSTRACT FROM AUTHOR]

Titanium (Ti), a typical rock-forming element, is traditionally considered to be lithophile, incompatible, and fluid-immobile, and is recognized as a significant proxy for understanding the oceanic environments, such as the content of terrestrial materials in modern marine sediments. However, recent investigations have revealed the production of various titania minerals through the alteration of volcanic rocks. Considering the occurrence of abundant volcanic rocks (e.g., volcanoclastics, seamounts, and oceanic crusts) in the oceanic environments, the activities of Ti may have been underestimated. Our study provides novel findings on the occurrence and growth mechanism of authigenic titania in the completely altered volcanic glasses collected from Line and Marshall seamounts by using multiple microanalytical methods. Both specimens primarily consist of mixed-layer illite/smectite (I/S), phillipsite, and carbonate-bearing fluorapatite, revealing that the volcanic glasses underwent palagonization processes. Scanning electron micrographs reveal numerous spherical Ti-rich shells with thicknesses of 450–1000 nm, enveloping spherical mixed-layer I/S aggregates with diameters of dozens to hundreds of microns. From the center to the edge of the spherule-shell structures, the concentration of Ti significantly increased. Further analysis using transmission electron microscopy confirms the presence of authigenic Fe-bearing titania particles within these Ti-rich shells. These titania shells likely form as a result of the migration of dissolved Ti(IV) ions and titania nanoparticles, which fill, nucleate, and aggregate at the interfaces of microspherules originally present in the volcanic glasses, ultimately coalescing into micron-sized particles through oriented attachment. Additionally, numerous titania nanoparticles, with aggregate sizes of 4–32 nm, were observed in the pore spaces of the mixed-layer I/S aggregates, likely be those trapped during Ti migration. Brookite is the dominant titania phase in both the titania shells and the smectite pores, with rutile and anatase occasionally present in the titania shells, implying the continuous mineral phase evolution during the growth of titania particles. The occurrence and distribution of titania suggest short-distance migration of Ti during palagonization processes. These findings offer new insight into the brookite formation and the Ti mobilization in basic and oxygen-rich marine environments, which is crucial for understanding the marine geochemical behaviors of Ti. [ABSTRACT FROM AUTHOR]

In fewer than fifteen years, the study of Ni stable isotopes has advanced from early method development to application of a powerful tool for resolving a long-standing question: why does it appear that output fluxes of Ni from the global oceans far exceed input fluxes? The seawater concentration of Ni, a bioessential trace metal, is almost certainly at steady state on timescales comparable to its residence time of ∼20 kyr, so some of the current flux estimates must be inaccurate. Just as the input and output fluxes should balance, so should the flux-weighted isotopic compositions of the inputs and outputs. Thus, isotopic characterization of inputs and outputs provide an additional constraint on a balanced model of the marine Ni budget. Here, we report on experiments designed to elucidate fractionation mechanisms and magnitudes for sorption of Ni to Mn oxyhydroxide (birnessite), because Mn-rich sediments accumulating on abyssal plains represent the largest sink flux of Ni from seawater to marine sediments. Our results show remarkably large fractionations at low ionic strength (average Δ60/58Ni dissolved-sorbed = +1.38 ‰). Neither closed-system equilibrium trends nor Rayleigh curves fit the data well. Fractionations are even larger at high ionic strength (Δ60/58Ni dissolved-sorbed ranging from +2.0 to +4.0 ‰), and they decrease with experimental duration from 2 d (49 h) to 27 d. The high ionic strength data fit Rayleigh trends well. Here, we use X-ray absorption fine-structure spectroscopy (EXAFS) and results from previous studies to support interpretation of our data as combinations of kinetic and equilibrium isotope effects that vary in their proportional contributions to the total fractionation with time and with surface loading. One important consequence of this study is that none of the experimental results reported thus far, including ours, are directly applicable to building steady-state models of the Ni cycle. Even our longest duration experiments did not achieve equilibrium, which is likely to be manifest in the very slowly accumulating sediments on abyssal plains. Our work constrains further the mechanisms of Ni sorption to birnessite and clearly indicates that determination of equilibrium fractionation in this system, although challenging, will be a crucial step toward resolving the apparent marine Ni imbalance. [ABSTRACT FROM AUTHOR]

A significant proportion of marine calcium carbonate sediments are comprised of metastable minerals that are susceptible to diagenetic alterations during burial. These reactions can reset the geochemical signature of sediments and pore fluids and influence elemental cycling in the ocean. However, the timing and mechanisms by which these reactions take place are poorly constrained. This study uses cores drilled on the slope of the Great Bahama Bank to provide quantitative constraints on important diagenetic reactions; namely respiration-driven dissolution, authigenic carbonate mineral formation, and conversion of aragonite to low Mg calcite (LMC). We perform detailed mineralogical characterization using newly acquired, high resolution X-ray diffraction (XRD) data and over 1000 reanalyzed XRD scans, characterize sediments texturally and elementally using electron microprobe data, calculate pore fluid saturation state with respect to aragonite using a Pitzer ion interaction approach, and use pore fluid chemistry and experimental distribution coefficients to predict authigenic carbonate compositions. These data suggest that aerobic organic matter oxidation, enabled by the advection of oxygenated seawater throughout the upper ∼ 30 m interval of sediment, causes undersaturation and thus dissolution of biogenic high Mg calcite (HMC) and aragonite. Deeper, anaerobic organic matter oxidation takes over and causes supersaturation, promoting authigenic precipitation in the form of HMC, which in turn decreases pore fluid Mg/Ca and promotes aragonite conversion to LMC. One novel aspect of this study is the identification of three types of calcites using the newly acquired XRD and electron microprobe data. Based on their unique crystallographic characteristics and chemical compositions, these types of calcites are interpreted to represent pelagic biogenic LMC, bank-derived biogenic HMC, and authigenic HMC precipitated from pore fluids. Notably, the composition of the authigenic calcite matches that predicted to precipitate from pore fluids using an empirical Mg partition coefficient in calcite. Calcites that form authigenically and from aragonite via replacement are suggested to recrystallize with burial as evidenced by the decrease in Mg content and micro-strain. This process-based geochemical framework assigns diagenetic processes to a specific depth window within the sediment column and paves the way for a mechanistic understanding of carbonate diagenesis, one that is rooted in thermodynamic and kinetic bases. [ABSTRACT FROM AUTHOR]

Constraining the role of microbes in the structural iron (Fe) reduction of iron-bearing minerals improves our understanding of sediments and ice sheets as a source of dissolved Fe (dFe) to the oceans. However, bio-mediated structural Fe-reduction has yet to be studied in cryospheric environments. Here, we show that the Fe reducing psychrophile bacterium Shewanella vesiculosa, isolated from sea ice in Antarctica, reduced structural Fe in nontronite (NAu-2) and maghemite (γ-Fe 2 O 3), common mineral phases in glacial ice, and marine sediments in Antarctica, during two freeze–thaw cycles (−10 °C to +15 °C), resulting in the release of dFe. The modification of turbostratically disordered nontronite (ferric iron dominant phase) to discrete ordered illite-like structure (ferrous iron dominant phase), and the aggregation of altered small maghemite particles with neoformation of vivianite (Fe 3 (PO 4) 2 ·nH 2 O) indicated the microbially induced reductive dissolution of nontronite and maghemite, respectively. The biotic Fe-reduction gradually decreased and ceased as the temperature approached freezing (−8 °C), however the rection reactivated in the thawing cycle (−7 to +15 °C). No discernable biotic Fe-reduction was measured for either mineral under freezing conditions, suggesting that temperature limits the activity of the microbes. Further, and regardless of temperatures during two freeze–thaw cycles, Fe-reduction was not observed in abiotic control. Overall, these results highlight the importance of microbially induced Fe reduction during seasonal freeze–thaw cycles of ice and sediments in continuous supplying bioavailable dFe to cryospheric environments and the often Fe-limited polar oceans. [ABSTRACT FROM AUTHOR]

Methane release from marine sediments strongly influences the local seafloor environment and ecosystems, and may impact Earth's climate system. Recent studies revealed anomalous molybdenum (Mo) enrichment in seep sediments, which was linked to methane release events. Marine seep sediments are a potential sink of Mo for the global ocean, while the mechanisms leading to local Mo enrichment are not fully understood. The sediments from a gas hydrate-bearing area of the South China Sea analyzed herein reveal authigenic Mo (Mo auth) contents ranging from 0 and 31.4 µg/g and δ98Mo auth values ranging from 0.18 ‰ to 3.31 ‰. The range of δ98Mo auth values of seep sediments is therefore similar to values of modern iron-rich sediments with low concentrations of dissolved porewater hydrogen sulfide and sediments deposited under weakly euxinic sediments. Among the obtained South China Sea data, the more positive δ98Mo auth values (>ca. 1.5 ‰) are interpreted to reflect diffusion of seawater Mo into the sediment at moderate seepage rates and Mo isotope fractionation during the formation of thiomolybdates in the sulfidic seep environment. The lower δ98Mo auth values (

The impact of oxygen on the preservation of organic matter in marine surface sediments is still controversial. We revisited this long-standing debate by determining the burial efficiency of sedimentary organic matter in the Black Sea, the largest anoxic and euxinic basin in the modern ocean. Surface sediments were sampled in the Danube paleodelta on the northwestern margin of the Black Sea at 420–1550 m water depth. Steady-state modeling of solid species (particulate organic carbon and nitrogen) and solutes (ammonium, sulfate, and total alkalinity) in sediments was performed to quantify rates of mass accumulation, particulate organic matter (POM) degradation, and POM burial. We develop a novel analytical model to quantify these rates applying an inverse modelling approach to down core data accounting for molecular diffusion, sediment burial and compaction. Our model results indicate that 56.7 ± 6.6 % of the particulate organic matter deposited in the study area is not degraded in surface sediments but accumulates below 10 cm sediment depth. This burial efficiency is substantially higher than those previously derived for seafloor areas underlying oxygenated bottom waters. Hence, our study confirms previous studies showing that euxinic bottom water conditions promote the preservation of particulate organic matter in marine sediments. [ABSTRACT FROM AUTHOR]

A common technique for determining the mass accumulation rates of marine sediments is through measurements of constant flux proxies. These proxies, like unsupported 230Th and extraterrestrial 3He, are buried at a known rate at the seafloor, and thus their concentration in sediments is inversely proportional to the vertical mass accumulation rate of ambient sediments. These two proxies have varied assumptions regarding their behavior that have been difficult to test, particularly in regions of very low sedimentation. We present new measurements of helium and thorium isotopes in coretop sediments from the South Pacific Gyre. Our main finding is that 230Th- and 3He-derived mass accumulation rates of these sediments differ by a factor of 2–10, with 230Th-based mass accumulation rates systematically higher than those derived from 3He. While the final cause of the discrepancy is difficult to elucidate, we suggest that up to a factor of 2 worth of the sedimentary 230Th deficit can be explained by lateral transport of 230Th, while the remainder must be explained by other processes, such as ancient coretops undercorrected for post-depositional 230Th decay. Regardless of the mechanism, our findings have critical implications for the application of constant flux proxies in the South Pacific Gyre, with one example being the calibration of dust deposition models in this region. Ultimately, additional testing is required to determine the accuracy of the 3He and 230Th techniques for estimating sediment accumulation rates in regions of the open ocean with extremely low sedimentation rates. [ABSTRACT FROM AUTHOR]

The quantification of anaerobic oxidation of organic matter in the global seabed is to a large extent based on transport-reaction modeling of pore water ions involved in the mineralization processes. As the predominant of these processes, sulfate reduction can be modeled from the depth distribution of sulfate and other relevant solutes. An active organoclastic sulfate reduction is typically characterized by sulfate profiles with a concave-down shape. We use here a comprehensive database to show that half of all competent sulfate profiles have an opposite, concave-up shape, which may appear inconsistent with this concept. We also show that there is a strong discrepancy between sulfate profiles obtained by gravity coring and by IODP coring, with generally much higher sulfate flux and shallower sulfate penetration depth in the gravity cores (the term IODP here covers the international ocean drilling programs, DSDP, ODP and IODP). The discrepancy is correlated with a selectivity for coring sites in the published studies, by which gravity coring is focused towards the ocean margins and continental shelf and towards high surface water productivity and high sedimentation rate. In contrast, IODP coring is more frequently done in low sedimentation regions and is largely absent from the continental shelf. As a result, estimates of sulfate reduction in the global seabed may be biased by a selection of only IODP core data for the modeling. Furthermore, the modeling of pore water profiles shows net rates of sulfate reduction, while 35S-radiotracer experiments show the higher gross rates of the process. Estimates from 35S-radiotracer measurements suggest that dissimilatory sulfate reduction oxidizes 77 Tmol yr−1 of organic carbon globally, which is 3- to 4-fold higher than recent data based on modeling of IODP data. The potential biases by global estimates of sulfate reduction in marine sediments are discussed. [ABSTRACT FROM AUTHOR]

The Cambrian explosion is a critical evolutionary milestone in life history, but the mechanistic relationship between the Cambrian explosion, rising atmospheric and oceanic oxygen levels, and the primary productivity remains controversial. Here, we present new mercury (Hg) isotope data from Cambrian marine sediments of the ∼521–514 Ma Yu'anshan and Shuijingtuo Formations (Nanhua Basin, South China), which preserve the famous ∼518 Ma Chengjiang and Qingjiang Cambrian Biotas, respectively. We find evidence that, prior to Cambrian animal diversification, local terrestrial and/or atmospheric inputs are important drivers of Hg enrichment in the shallow shelf Yu'anshan and Shuijintuo Formations. Elevated Hg and total organic carbon (TOC) concentrations of coeval deeper shelf and slope sections of the Niutitang Formation are mainly attributed to upwelling of Hg associated with dissolved organic carbon (Hg-DOC) from pelagic seawater, unrelated to locally high primary productivity. During the deposition of fossiliferous strata, negative shifts of Δ199Hg and δ202Hg values in the shallow water shelf shales from the Shuijingtuo Formation, combined with similar Hg isotope characteristics in the deeper shelf and slope shales, demonstrate a significant shallow and deep-water oxygenation event took place in the Nanhua Basin. A comparable negative shift of Δ199Hg values occurs in coeval Indian Craton sediments, suggesting this oxygenation event could be regional, or possibly even global, in scale. Our newly-collected Hg isotope data provide strong evidence that rising molecular oxygen levels in both surface and deep seawater are associated with enhanced marine primary productivity and could be a critical driver of the Cambrian explosion. Finally, we also argue that Hg isotopes are an emerging and promising redox proxy for studies of Precambrian seawater, but the chemical response of Hg to atmospheric and ocean oxygenation requires further calibration. [ABSTRACT FROM AUTHOR]

Sedimentary molybdenum (Mo) and uranium (U) enrichments have been widely used as a proxy for redox conditions in oxygen-depleted marine paleo-environments. However, in a dynamic upwelling system the seasonal fluctuations from oxic to completely anoxic-sulfidic bottom waters and lateral sediment transport can modify the primary Mo and U signal of the sediment, which in turn may impact paleo-redox interpretations. In this study we present pore water and solid phase data collected at two cross shelf transects during the 'more oxygenated' austral winter and 'anoxic' austral summer to study the influence of spatially and seasonally contrasting redox conditions on the formation of authigenic Mo and U enrichments in organic carbon (TOC) rich mud belt sediments on the Namibian shelf. A mass balance was established for each element based on diffusive fluxes and element mass accumulation rates to evaluate the respective mechanisms of trace metal delivery, accumulation and recycling. Mo is delivered to the sediment in its dissolved form via diffusion across the sediment–water interface, especially during austral summer when bottom waters are anoxic and surface sediments are highly sulfidic. In the center of the inner shelf mud belt, the benthic Mo fluxes of up to 37 nmol cm−2 yr−1 into sulfidic surface sediments are the highest ever reported for reducing sulfidic systems and agree with the rate of Mo accumulation in the solid phase. Concurrently, high sedimentation rates and low terrigenous input limit solid phase Mo accumulation on the Namibian shelf. In ancient marine sediments, this mode of Mo cycling can be identified by low Mo/TOC ratios of ∼2 similar to those found in sediments deposited below the perennial oxygen minimum zone on the Peruvian shelf and to those found in deposits of the Cretaceous Oceanic Anoxic Event 2. Diffusive U fluxes into the sediment are generally too low to account for the sedimentary enrichment leading to the conclusion that U is delivered mainly in particulate form. In areas with anoxic bottom water, shallow dissolved U maxima directly below the sediment water interface and rather low sedimentary U content indicate that particulate U is recycled and largely released back into the bottom water. At sites where bottom water oxygen concentrations vary from anoxic to completely oxic on seasonal timescales, the depth at which Mo and U are removed from pore waters moves vertically within the sediment column thus defining a layer between the sediment surface and ∼20 cm depth, in which Mo and U accumulate in the solid phase. Our results emphasize the importance of short-term redox fluctuations in the bottom waters and underlying sediments, as well as lateral sediment transport for the authigenic enrichment of redox-sensitive trace metals in reducing shelf sediments. The relative enrichment patterns identified might be useful for the reconstruction of open marine anoxia in the geological past. [ABSTRACT FROM AUTHOR]

We searched late Miocene sedimentary rocks in an attempt to recover fossil micrometeorites derived from the Veritas asteroid family. This study was motivated by the previous identification of a pronounced 3He peak (4-5x above background) within marine sediments with ages between ∼8.5–6.9 Ma ago (Montanari et al., 2017. GSA Bulletin, 129:1357–1376). We processed 118.9 kg of sediment from the Monte dei Corvi beach section (Italy), the global type-section for the Tortonian epoch (11.6–7.2 Ma). Samples were collected both before and within the 3He peak. Although a small number of iron-rich (I-type) fossil micrometeorites were recovered from each horizon studied (N total = 20), there is no clear difference between the pre- and intra- 3He peak samples. All micrometeorites are compositionally similar, and three out of five horizons yielded similar abundances and particle sizes. Micrometeorites extracted from sediments at the base of the 3He peak were exclusively small (ø <75 µm), while micrometeorites extracted from sediments near the highest 3He values were relatively large (ø <270 µm). The recovered fossil micrometeorites are interpreted as samples of the background dust flux derived from metal-bearing chondritic asteroids. The presence of a 3He signature combined with the absence of fossil micrometeorites or extraterrestrial spinels (Boschi et al., 2019, Spec. Pap. Geol. Soc. Am. 542:383–391) unambiguously related to the Veritas event suggests that the Veritas family is composed of highly friable materials that rarely survive on the sea floor to become preserved in the geological record. Our data supports the existing hypothesis that the Veritas asteroid family is an aqueously altered carbonaceous chondrite parent body, one that contains minimal native metal grains or refractory Cr-spinels. The low yield of fossil micrometeorites at Monte dei Corvi is attributed to loss of particles by dissolution whilst they resided on the sea floor but also due to high sedimentation rates leading to dilution of the extraterrestrial dust flux at this site. As with other fossil micrometeorite collections (e.g. Cretaceous chalk [Suttle and Genge, EPSL, 476:132–142]) the I-type spherules have been altered since deposition. In most particles, both magnetite and wüstite remain intact but have been affected by solid state geochemical exchange, characterised by partial leaching of Ni, Co and Cr and implantation of Mn, Mg, Si and Al. In some particles Mn concentrations reach up to 16.6 wt%. Conversely, in some micrometeorites wüstite has been partially dissolved, or even replaced by calcite or ankerite. Finally, we observe evidence for wüstite recrystallisation, forming a second generation of magnetite. This process is suggested to occur by oxidation during residence on the seafloor and has implications for the use of fossil I-type micrometeorites as a potential proxy for probing Earth's upper atmospheric composition (oxidative capacity) in the geological past. However, solutions to the limitations of post-depositional recrystallisation are suggested. Fossil I-type spherules remain a potential tool for palaeo-climatic studies. [ABSTRACT FROM AUTHOR]

In marine sediments, anaerobic methane oxidation (AOM) carried out by consortia of methanotrophic archaea (ANME groups) and sulfate reducing bacteria (SRB) represents a major sink for methane (40–290 Tg of C yr−1). The variability of seafloor methane seepage and AOM is crucial to sedimentary biogeochemistry and global carbon/sulfur cycling, yet poorly constrained for Earth's history. Based on the rationale that a major group of ANME preferentially synthesizes certain tetraether lipids, Methane Index (MI) measured from sedimentary archaeal lipid biomarkers called GDGTs (glycerol dialkyl glycerol tetraethers) has been widely used as a qualitative indicator for methane-impact on sediments. However, it was unclear whether small amounts of diagenetic methane in porewater could cause high MI values or that high methane flux associated with, for example cold seeps, is required. Since not all ANME groups synthesize GDGTs, another contested issue is whether this index is broadly representative of AOM. Here, we use modern porewater and sedimentary lipid profiles from the world's ocean to further explore MI's potential to address these questions. The new data show that MI is quantitatively linked to sedimentary methane diffusive flux and the depth of sulfate-methane transition zone (SMTZ) which is the diagenetic front where AOM activity is mostly concentrated. In particular, high MI values (>0.3–0.5) are strongly associated with high methane fluxes (>∼0.1 mmol m−2 d−1) and shallow SMTZ depths (<1–3 m) commonly linked to gas hydrate dissociations. Sensitivity analyses suggest that when the variability of several key parameters (e.g., seawater sulfate concentration, geothermal gradient, and sediment porosity) is small, modern MI – methane flux and MI – SMTZ depth relationships can be applied to reconstruct methane history and diagenetic zonation of the geological past. Although only Group I of ANME archaea synthesizes GDGTs, the co-occurrence of AOM biomarkers (e.g., crocetane, PMI, and hydroxyarchaeol) that are attributed to ANME-2 or ANME-3 and high MI values suggest that MI is broadly representative of AOM. Lastly, we applied MI to probe the methane venting history by using new data from a Cascadia Margin site (Hydrate Ridge, IODP U1328) since the penultimate interglacial, and reinterpreted recently reported MI data from three Southern Ocean sites (ODP 1168, 1170, and IODP U1356) during the late Oligocene – early Miocene. Overall, these applications demonstrate that MI can serve as a sensitive and quantitative proxy to help broadly establish Cenozoic and Mesozoic history of marine methane biogeochemical cycling. [ABSTRACT FROM AUTHOR]

Multistep physical and biological processing of organic matter in marginal seas modifies its composition, sedimentary pathway, and burial efficiency. This study examines how organic geochemical signals pertaining to the source and transformation in surface sediments are transported and preserved in the conduit portion of source-to-sink sedimentary systems in marginal seas such as the Taiwan Strait (TS). The aim is to gain more insight in not only the total OC burial in this highly dynamic region, but also to establish a quantitative assessment of the provenance and age of this carbon. Our study revealed that terrestrial plant wax n -alkanols represent a portion of terrestrial organic matter, characterized by refractory property and strong mobility leading to efficient transfer from the river mouth to the shelf. Soil bacteria-derived branched glycerol dialkyl glycerol tetraethers (br-GDGTs) represent the portion of terrestrial OM characterized by labile properties and low transmissibility restricted within the river mouth under normal conditions, except for episodic and pulse delivery situations. Sedimentary OC in the TS is typically characterized by a large amount of ancient OC with intensive oxidation, indicated by extremely old 14C ages (<13000 ± 180 yr) and lower petrogenic OC content in marine sediments than that of rocks sourced from the land. Diverse sourced OC supply and accumulation patterns in shallow marine conduit systems mainly influenced by complex physical processes. Quantitative source apportionment of sedimentary OC using a ternary mixing model based on the bulk δ13C and Δ14C proxies combined with sediment mass accumulation rates revealed 0.01–3.44, 0.002–3.79, and 0–3.38 mg C cm−2 yr−1 of marine, terrestrial biospheric, and petrogenic OC burial loadings in the TS. Marine OC burial could only explain 30% of net air–sea CO 2 sequestration in a narrow conduit system such as the TS, which is characterized by high sediment resuspension and strong hydrodynamic processes due to strong tidal currents and wind-driven circulation. Our findings revealed the net C buried in different marginal seas varies as a function of local couplings between physical processes and biogeochemical characteristics. [ABSTRACT FROM AUTHOR]

The deposition of fluvially derived terrestrial organic carbon (OC) together with marine OC in marine sediments has important implications for the global carbon cycle. However, dispersal extent and fates of terrestrial soil and petrogenic OC on the continental shelf have remained unclear and debated. Here, we present OC compositions and mineral properties of marine sediments from the Gulf of Thailand and the adjacent Mekong shelf, as well as river sediments from continents surrounding them in order to determine the provenance of sedimentary OC in this tropical epicontinental sea. We find that stable carbon isotope composition (δ13C) and radiocarbon activity (Δ14C) of sedimentary OC fall between those of marine OC and of river sediments, mainly composed of C3 plant-dominated pre-aged soil and petrogenic OC. Mixing model reveals that the OC in river sediments is predominantly sourced from pre-aged deep soils, accounting for 73 ± 5%, with the remaining consisting of modern surface soil (25 ± 6%) and bedrock (2 ± 1%). The sedimentary OC on the shelf is primarily derived from marine OC, accounting for 65 ± 15%, with terrestrial soil OC and petrogenic OC contributing 24 ± 14% and 10 ± 5%, respectively. The sources, degradation, and aging of OC and mineral surface area determine the spatial pattern of sedimentary OC compositions in the Gulf of Thailand and the Mekong shelf. The contents of marine, soil, and petrogenic OC decrease with increasing distance offshore, consistent with changes in spatial patterns of sedimentation rate of terrestrial materials and of marine primary production in the overlying water column. Extensive degradation of terrestrial OC and extremely low OC burial rate in this tropical epicontinental sea suggest a minor role on OC sequestration in marine sediments, but an important CO 2 source to the atmosphere in the context of the global carbon cycle. [ABSTRACT FROM AUTHOR]

Volcanism is a dominant natural source of mercury (Hg) to the atmosphere, biosphere, ocean and sediments. In recent years, sedimentary Hg contents have emerged as a tool to reconstruct volcanic activity, and particularly activity of (subaerially emplaced) large igneous provinces in geological deep time. More specifically, Hg has shown potential as a useful proxy to illuminate the previously elusive impact of such large-scale volcanism on marine and terrestrial paleo-environments. While Hg is now widely applied as volcanism tracer, non-volcanic factors controlling sedimentary Hg content are generally not well constrained. Part of this uncertainty stems from our inability to directly observe a natural unperturbed "steady-state" environment as a baseline, as the modern Hg cycle is heavily influenced by anthropogenic activity. Here we focus on the effects of ambient redox conditions in the water column and shallow sediments (early diagenesis), quantify their influence on the geological Hg record and thereby contribute to constraining their potential impact on the use of Hg as a proxy for deep-time volcanic activity. Constraining these factors is of critical importance for the application of Hg as such a proxy. Many periods in the geological past for which records have been generated, such as the Mesozoic Oceanic Anoxic Events, are marked by a variety of high-amplitude environmental perturbations, including widespread deoxygenation and deposition of organic-rich sediments. We estimate the impact of redox changes and early diagenesis on the geological Hg record using a suite of (sub)recent–Pleistocene and Upper Cretaceous sediments representing oxic to euxinic marine conditions. Our sample set includes a transect through an oxygen minimum zone and cores that record transient shifts in oxygenation state, as well as post-depositional effects – all unrelated to volcanism, to the best of our knowledge. We find substantial alterations to the Hg record and the total organic carbon and total sulfur content, which are typically assumed to be the most common carrier phases of Hg in marine sediments. Moreover, these biases can lead to signal alteration on a par with those interpreted to result from volcanic activity. Geochemical modifications are ubiquitous and their potential magnitude implies that the factors leading to biases in the geological record warrant careful consideration before interpretation. Factors of particular concern to proxy application are (1) the disproportionate loss of organic carbon and sulfur relative to Hg during oxidation that strongly modulates normalized Hg records, (2) the evasion of Hg in anoxic and mildly euxinic sediments and (3) sharp focusing of Hg during post-depositional oxidation of organic matter. We suggest that paired analyses of additional redox-sensitive trace elements such as molybdenum, and organic-matter characteristics, particularly the type of organic matter, could provide first-order constraints on the role that redox and diagenetic changes played in shaping the Hg record as part of checking the attribution of enrichments to volcanic activity. [ABSTRACT FROM AUTHOR]

In marine sediments, formation of pyrite (FeS 2) is promoted by both organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM), and these two microbial pathways might yield differing patterns of sulfur and nickel isotopic fractionation and trace-element enrichment. To better understand these pathways, we analyzed the geochemistry of authigenic pyrite aggregates from the Upper Quaternary of the western Andaman Sea (International Ocean Discovery Program, Expedition 353, Site U1447A). 34S-enriched pyrites (to ∼+41‰) in Unit Ib are interpreted as products of SD-AOM, and their enrichments in Co and Ni and low δ60Ni values (−0.63‰ to −0.09‰) may represent diagnostic signatures of a reverse-methanogenesis microbial pathway. In contrast, 34S-depleted pyrites (∼–46‰ to –38‰) in both Units I and II are consistent with sulfide formation through early diagenetic remineralization of organic matter, and their relative enrichments in Cu and V and heavier δ60Ni values (to +0.41‰) may be diagnostic of this alternative microbial pathway. This study reports for the first time a fractionation of Ni isotopes linked to preferential uptake of isotopically light Ni by the enzyme Mcr (M reductase enzyme) in reverse methanogenesis and demonstrates that OSR- and SD-AOM-associated pyrites are potentially distinguishable on the basis of their δ60Ni compositions. Such geochemical signatures may prove useful in determining processes of pyrite formation in paleo-depositional systems and in identifying ancient methane emission events. [ABSTRACT FROM AUTHOR]

Sediments of the continental shelf anoxic zones of the Benguela upwelling system (BUS) and the Peruvian upwelling system are present-day hotspots of trace element accumulation. However, contribution of the lithogenic trace element fraction and early diagenetic transformation processes are poorly constrained. The identification of source and accumulation mechanisms is necessary for the validation of trace elements as proxies for productivity and redox cycling, notably in highly dynamic upwelling systems such as the BUS. Here, we analyzed redox- and biosensitive elements (U, Ba, Ni), lithogenic tracers (Al, Ti, Zr), total organic carbon (TOC) and P in eleven short sediment cores from the Namibian shelf (ca. 22–25°S) as well as grain size fractionated hinterland samples from the Tsauchab Valley at Sossusvlei (∼25°S). These samples help to constrain the lithogenic trace element contributions, a prerequisite for a realistic interpretation of marine authigenic trace element data. Our findings corroborate previous findings that Zr is a sensitive tracer of the coarse fraction in marine sediment for dust input and/or sediment reworking. Hence, the combined analysis of the coarse fraction (Zr), organic matter, and P enrichments (TOC/P) differentiates between a calm, organic matter-rich central shelf environment and a more energetic phosphorite-rich southern shelf environment. A significant correlation of U with P in cores from the southern shelf corroborates previous findings of U incorporation into apatite, the initial formation of which requires oscillating oxic to sulfidic redox conditions. Non-apatite associated U dominates in the cores from the central shelf, where it is only enriched in the buried, anoxic parts of the sediment. This also supports oscillating oxic to sulfidic redox conditions in surface sediment, where U may be recycled. Hence, U accumulates either (i) in apatite under oscillating oxic to sulfidic conditions or (ii) in buried anoxic sediment sections. This strongly questions the use of U as indicator of suboxic conditions but rather anoxic conditions. While lithogenic fractions of U were negligible, the lithogenic fractions of Ba and Ni were found to be elevated. The calculation of authigenic Ba when accounting for lithogenic Ba from the Sossusvlei fine fractions gives more realistic authigenic Ba values. The high Ba enrichment in the BUS is interpreted as uptake of Ba by diatoms and/or nucleation of barite in P-rich diatom remains, as suggested previously. Given the shallow water depth of the cores, barite formation must already take place in subsurface waters (<50 m water depth) as opposed to previous suggesting greater water depths. The lithogenic background of Ni strongly varies from 23°S to 25°S based on Sossusvlei data and the literature. When authigenic Ni contents are calculated accordingly and plotted versus TOC, more systematic trends are seen (compared to total Ni versus TOC). Essentially all cores show an increase in the authigenic Ni/TOC ratio with sediment depth suggesting better preservation and retention of Ni as compared to TOC consistent with previous observations in sediments from the Peruvian upwelling system. This trend corroborates the use of Ni as a productivity indicator for upwelling sediments. [ABSTRACT FROM AUTHOR]

In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (C org)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic C org -rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records. [ABSTRACT FROM AUTHOR]

Reactive iron (Fe R) plays an important role in the preservation of organic carbon (OC) in coastal sediments, yet changes in the OC bound to Fe R (OC-Fe R), during transport and deposition, remain poorly understood. The main goal of this work is to investigate the variation of the age and composition of OC-Fe R from estuarine suspended particulate matter (SPM) to coastal sediments, to further understand the role of Fe R in the preservation of terrestrial OC exported from large rivers into marginal seas. We examined OC and its carbon isotopic composition (Δ14C bulk , δ13C bulk), specific surface area (SSA), grain size composition, lignin phenols, Fe R , Mössbauer spectroscopy, and isotopic signatures of OC-Fe R (Δ14C OC-FeR , δ13C OC-FeR) in SPM and surface sediments of the Changjiang Estuary. Particulate OC (POC) and Fe R concentrations in SPM are significantly higher than in surface sediments, with no significant differences between surface- and bottom-water SPM. This indicates that loss of OC and Fe R largely occurs at the sediment–water interface due in part, to rapid Fe cycling. The percentage of OC-Fe R (f OC-FeR) in SPM (6.6 ± 1.9%) is similar to that in mobile-mud sediment (8.8 ± 1.8%). There are no significant differences in OC-Fe R content (p > 0.05) from SPM to mobile-mud sediments, but non-OC-Fe R largely decreases, suggesting that terrestrial OC-Fe R has greater stability compared to terrestrial non-OC-Fe R. Both δ13C OC-FeR and Δ14C OC-FeR are lower than bulk OC, indicating that Fe R is mainly associated with pre-aged soil OC of terrestrial plant origin, especially in estuarine SPM and mobile-mud sediments. Taken together, binding with Fe R is a potential long-term protection mechanism for terrestrial OC. Both Δ14C bulk and Δ14C OC-FeR decrease with an increase in the ratio of hematite to (super)paramagnetic Fe3+, indicating that high-crystallinity iron oxide is largely associated with pre-aged terrestrial OC, and there is a potential joint maturation mechanism between Fe R and its associated OC. Based on literature comparisons of soils, estuarine SPM, and marine sediments, OC-Fe R associations are controlled mainly by sedimentary regimes, Fe R compositions, and OC sources. This work supports the notion that Fe R plays an important role in the stabilization and transport of river-derived terrestrial OC. [ABSTRACT FROM AUTHOR]

Zinc and Ni are essential micronutrients whose stable isotope systematics in marine sediments represent promising, but still developing, tracers of past ocean chemistry and biology. Sediments from upwelling continental margins have been identified as important sinks for Zn and Ni, driven by high productivity, incorporation of the metals into cells and organic carbon burial. At present, however, our understanding of how Zn and Ni isotope composition of upwelling sediments reflects specific processes in the water column is incomplete. Here, we present coupled Zn and Ni abundance and isotope data for both solid phase and porewater in a series of sediment cores collected on a shelf-to-slope transect across an oxygen minimum zone (OMZ) from the southwest African margin off Namibia. Zinc/Al and Ni/Al ratios in Namibian margin sediments are elevated relative to the lithogenic background, by factors of 1.4–2.4 and 1.7–5.7, respectively. Systematic relationships between solid phase Zn and Ni concentrations and organic carbon accumulation corroborate the view that authigenic Zn and Ni are mainly delivered to these sediments via export production from the photic zone. Corrections for detrital Ni are sometimes substantial, but authigenic δ60Ni values are within uncertainty of the modern deep ocean, at 1.38 ± 0.18 ‰ (mean and 1SD, n = 42). Authigenic δ66Zn is more variable, at −0.09 to 0.50 ‰, at or below the value for the deep ocean average. This latter observation can be attributed to Zn isotope fractionation during sequestration into authigenic ZnS phases in the sediments, either quantitatively, or partially. Porewater systematics are more complex and the profiles do not necessarily reflect the redox state of the sediment-porewater system at the time of sampling, but rather characteristics inherited from more reducing conditions in a temporally heterogeneous system. Porewater zinc concentrations (30–369 nM) are much higher than the deep ocean and increase with depth beneath the sediment–water interface. Despite this prominent increase in Zn concentrations, δ66Zn is rather constant and lighter than the deep ocean average, at 0.18 ± 0.06 ‰ (mean and 1SD, n = 33). These observations are most consistent with the buffering of the small porewater pool by the dissolution of a previously formed sulfide phase. Porewater Ni concentrations are closer to the deep ocean, mostly at 5–15 nM. The lightest porewater isotope compositions (δ60Ni as low as 0.15 ‰) are consistent with a Mn-oxide source of Ni, whereas the heaviest isotope compositions (up to 1.76 ‰) clearly reflect uptake of light Ni into sulfide at depth within the sediment. Our data, for the largest upwelling site in the modern ocean, add to sparse data from the eastern Pacific, and confirm that upwelling margin sediments bury Ni that is close to the deep ocean in isotope composition, but Zn that is generally lighter. The data thus confirm the importance of such margins in setting the heavy isotope composition of oceanic Zn. Sediments from this kind of setting hold significant potential for the construction of records of past oceanic Ni isotopes. [ABSTRACT FROM AUTHOR]

Understanding subduction processes is critical in assessing the long-term evolution of the upper mantle and continental crust. We present new geochemical data on glassy submarine lavas from the Bransfield Strait, the Phoenix and West Scotia ridges, and previously unpublished data of marine sediments from atop the Phoenix Plate. We combined new and published geochemical data from across the northern sector of the Antarctic Peninsula to unravel both large-scale mantle composition and flow across the region. The geochemistry of Phoenix and West Scotia Ridge basalts supports the hypothesis that both ridges are underlain by Pacific MORB mantle, brought into the region through the eastward expansion of the Scotia Plate. Comparisons among lavas from the Phoenix/West Scotia ridges, the South Shetland Islands volcanic arc, and the Bransfield Strait/Prince Gustav Rift back-arc region reveal that the Pacific upper mantle flowed into the mantle wedge and was subsequently modified by subduction processes. The compositions of Bransfield Strait lavas range from strongly subduction-influenced near the strait's center to akin to Phoenix Ridge MORB toward the strait's edges. This suggests that the Phoenix MORB mantle has flowed around the slab edges into the mantle wedge, diluting the subduction signal and focusing the subduction-modified mantle towards the center of the strait. Monte Carlo simulations indicate that mixing of Phoenix MORB mantle with 0 to 3 % subduction component having a fluid/sediment ratio of ∼1 can explain the compositional range in the Bransfield Strait. Furthermore, our modeling suggests the presence of a more depleted Phoenix MORB mantle beneath the South Shetland Islands modified by the addition of ∼3 % subduction component with a fluid/sediment ratio ranging from ∼0.18 to 4. The increase in fluid/sediment ratios in the South Shetland Island lavas corresponds to a spatiotemporal progression of volcanism from the southwest (40–140 Ma) to the northeast (30–60 Ma). Finally, we have identified a set of lavas with unique trace element and isotope compositions typical of alkaline volcanism found across other parts of the Antarctic Peninsula. Surprisingly, we find occurrences of these lavas on both sides of the South Shetland Trench, suggesting the presence of a distinct enriched source in the upper mantle throughout the region. [ABSTRACT FROM AUTHOR]

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. We explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O 2) bottom waters near the coast and oxygen-deficient waters (∼4 µM O 2) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling. The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (∼45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates). The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe2+. Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. This study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm. [ABSTRACT FROM AUTHOR]

The continental crust is an important reservoir for incompatible elements, including the halogen elements (F, Cl, Br, and I), but their concentrations remain poorly known, thus hindering better understanding of the role of the crust in Earth's halogen cycle. We present halogen data (F, Cl, Br, and I) for twenty-four well-characterized glacial diamictite composites that derive from the upper continental crust (UCC) and were deposited during discrete glacial events at ∼2.9 Ga, ∼2.4–2.2 Ga, 0.75–0.58 Ga, and ∼0.30 Ga. A good correlation between Cl and the highly soluble Na (R2 = 0.70), together with low and scattered Cl concentrations in the diamictites (2–279 ppm), indicates significant Cl loss during chemical weathering of the continents. The other halogens (F, Br, and I), however, are not strongly affected by chemical weathering as revealed by their correlations with less soluble elements like K, P, Nd, and Lu, which may be due to their retention in secondary minerals and/or organic matter. Increasing concentrations of F in the composites through time may reflect the evolving composition of the UCC. Using the median values of the Neoproterozoic and Paleozoic diamictite composites, halogen concentrations of the present-day weathered UCC are estimated to be: 575 ± 87 ppm F, 29 ± 20 ppm Cl, 0.65 ± 0.14 ppm Br, and 0.05 ± 0.01 ppm I (errors quoted at the median absolute deviation). Linear correlations between halogens and other elements provide estimates for minimum halogen concentrations of the present-day crystalline UCC: 394 ± 67 ppm F, 83 ± 24 ppm Cl, 0.41 ± 0.04 ppm Br, and 0.03 ± 0.01 ppm I (with 2σ uncertainties). These estimates are all lower than normalized concentrations of elements of similar incompatibility during igneous differentiation, which may reflect loss of halogens via magmatic degassing/exsolution and/or chemical weathering during the formation of the continental crust. The distinct behavior of Cl compared to Br and I during continental weathering leads to a wide range of Br/Cl (2–265 * 10−3) and I/Cl (122–197,952 * 10−6) ratios, and Br/I ratios that are distinctly higher than those of pelagic sediments and marine pore fluids. Similar halogen signals have been reported from the lithospheric mantle and may reflect recycling of terrigenous sediments. The calculated weathering flux of Cl from the continents is quite small compared to the total Cl content of seawater (<8–34 %), suggesting that Cl in seawater is mainly derived from outgassing of the mantle and/or late volatile accretion. On the other hand, the significantly higher Br and I contents in terrigenous organic-rich sediments compared to those of crystalline bedrocks suggest that significant amounts of Br and I were transported from the oceans to the continents. [ABSTRACT FROM AUTHOR]

Riverine export of petrogenic organic carbon (OC petro) from continents to coastal oceans is a dynamic component of the global carbon budget and affects the long-term atmospheric carbon reservoir. In large fluvial systems, oxidation of OC petro during transit releases a large flux of carbon dioxide to the atmosphere, influencing climate changes; however, the transport and fate of OC petro and their controls along the fluvial–marine transition remain poorly constrained. Here, we combined Raman spectral, radiocarbon activity (F14C), mineralogical, and sedimentological techniques with multiple geochemical analyses to characterize the dynamics of OC petro in the water column and sediment particles from the Yangtze River channel–estuary–shelf continuum systems. Our data show that much of the OC petro present in suspended sediment (POC petro) exported by the Yangtze River is "labile" fractions (mostly disordered materials) that can be degraded or lost during transport across the estuarine continuum, whereas the OC petro deposited in seabed sediment are characterized by highly recalcitrant, unreactive, and graphitic carbon phases. As discrete "free" particles, coarse plant debris (>63 μm) with ages of several thousand years observed in the proximal delta of the Yangtze River exhibit nearly identical characteristics of disordered materials, and the presence of aged vascular plant detritus (carbon-rich and 14C-depleted materials) may lead to an overestimate of OC petro in marine sediments. Using a Bayesian endmember mixing approach, a binary mixing model, and the ratio of fraction modern carbon (F14C) to Al/OC, we found a large decrease in POC petro concentration and loading from the suspended sediments to seabed sediments, suggesting a loss of mineral-bound OC petro fraction during sediment transport through the estuary and deposition on the shelf. We estimated that, on average, 46 ± 35 % of the POC petro initially present in suspended sediments delivered to the Yangtze River Estuary during a flood event was primarily oxidized at the sediment–water interface, leaving the most graphitic carbon components transported laterally and efficiently reburied in shelf sediments. We found that during estuarine mixing, flocculation process-induced microaggregates may provide transient physical protection for POC petro in the form of inclusions/aggregates with carbonate minerals; however, when POC petro is physically and chemically separated from its mineral matrix via disaggregation and dissolution, it may be easily oxidized by microbial activity. In contrast, OC-phyllosilicates interactions exert a first-order control on the preservation of OC petro in marine sediments. Our findings suggest that the importance of POC petro oxidation and loss in carbon cycling and budget assessments of estuaries may be underestimated. [ABSTRACT FROM AUTHOR]

Marine sediments represent the most important sink for natural organic matter (NOM) across geological time spans. Strong associations between minerals, including iron oxides, and organic matter reaching the seafloor play a fundamental role in this preservation and have been known for some decades. Despite the importance of this protective mechanism in the balances of the global carbon budget, very little is known about the affinity of NOM for reduced iron species such as mackinawite (FeS) in the anoxic layers of sediment. In this study, equilibrium partition coefficients (K d) for three types of NOM (soil extract, corn leaf extract and plankton extract) on FeS were determined through batch sorption experiments. Models were then built via multiple linear regression (MLR) and partial least squares regression (PLSR) in order to predict sorption K d 's based on the chemical characteristics of the NOM. Investigation of the PLSR regression coefficients indicates that functional groups characteristic of polysaccharides are the greatest positive predictors of NOM sorption onto FeS at marine sediment porewater pH. This conclusion was independently verified by analyses of NOM FTIR spectra pre- and post-sorption. PLSR outperformed MLR with a lower root mean square error of prediction (RMSEP) of 53.4 L/kg compared to 64.0 L/kg. To our knowledge, this research presents a novel machine-learning approach to the quantitative modelling of NOM sorption to minerals found in anoxic marine environments. [ABSTRACT FROM AUTHOR]

Records of the lithium isotopic composition of seawater (δ7Li sw), preserved in the lithium isotopic composition of shallow-marine carbonate sediments (δ7Li carb), provide information about the links between silicate weathering and clay formation, the global carbon cycle, and Earth's climate on geologic timescales. However, the record of δ7Li sw values in shallow marine carbonates is complicated by the effects of mineralogy (e.g., calcite vs aragonite) and diagenesis. Here we present measurements of bulk carbonate δ7Li values paired with a suite of stable isotope systems (δ44/40Ca, δ26Mg) and element abundance ratios (Li/(Ca + Mg), Sr/(Ca + Mg), Mg/(Ca + Mg)) in Neogene shallow-marine carbonates from sites in the Bahamas and southwest Australia. The studied sites span a range of depositional and diagenetic settings and exhibit large stratigraphic trends in δ7Li values that correlate with mineralogy, δ44/40Ca values, and/or element abundances. These trends differ from coeval planktonic foraminifera records of δ7Li sw and instead predominantly reflect local processes. We show, using a suite of geochemical analyses and a numerical model of early marine diagenesis, that the observed variability in bulk sediment δ7Li values can be quantitatively explained by the effects of mineralogy and diagenetic alteration under both fluid-buffered and sediment-buffered conditions. Using this framework, we show that it is possible to produce robust and accurate 'snapshots' of the δ7Li value of seawater in the geologic past from shallow-water marine carbonate sediments. [ABSTRACT FROM AUTHOR]

Characterizing the K-isotope compositions of marine sediments is a necessary step to using this novel isotope system to investigate K cycling both in the ocean system and in subduction zones. Here we report data for 70+ samples in order to characterize the K-isotope compositions of deep-sea sediments for two drill sites in the western Pacific: (1) IODP Site C0011 adjacent to the Nankai Trough and Southwest Japan arc and (2) Site 1149 adjacent to the Izu-Bonin trench and arc. Variation in δ 41 K at both sites is mostly subtle, reflecting a consistently strong contribution of K from sources that have δ 41 K similar to the upper continental crust (UCC). Yet, in detail, the mean δ 41 K at both sites is about 0.05–0.10 ‰ lower than a recently proposed best estimate for UCC ( δ 41 K = −0.44 ‰). We infer that the slightly low mean δ 41 K values relative to UCC are likely caused by secondary processes acting on the volcanogenic component of the sediments, though chemical weathering of (non-volcanogenic) terrigenous materials may also play a role. We measured a very low δ 41 K value (−1.33 ± 0.04 ‰) for one discrete ash layer at Site C0011, so volcanoclastic materials may lower the δ 41 K values of the bulk sediments, despite only accounting for a small fraction of the K in the sediments. Correlations between δ 41 K , Cr/Al, and K/Al in the upper sediments of Site 1149 were used to investigate mixing between volcanic ash and terrigenous materials. This approach indicates that mixing of isotopically light volcanic ash (with δ 41 K about −0.75 ‰) and terrigenous materials (about −0.46 ‰) can account for the observed variation in δ 41 K values in these sediments. In addition, we observe that at Site C0011 K isotopes exhibit a shift (by ~0.08 ‰) at ~250 m below the seafloor from UCC-like compositions in the upper sediments to slightly lighter compositions in the lower sediments. This shift in δ 41 K coincides with an abrupt change in certain physical properties (porosity and cementation) of the sediments that may relate to the extent of weathering/degradation of the dispersed volcaniclastics, with more extensively weathered materials present in the lower sediments. Finally, we find evidence for variable admixture of a high δ 41 K silicic volcanic ash in the lowermost sediments at Site C0011, supporting the view that heterogeneous volcaniclastics can give rise to significant δ 41 K variations in marine sediments. [ABSTRACT FROM AUTHOR]

We report 3He and 4He concentrations in 57 sediment samples from the southeast Indian Ocean where 60Fe excesses were previously identified in a subset of the same samples (Wallner et al., 2016). The coupled 60Fe-3He data allow further evaluation of two competing hypotheses: (1) a nearby supernova (SN) showered Earth with exotic radionuclides such as 60Fe during the last 3 million years, or (2) 60Fe in terrestrial archives was generated by reactions of galactic cosmic rays (GCRs) on micrometeorite grains that were irradiated for hundreds of millions of years in the interstellar medium, where 3He production by GCRs is larger than the solar wind 3He flux. Piston core ELT49-53 sediments show no correlation between 3He and 60Fe, and sedimentary 3He appears to be dominated by the presence of interplanetary dust particles (IDPs). Because 3He is not supplied in significant amounts by SN ejecta, the absence of a 3He-60Fe correlation provides additional, although circumstantial evidence for the supernova hypothesis. Large uncertainties in the relatively small number of sediment 60Fe measurements currently limit a firmer conclusion. The extraterrestrial 3He accumulation rate in ELT49-53 from 3.2 to 1.7 Ma was 0.88 ± 0.26 × 10−12 cm3 STP/g/kyr, similar to IDP 3He flux estimates from previous sedimentary and ice core records that span both shorter and longer time scales. 4He and 60Fe accumulation rates during this time interval were 0.11 ± 0.04 × 10−6 cm3 STP/cm2/kyr and 1.9 ± 0.5 × 104 atoms/cm2/kyr. Bulk sediment [4He] is strongly anti-correlated with sediment CaCO 3 content, evidence for modulation of the terrigenous and cosmic sedimentary fractions primarily by changes in biogenic carbonate deposition. Although the dominant terrigenous source has not been uniquely identified at the Indian Ocean deposition site, it resembles eolian material from the continental interior of Australia, and shows a narrow range of 3He/4He (from 2 to 4 × 10−8, 0.015–0.030 R A) over the last ∼3 Myrs. [ABSTRACT FROM AUTHOR]

The speciation of iron in sediments and sedimentary rocks is a widely used proxy for the chemistry and oxidation state of ancient water bodies. Specifically, the fraction of reactive iron out of the total iron (Fe HR /Fe T) and the fraction of pyrite iron out of the reactive iron pool (Fe PYR /Fe HR) are thought to constrain the oxidation state and the presence of sulfide in the water column, respectively. This approach was developed and tested against modern core-top sediments, but application to sedimentary rocks requires consideration of the effects of diagenesis and lithification on iron speciation. Furthermore, the effects of deep burial, metamorphism, and late-stage alteration during exhumation or sampling (e.g., oxidative weathering) have not been systematically explored. To bridge this gap, we combined new data from four sediment cores (n = 54) with an extensive literature compilation of modern sediments (2936 measurements from 316 cores) and ancient sedimentary rocks (12,173 measurements spanning the Neoarchean to Quaternary). The modern data include both surface and buried sediments, allowing an investigation of the effects of diagenesis on iron speciation. Depending on the thresholds used to distinguish oxic from anoxic environments and ferruginous from euxinic environments, interpretation of the modern sedimentary iron speciation data within the existing framework yields incorrect environmental classifications up to ≈70% of the time. In modern sediments, diagenesis is the main reason that iron speciation does not represent the chemistry and oxidation state of the water column. We find that iron speciation correlates with porewater chemistry and that it changes with progressive burial along three distinctive Fe HR /Fe T –Fe PYR /Fe HR arrays, each of which represents a different set of diagenetic processes. We suggest that similarly to modern sediments, stratigraphic variation in iron speciation in sedimentary rocks primarily reflects progressive burial diagenesis or variation in depositional conditions rather than temporal variation in water-column chemistry and oxidation state. Indeed, analysis of the geologic iron speciation data reveals no statistically significant trends in either Fe HR /Fe T or Fe PYR /Fe HR from the Archean to the present day. The diagenetic Fe HR /Fe T –Fe PYR /Fe HR arrays that we identified in modern marine sediments suggest that under certain conditions, iron speciation analyses may be used to constrain Fe HR /Fe T in the local sediment source(s). Hence, we suggest that iron speciation data, together with complementary petrographic, mineralogical and geochemical constraints, may be used to constrain the local iron source(s) and early and late diagenetic processes, but rarely the chemistry or oxidation state of ancient water columns. [ABSTRACT FROM AUTHOR]

River-dominated ocean margins (RiOMar) are major terrestrial organic carbon (OC terr) repositories that play an important role in the global carbon cycle. However, riverine inputs of sediment and associated OC terr have decreased substantially due to intensifying human activity. Thus, studying OC terr processing during transport to and within RiOMar is crucial. The East China Sea (ECS) receives reduced sediment loads from the Changjiang River (CJR), which is compounded further by the impoundment of the Three Gorges Reservoir. Here, we examined the CJR-ECS source-to-sink system to understand the fate of OC terr in a typical RiOMar. We analyzed the sedimentary properties (grain size and the specific surface area), bulk organic carbon properties (C/N ratio and δ13C), and molecular biomarkers (n -alkanes and GDGTs) of riverine suspended particulate matter (SPM) and surficial marine sediment collected in 2006 and 2018. The C/N ratio, δ13C value, and short-chain n -alkanes abundances in the riverine SPM indicate that phytoplankton productivity could be an important source of OC terr in the basin due to the reduced sediment loads. Seabed erosion occurred in the estuarine–inner shelf areas of the ECS as a result of reduced riverine inputs, which resulted in a change in the distribution of sedimentary OC terr. The reduced total organic carbon content and n -alkanes abundance are indicative of the low sedimentary OC terr content. Variations in GDGT-based indices are further manifestation of reduced sediment load, as they show increased in situ production of GDGTs. Spearman correlations indicate that the biomarker abundances were positively correlated with silt, which is in accordance with silt being easily shaped by hydrodynamic sorting. Biomarker abundances along four estuarine–inner shelf transects also exhibited pronounced alongshore or cross-shelf OC terr transport. Furthermore, the relationship between the biomarkers and sedimentary properties indicates that mineral protection plays an important role in regulating the fate of OC terr on continental margins. Therefore, variations in riverine inputs and the sedimentary environment caused by anthropogenic perturbations have affected the abundance, distribution, composition, and transport of sedimentary OC terr in the study area. These findings can be applicable to other RiOMar, as humans continue to shape riverine inputs globally. [ABSTRACT FROM AUTHOR]

Tectomanganate todorokite and phyllomanganate vernadite are the two major manganese minerals in marine ferromanganese sediments that contain large quantities of trace metals. Todorokite has a less clear metal partitioning mechanism than vernadite, mainly because the metal cation and water structures in the tunnel cavities remain poorly understood. Here, we report the composition-dependent tunnel-cation site disorder of todorokite obtained from molecular dynamics (MD) simulations. Our simulations of homocationic Ni2+-, Zn2+-, Mg2+-, Ca2+-, or Na+-todorokite revealed that tunnel cations form inner-sphere (IS) complexes with Mn octahedral surface at low hydration states, but at higher hydration states, outer-sphere (OS) complexes are the dominant cation species located at the center of the tunnel. However, K+ and Cs+ form only IS complexes regardless of the tunnel hydration state. Optimum water contents were determined based on the free energy changes associated with water intercalation into the tunnel cavities calculated as a function of water content for two heterocationic todorokite models: Mg 0.5 Na 0.4 Ca 0.1 Mn 6 O 12 · n H 2 O (Mg/Mn = 0.08, average Mn oxidation state = +3.73) and Mg 1.1 K 0.1 Ca 0.1 Mn 6 O 12 · n H 2 O (Mg/Mn = 0.18, average Mn oxidation state = +3.58). These models emulate the chemical compositions of well-characterized terrestrial and marine todorokite samples, respectively. At each optimum water content, MD simulations revealed that OS complexes are the major Mg2+ species in the former model. However, IS complexes are the major Mg2+ species in the latter model, indicating that the tunnel cation speciation of diagenetic todorokite can be influenced by the sediment pore-fluid chemistry. The atomic tunnel cation and water structures of todorokite provide a molecular basis for understanding of metal partitioning to Mn oxides and interpretation of metal stable isotopes recorded in ferromanganese nodules. [ABSTRACT FROM AUTHOR]

Microbial methanogenesis produces a range of isotope (13C/12C and D/H) and isotopologue (13CH 3 D and 12CH 2 D 2) fractionations. Differential reversibility of enzymatic reactions qualitatively explains the isotope and isotopologue fractionations observed in both laboratory cultures and environmental samples. We applied pathway thermodynamics and isotopologue flow network models to quantitatively describe 13C/12C, D/H, 13CH 3 D, and 12CH 2 D 2 fractionations during hydrogenotrophic methanogenesis. The model consists of the 10 enzymatic reactions of the methanogenesis pathway and tracks mass balance of isotopologues by taking into account the reaction symmetries of singly- and doubly-deuterated isotopologues. Based on the thermodynamics and enzyme kinetic data, the model estimates the reversibilities of 8 reactions from predicted in vivo concentrations of 17 metabolites and cofactors. The isotopologue flow network model calculates the isotopologue composition of product methane as well as all intermediates as a function of reversibilities and prescribed fractionation factors. The model explains a number of observations for laboratory culture experiments, including the range of 13C/12C fractionation up to 80‰ between CH 4 and CO 2 , with increasing magnitudes while decreasing pH 2. Relatively constant D/H fractionations of 300 ± 40‰ between methane and water can be explained when methane is produced from three near-equilibrium H in methyl-coenzyme M with the addition of one kinetic D-depleted H during the last step of methanogenesis. Abundances of the doubly substituted isotopologues, 13CH 3 D and 12CH 2 D 2 , reflect kinetic and equilibrium end-members with additional complications due to non-linear mixing and/or combinatorial effect. Our model can make predictions for isotopologue fractionations under slow rates of methanogenesis in energy-limiting deep sedimentary environments, where a large quantity of methane is produced. Near-equilibrium isotopologue ratios, often observed in marine sedimentary environments, are produced when pH 2 is less than 10 Pa. Our model results indicate that methanogenesis does not occur or only proceeds at extremely slow rates at this low pH 2 because low concentration of methyl-tetrahydromethanopterin limits the rate and thermodynamic feasibility of methanogenesis. Accordingly, it is proposed that near-equilibrium methane isotopologue signals in deep marine sediments are produced by the catalytic reversibility of methyl-coenzyme M reductase, likely from anaerobic methanotrophic archaea performing either anaerobic methane oxidation or net methanogenesis. The pathway thermodynamics and isotopologue flow network model scheme presented herein can be applied and expanded to predict isotopologue fractionations for a range of metabolisms beyond methanogenesis. [ABSTRACT FROM AUTHOR]

This study is aimed at precise measurement of thermodynamic constants of disulfide (S 2 2−) formation. It was demonstrated that these constants, K , for formation of longer polysulfides for reaction between hydrogen sulfide and orthorhombic cyclooctasulfur (α-S 8) measured by independent techniques (potentiometry, spectrophotometry, chromatography) are in good agreement. For the most abundant polysulfides, S 4 2−, S 5 2− and S 6 2−, the reported ranges of p K values are ≤0.72 p K units. On the other hand, p K 2 values of the formation of S 2 2− in this reaction measured by different techniques span from 11.46 to 14.43. The main difficulty in measurement of K 2 is low abundance of disulfide in the solutions saturated with respect to α-S 8. In this work, we applied chromatographic analysis for the samples, which are highly undersaturated with respect to α-S 8. The results show that robust determination of K 2 may be achieved at the molar ratio of S0 to S(II) ≤ 0.064. At these conditions the value of p K 2 at 25 °C was found to be 12.77 ± 0.08. Based on this value, the standard Gibbs free energy of S 2 2− formation was calculated. The standard enthalpy of formation and molar entropy were derived from the data obtained in experiments at the temperature range of 10 °C to 70 °C. Calculations based on these thermodynamic values show that while disulfide accounts for only a minor fraction of polysulfide zero-valent sulfur at saturation with α-S 8 , it can become the most abundant polysulfide at low S0 to S(II) molar ratios. In marine sediments and water columns low molar polysulfide S0 to S(II) ratio may exist in hydrogen sulfide-rich zero valent sulfur-poor systems as well as, due to kinetic constraints, in the zero valent sulfur-rich systems. Results of our work suggest that at the molar ratio of polysulfide S0 to S(II) > 0.064, the calculation of disulfide concentration should be based on concentrations of hydrogen sulfide and other polysulfides and the set of thermodynamic constants provided in this work. At the lower polysulfide S0 to S(II) ratios, the disulfide concentration should be either measured directly or calculated in case that it is below the detection limit of quantification method. [ABSTRACT FROM AUTHOR]

The oxygen-18 isotopic composition (δ18O) of silica preserved in oceanic sediments is an important archive of Earth's temperature and/or seawater δ18O from the Archean to present. Recent advances in high-precision measurements of both δ18O and δ17O values have been used to provide additional constraints on what the oxygen isotopic composition of chert reflects about past conditions. Here, we examine the effects on the triple oxygen isotopic composition of chert that occurs during transformation and recrystallization of biogenic opal-A to opal-CT to microquartz in deep sea sediments. We studied late Miocene to present samples from the Sea of Japan at ODP Site 795 and measured biogenic diatom opal-A, opal-CT, microquartz chert, and 'altered' opal-A samples—previously measured for δ18O values only—for both δ18O and δ17O values. We find that δ18O decreases and Δ′17O increases (where Δ′17O = δ17O – 0.528 × δ18O) with depth, coincident with the conversions from diatom opal-A to opal-CT to microquartz. Silica samples deviate from the trend expected for triple oxygen isotopic equilibrium with modern seawater. To explain these data, we developed a model that shows that local temperature gradients and pore fluid δ18O profiles in combination lower the measured opal-CT and microquartz δ18O values and raise the Δ′17O values relative to the initial opal-A, but deviate from triple oxygen isotopic equilibrium with seawater. We find that a steeper local temperature gradient and a larger influence of hydrothermal alteration of basalt at the base of the sediment column (which lowers pore fluid δ18O values) in the past explain both the measured δ18O and Δ′17O values of the opal-CT and microquartz. These data and our modeling show that the transformation of opal-A to microquartz in marine sediments at elevated temperatures and in the presence of lowered pore water δ18O values leads to an array that falls below the theoretical triple oxygen isotope line of equilibrium for SiO 2 with modern seawater. Further, our model indicates that opal-CT and microquartz do form in triple oxygen isotopic equilibrium with pore fluids that are offset in their triple oxygen isotopic composition compared to seawater due to fluid-rock alteration of igneous rocks at the base of the sediment column. The diagenetic processes taking place in the Japan Sea do not explain a large portion of the existing Archean to present triple oxygen isotope chert data, which likely require either changes in the oxygen isotopic composition of the source water (i.e., ocean water) and/or alteration by meteoric fluids. Further, our data demonstrate that the triple oxygen isotopic composition of preserved chert need not represent surface conditions, but instead may reflect processes that occur in subsurface sediments at elevated temperatures and with modified pore fluid oxygen isotopic compositions. [ABSTRACT FROM AUTHOR]

Compared to continental crust, marine sediments accumulating beneath O 2 depleted waters are enriched in Re and Mo, with Re/Mo ratios that vary by more than two orders of magnitude, a remarkably large range. Deposition of both elements begins simultaneously, and both come to finite aqueous concentration asymptotes together, neither being drawn down to analytical detection limits. To explain these aqueous-phase observations and to reconcile them with laboratory evidence, a previous coprecipitation hypothesis is further developed here. The proposed coprecipitate is a nanoscale sulfide, Fe(Mo,Re)S 4 that transforms irreversibly by internal electron transfer to a product represented as Fe(Mo,Re)(S 2)S 2. Irreversibility preserves information about redox conditions at the time of sedimentation unless sedimentary rocks later become subjected to oxidation or thermal maturation. Compelling support for this mechanism comes from the continuously euxinic Black Sea. A Rayleigh fractionation process characterized by a partition coefficient of 0.38 explains Re/Mo ratios in both its water column and its sediments. On the other hand, in sediments where overlying waters range from oxic to intermittently euxinic, and where Re and Mo deposition occurs only beneath the sediment–water interface, the observed >100-fold range of Re/Mo ratios is too large to be explained solely by Rayleigh fractionation. Instead, it is attributed to modification of pore waters by decomposition of unstable precursory phases. Low solid phase Re/Mo ratios are produced by pore waters modified by dissolution of Mo-rich, Mn,Fe oxyhydroxides; high ratios reflect dissolution of the so-far uncharacterized Re-rich particles that are known to create dissolved Re anomalies in shallow pore waters. Rhenium often follows iodine in biology, suggesting that the Re-rich particles could be biogenic and might participate in the marine iodine cycle. A significant correlation between particulate Re/Mo ratios and biogenic CaCO 3 in the Cariaco Basin water column suggests that some of these Re-rich particles could be unstable biocalcification precursors like vaterite and amorphous CaCO 3. Compared to δ98Mo, another redox proxy, Re/Mo ratios provide more nuanced redox information, especially under conditions that fall between oxic and sulfidic extremes. Thus Re/Mo ratios are potentially advantageous redox proxies that so far have been underutilized. [ABSTRACT FROM AUTHOR]

The marine sulfate inventory represents the largest standing pool of electron acceptors, which, via microbial sulfate reduction, is responsible for roughly half of the organic matter mineralization globally in marine sediments. In addition to the oxidation of buried organic matter, sulfate reduction can be coupled to the oxidation of methane migrating upward. Multiple sulfur isotope ratios were measured for porewater sulfate, sulfide, elemental sulfur and pyrite from core samples collected from continental shelf (19–96 m water depth) in the Baltic Sea and slope (1098 m water depth) in the Andaman Sea, in order to test if their isotope systematics can be used to trace the two different sulfate reduction processes. For shallow shelf sediments (<43 cm below seafloor), both δ34S and Δ33S values of porewater sulfate increased with increasing depth as a result of organoclastic sulfate reduction (OSR). However, the Δ33S values of both porewater sulfate and sulfide decreased as the δ34S values increased downcore at 43–73 cm depth where sulfate reduction was coupled to anaerobic oxidation of methane (AOM). Pyrite in shelf sediments yielded positive Δ33S values, reflecting Δ33S of porewater sulfide produced by OSR. In contrast, pyrite in slope sediments yielded negative Δ33S values as low as −0.15‰, as a result of mixing of sulfides derived from OSR and AOM. This is consistent with the slowly migrating sulfate–methane transition (SMT) in slope sediments inferred from sulfur and iron speciation, carbon isotope ratios of carbonates, and magnetic susceptibility data. A stable SMT, focusing AOM at roughly the same depth over the past few millennia, further provides favorable conditions for prolonged pyrite formation with the development of cubic crystals, while the sulfur isotope difference between bulk pyrite and macroscopic pyrite reflects the significance of OSR throughout the sediment column. We conclude that minor sulfur isotopes provide a unique proxy that can be applied to differentiate OSR and AOM and the origin of pyrite in diverse sediments and sedimentary rocks. This contribution highlights strong local diagenetic controls on pyrite formation and its multiple sulfur isotopic composition in various marine settings. [ABSTRACT FROM AUTHOR]

Marine cyanobacteria play an important role in trace metal cycling in the oceans. However, the influence of bacterial detritus following cell lysis – that includes both particulate organic matter (POM) and dissolved organic matter (DOM) – is less understood. Previous investigations have shown that the ratio of bacterial detritus to living cells increases significantly with ocean depth, indicating that the former plays a central role in trace metal cycling and eventual sequestration in deep marine sediments. Thus, in this study we produced detritus from the mechanical lysis of the common marine cyanobacterium Synechococcus sp. PCC 7002 (referred to as cyPOM and cyDOM), and then measured their buffering capacity through proton adsorption and release via potentiometric acid-base titrations. Both cyPOM and cyDOM were best modelled using a 2-site non-electrostatic protonation model. The cyPOM fraction possessed ligands with pK a values of 5.78 (±0.07) and 9.01 (±0.29) with corresponding site concentrations of 41.8 (±8.15) µmol g−1 and 41.2 (±5.28) µmol g−1, while cyDOM had pK a values of 4.89 (±0.22) and 6.80 (±0.22) and corresponding site concentrations of 42.8 (±14.6) µmol g−1 and 37.3 (±16.5) µmol g−1. As a comparison, intact Synechococcus cells were previously reported to be best modelled by invoking 3-sites with overall ligand densities more than double that of cyPOM and cyDOM. Trace metal (Cd, Co, Cu, Ni, and Zn) adsorption experiments indicate that cyPOM has a lower affinity towards trace metals than intact Synechococcus cells, evidenced by lower trace metals adsorption per gram of dry mass and therefore less trace metal sequestration potential. This implies that intact Synechococcus cells are chiefly responsible for trace metal sequestration, even at high cyPOM proportions (10:1 – cyPOM: Synechococcus) that are more representative of POM that reaches the seafloor. The cyDOM-trace metal association could not be determined experimentally; thus we applied existing thermodynamic data from modern marine DOM studies acquired via potentiometric titrations and metal-binding constants. Unlike cyPOM, metal speciation is almost entirely accounted for in the dissolved fraction (>99.9%). These results further the view that DOM is the most important microbial fraction in controlling metals speciation in the water column. [ABSTRACT FROM AUTHOR]

Interactions between organic and detrital mineral phases strongly influence both the dispersal and accumulation of terrestrial organic carbon (OC) in continental margin sediments. Yet the complex interplay among biological, chemical, and physical processes limits our understanding of how organo-mineral interactions evolve during sediment transfer and burial. In particular, diverse OC sources and complex hydrodynamic processes hinder the assessment of how the partnership of organic matter and its mineral host evolves during supply and dispersal over continental margins. In this study, we integrate new and compiled sedimentological (grain size, surface area), organic (%OC, OC-δ13C, OC-F14C), and inorganic isotopic (ε Nd , 87Sr/86Sr) geochemical data for a broad suite of surface sediments spanning the Western Arctic Ocean from the Bering Sea to the Mackenzie River Delta that capture diverse sources and ages of both terrestrial and marine material deposited in contrasting shelf and slope settings. Spatial gradients in sediment properties were used to delineate regional sources and transport processes influencing the dispersion and persistence of OC-mineral particle associations during export and burial. We found strong relationships between physical parameters, aluminum content, and OC-14C suggesting that terrestrial OC remains tightly associated with its detrital mineral carrier during source-to-sink transport. Notably, carbon and neodymium isotopic data yield consistent information regarding organic matter provenance. Results obtained highlight the potential for coupled organic-inorganic tracer measurements to elucidate sediment sources and to constrain physical and geochemical processes during sediment mobilization and transport in the Western Arctic Ocean. Tandem measurements of carbon and Nd isotopes may provide a new way to identify large-scale biogeochemical and ecological changes in the sources, nature, and fate of OC stemming from predicted increases in sea ice loss and fluvial inputs of dissolved and particulate OC to this complex and dynamic high latitude marginal sea. [ABSTRACT FROM AUTHOR]

Zinc (Zn) is a bioessential element whose cycling in the marine environment is closely linked to the biological pump. As a vital micronutrient, Zn is depleted in marine surface waters and enriched in deep waters. This has given rise to the longstanding hope that Zn could serve as a robust paleoproductivity proxy. There has been a recent focus on how Zn isotope signatures can be used to track the evolution of the biological pump. However, the factors controlling variations in the sedimentary Zn isotope composition of core-top sediments are debated and these values are influenced by changes in the relative contributions of biological uptake and scavenging processes and by mineral fractionations. In order to provide a new perspective on the Zn isotopic signature of marine core-top sediments and their potential for tracing ocean biogeochemical processes, we developed a sample preparation procedure to extract organically bound Zn (excluding inorganic Zn) without a significant isotope fractionation. We tested five potential organic solvents and found that the isopropanol extraction procedure provided a reproducible and robust result that yielded the highest recovery rate of organically bound Zn without a significant associated isotopic fractionation and appeared to exclude common mineral bound forms of Zn. This extraction procedure was used to analyze the Zn concentrations and isotopic compositions (δ66Zn) of core-top sediment samples from Long Island Sound and the Peruvian continental margin. Our results suggest that the δ66Zn value of organic Zn increases with water depth, thus providing additional support for the finding that burial of isotopically light Zn occurs predominantly in shallow high-productivity sediments. However, we also found that the δ66Zn values of the estimated authigenic Zn component are consistently lighter than those of the organic Zn fraction, consistent with diagenetic (sediment pile) scavenging of organic derived Zn in sulfides imparting an isotope fractionation. [ABSTRACT FROM AUTHOR]

Sediment-hosted marine sulfur cycling has played a significant role in regulating Earth's surface chemistry over our planet's history. Microbially-mediated reactions involving sulfur are often accompanied by sulfur isotope fractionation that, in turn, is captured by sulfate and sulfide minerals, providing the opportunity to track changes in the microbial utilization of sulfur and thus the marine sulfur cycle. Studying sulfur diagenesis within the Bornholm Basin, Baltic Sea, we explore the interplay between carbon, sulfur and iron, focusing on the fate of sulfur and the dynamics of the sulfur and oxygen isotopic response as a function of the varying thickness of the organic carbon-rich Holocene Mud Layer (HML) across the basin. Using a one-dimensional reaction-transport model, porewater sulfate and sulfide profiles were used to calculate net sulfate reduction rates (SRR) and net sulfide production rates, respectively. These calculations suggest a positive relationship between the thickness of the HML and net rates of sulfate reduction and sulfide production. Given that ascending sulfide is enriched in 34S relative to that produced in-situ , a heightened sulfide flux promotes spatially variable precipitation of 34S-enriched pyrite (δ34S ≈ −10‰) close to the sediment–water interface. Modeling results indicate that this isotopically "heavy" sulfide is formed as a consequence of mixing between ascending sulfide (up to +6.3‰) and that produced in-situ (ca. −40‰). Further, we show that the sulfur and oxygen isotopic composition of porewater sulfate is controlled by the net SRR: when the net SRR is high (i.e., in sulfide-replete settings) the downcore increase in δ18O SO4 is dampened relative to increase in δ34S SO4 , whereas when net SRR is low (i.e., in iron-rich parts of the basin) downcore δ18O SO4 values increase while δ34S SO4 values remain invariant. We conclude that sedimentation rates and open system diffusion strongly influence the distribution of sulfur species and their sulfur isotopic composition, as well as the oxygen isotopic composition of sulfate, through the interaction between iron, sulfur and methane. This work highlights the importance of considering diffusion to better understand open system diagenesis and the δ34S signatures of sulfate and sulfide in both modern settings and ancient rocks. [ABSTRACT FROM AUTHOR]

Microbial and hydrothermal venting activities on the seafloor are important for the formation of sediment-hosted stratiform sulfide (SHSS) deposits. Fe isotopic compositions are sensitive to both microbial and hydrothermal activities and may be used to investigate the formation of these deposits. However, to the best of our knowledge, no Fe isotopic studies have been conducted on SHSS deposits. In the Devonian Dajiangping SHSS-type pyrite deposit (389 Ma), South China, laminated pyrite ores were precipitated from exhalative hydrothermal fluids, whereas black shales were deposited during intervals with no exhalation. Pyrite grains from black shales mostly display positive δ56Fe -py (0.01–0.73‰), higher than marine sediments (ca. 0‰), due to pyrite deriving Fe from basinal shuttled Fe(III) (hydr-)oxides and slowly crystallizing in pores of sediments with equilibrium fractionation, except for negative δ56Fe -py (−0.17‰ to −0.24‰) of two samples caused by mixing of Fe from underlain laminated ores. The positive δ34S -py (3.50–24.5‰) of black shales reflect that sulfur of pyrite originated from quantitative reduction of sulfate in closed pores of sediments. In contrast, pyrite grains of laminated ores have negative δ56Fe -py (−0.60‰ to −0.21‰), which were not only inherited from the negative δ56Fe of hydrothermal fluids but also caused by kinetic fractionation during rapid precipitation of a pyrite precursor (FeS) in hydrothermal plumes. These ores have negative δ34S -py (−28.7‰ to −1.82‰), because H 2 S for pyrite mineralization was produced by bacterial sulfate reduction (BSR) in a sulfate-rich seawater column or shallow sediments. The δ56Fe -py values of laminated ores co-vary positively with δ34S -py and δ13C -carbonate along the ore stratigraphy, with δ13C -carbonate values ranging from −12.0‰ to −2.50‰. However, they correlate negatively with aluminum-normalized total organic carbon (TOC/Al 2 O 3). Organic carbon is thus considered to enhance the production of H 2 S by BSR activities, increase pyrite precipitation rates and promote the expression of kinetic fractionation of Fe isotopes. Intriguingly, in the ore units with vigorous hydrothermal venting activities, δ56Fe -py , δ34S -py and δ13C -carbonate values display a consistently increasing trend. Such results suggest that venting hydrothermal fluids significantly inhibited the H 2 S production of BSR, which then reduced the pyrite crystallization rate and decreased the kinetic fractionation of Fe isotopes. Our study reveals that the formation of SHSS deposits relies on H 2 S from microbial activities and metals from hydrothermal exhalation on the seafloor, but that vigorous exhalation can inhibit microbial activities and thus sulfide precipitation rates. The integrated use of Fe, S, and C isotopes can effectively elucidate these dynamic interactions between hydrothermal venting and microbial activities during the formation of SHSS deposits. [ABSTRACT FROM AUTHOR]

The isotopic composition of the detrital sediment record harbours a valuable proxy for estimating the composition of the erodible upper crust since the Archaean. Refractory elements such as titanium (Ti) and zirconium (Zr) can display systematic variations in their isotopic composition as a result of magmatic differentiation. Hence, the isotopic composition of such elements in detrital sediments could potentially be used to infer the average composition (e.g., SiO 2 content) of their source region, even when elemental systematics are obfuscated by weathering and diagenetic processes. A key premise of this approach is that the isotopic composition of sediments remains unbiased relative to their protolith. To what extent isotopic fractionation can occur during sedimentary processes, notably the hydrodynamic sorting of heavy mineral assemblages with contrasting isotopic compositions, remains poorly understood. We investigate the effects of such processes on the Ti and Zr isotope composition of a suite of detrital sediments from the Eastern Mediterranean Sea (EMS). These sediments are binary mixtures of two main provenance components, Saharan dust and Nile sediment, with strongly contrasting mineralogical and geochemical signatures. The EMS sediments display clear evidence for hydrodynamic sorting of zircon, expressed as a large variation in Zr/Al 2 O 3 and deviation of εHf relative to the terrestrial εNd-εHf array. Our new data, however, do not show pronounced Zr isotope variation resulting from either hydrodynamic sorting of zircon or sediment provenance. Although this agrees with theoretical models that predict negligible equilibrium zircon-melt Zr isotope fractionation, it contrasts with recent observations suggesting that kinetic Zr isotope fractionation might be a common feature in igneous rocks. For the EMS sediments, the negligible shift in Zr isotope composition through hydrodynamic sorting means that fine-grained samples accurately reflect the composition of their source. The nearly overlapping Zr isotope compositions of Sahara- and Nile-derived sediment, however, mean that Zr isotopes, in this case, have insufficient resolution to be a useful provenance proxy. Titanium behaves differently. A small but resolvable, systematic difference in Ti isotope composition is observed between the Sahara and Nile provenance components. Samples with a strong Saharan dust signature show some Ti isotope evidence for hydrodynamic sorting of oxides in tandem with zircon, but a much stronger effect is inferred for Nile sediment. Regression of the EMS sediment samples shows that the Ti isotope composition of the Nile-derived component is strongly fractionated compared to its protolith, the Ethiopian flood basalts. Whereas Ti in Nile sediment is carried in essentially unmodified concentration, and by inference isotope composition, from its sources to the delta, large-scale hydrodynamic sorting of Fe-Ti oxides occurs in the littoral cell. This process causes a decrease in TiO 2 /Al 2 O 3 of the residual fine-grained sediment fraction and shifts its Ti isotope composition to heavier compositions. The potential of such an "oxide effect" in detrital sediments has implications for crustal evolution models that use Ti isotopes as a proxy for the proportion of felsic crust and can account for the observed scatter in the shale record. [ABSTRACT FROM AUTHOR]

Burial of terrestrial organic carbon (OC terr) in marginal sea sediments is a key component of the carbon cycle, exerting long-term influence on atmospheric CO 2 and climate. Assessment of the burial efficiency of OC terr is of key importance, yet remains poorly constrained due to current gaps in our knowledge of mechanistic controls, including the influence of organic matter composition and age on the fate of OC terr in marine sediments. We measured bulk characteristics (δ13C and Δ14C of OC; mineral surface area, SA; grain size; n = 98 samples) and biomarker carbon isotopic compositions (fatty acid δ13C and Δ14C; n = 11) of a suite of surface sediment samples from the Bohai Sea and Yellow Sea (BS-YS). Combining with published results, bulk OC (n = 234) and biomarker (n = 19) carbon isotopic data are used to examine spatial variability in the sources and ages of OC terr in this shallow marginal sea system. Biomarker carbon isotopic values are used to constrain endmember values, and a dual carbon isotope mixing model was applied to all bulk samples to develop a spatially explicit assessment of contributions of different pools of OC terr. Although highly spatially variable, pre-aged OC (OC pre-aged) and fossil OC (OC fossil) when combined (i.e., "non-modern OC") on average accounted for 51 ± 10% of the OC in BS-YS surface sediments. This was equivalent to the proportion of OC terr (ave., 51 ± 14%) estimated from a δ13C OC binary mixing model, suggesting OC terr in the mixed layer of BS-YS sediments is predominantly composed of millennial-aged OC. The burial potential of pool-specific OC terr was then evaluated through comparison of corresponding mineral SA-normalized loadings of surface sediments with those of Yellow River suspended particulate matter. Both the regression slope and the arithmetic mean value approaches reveal high burial potential for all terrestrial OC pools delivered by Yellow River, which is attributed to the aged and refractory nature of OC exported from the Yellow River. However, differing relationships of pool-specific OC terr loadings between BS-YS and Yellow River sediments imply contrasting fates. In particular, we find that the burial potential of OC pre-aged is consistently greater than that of OC fossil. This surprising observation suggests either enhanced degradation of OC fossil during lateral transport (possibly as a consequence of different mineral associations and hydrodynamic sorting effects), or additional sources for OC pre-aged , such as from small rivers or aerosol deposition. Overall, OC age, mineralogical composition and hydrological settings contribute to the complex patterns of OC residing in northern China marginal sea surface sediments. This novel molecular-isotopic approach reveals significant spatial variability in proportions, contents and burial potential among terrestrial OC pools, and underlines the importance of considering organic matter age and composition in understanding and constraining the fate of OC terr in marine sedimentary environments. [ABSTRACT FROM AUTHOR]

• Origins, ages, and alterations of POC and sedimentary C org in YRE were investigated. • Hydrodynamic processes exert first-order control on POC transport and burial. • Significant degradation of POC occurs in the water column-seabed interface. • Aluminosilicate minerals control the fate of sedimentary C org. Climate change-triggered episodic and intensive flood events are increasing in frequency globally; these events play a disproportionate role in the carbon cycle at land-ocean interfaces by influencing the delivery of terrestrial organic matter to the sea. However, the transport and burial of flood-driven terrestrial organic carbon (C org) in river-dominated marginal seas remains poorly understood. Here, water column particles (surface, intermediate, and bottom layers) and surface sediments from the Yangtze River estuary system were collected during a large flooding event (>60,000 m3 s−1) for a multiproxy geochemical study. We analyzed N/C, δ13C org , δ15N, F14C, grain size, and elemental (Al and Si) to characterize the sources, ages, and alterations of particulate organic carbon (POC) and sedimentary C org from the river channel to the estuarine mixing zone to the continental shelf and fingerprint the fate of C org burial in marine sediments. We found that terrestrial POC delivered by the Yangtze flood is characterized by low F14C (0.625 ± 0.002; Δ14C = −379.8 ± 2.3‰, 14C age = 4,135 yr before present (BP)) and δ13C org (−27.1 ± 0.5‰) values and high δ15N (3.9 ± 0.6‰), and N/C (0.15 ± 0.01) values, and was adsorbed on fine-grained particles. Using a Bayesian-Monte Carlo simulation approach, we estimated that terrestrial POC is dominated by C 3 plant detritus (42 ± 16% on average), followed by petrogenic organic carbon (33 ± 7%), and soil (26 ± 22%). Moving offshore, hydrodynamic sorting of lithogenic particles exerts first-order control on POC by selecting particles with unique signatures. Petrogenic organic carbon and aged plant debris associated with coarse-sized particles preferentially accumulated within the proximal delta, whereas POC derived from catchment soil and adsorbed on fine-grained particles was transported offshore along the sediment dispersion system. We estimated that, on average, 76 ± 18% of POC initially present in the water column is oxidized at the water column-seabed interface during seaward transport and constitutes a source of atmospheric carbon dioxide. In contrast, the stable form of the organic matter-aluminosilicate mineral association controls the preservation of the sedimentary C org. Our results suggest that frequent flooding events in the near future will likely increase lithospheric C org delivery to marine sediments and have the potential to promote petrogenic C org burial efficiency in the river-dominated marginal seas and accelerate biospheric POC oxidation and CO 2 release, thus generating a positive feedback to global warming. [ABSTRACT FROM AUTHOR]

The delivery of potentially reactive iron minerals to the marine environment exerts a major control on ocean and marine sediment biogeochemistry, including the preservation and burial of organic carbon. One aspect of the global iron cycle that has received little attention concerns the phase partitioning of iron in highly chemically-weathered sediments from (sub)tropical mountainous regions, where the sediment is commonly deposited directly onto adjacent continental margins. Here, we report the phase partitioning of particulate iron in surface seafloor sediments deposited from oxic bottom waters along the east coast of China, including the Bohai Sea, Yellow Sea and East China Sea, in addition to the continental shelf region adjacent to the (sub)tropical mountainous island of Hainan in the northern South China Sea. We document highly reactive (Fe HR) to total iron (Fe T) ratios for the Bohai Sea, Yellow Sea and East China Sea that are typical of global marine sediments deposited under oxic water column conditions. By contrast, Fe HR /Fe T ratios in Hainan offshore sediments are significantly elevated above normal oxic marine sediments. These Hainan offshore sediments display a strong positive correlation between Fe HR /Fe T ratios and the chemical index of alteration (CIA) weathering proxy, suggesting that the Fe speciation systematics are controlled by the intensity of chemical weathering. This observation is supported by additional geochemical data and Nd isotope analyses, which suggest a common source lithology for all the studied regions. The Hainan sediments thus document a specific scenario, whereby highly chemically weathered sediments from the mountainous Hainan region bypass the inner shore settings that commonly disproportionately trap Fe (oxyhydr)oxide minerals, depositing high concentrations of Fe HR on the adjacent continental margin. Such enrichments likely aid in the preservation of organic carbon in marine sediments, suggesting that organic carbon preservation and burial may be enhanced by elevated Fe HR in such settings. We also establish a set of essential criteria for potential recognition of chemical weathering-induced enrichments in Fe HR /Fe T ratios in ancient marine sediments. [ABSTRACT FROM AUTHOR]

An understanding of how the coupled cycles of carbon, iron and sulfur in sediments respond to environmental change throughout Earth history requires the reconstruction of biogeochemical processes over a range of spatial and temporal scales. In this study, sediment cores from the southwestern Black Sea were analyzed to gain insight into past changes in biogeochemical processes with particular focus on the cycling of dissolved organic carbon (DOC). The sediment consists of Late Pleistocene deposits of iron oxide-rich and organic-poor lacustrine sediments, a Holocene sapropel layer deposited after the inflow of saline Mediterranean seawater about 9300 yr BP, and overlying recent marine sediments. The porewaters displayed high concentrations of DOC, acetate, dissolved iron and an extended depth interval over which sulfate and methane were both present. The historical fluctuations of the fluxes of carbon, sulfur and iron species at the seafloor that led to these present-day geochemical profiles, and which cannot be easily interpreted from the measured data alone, were hindcasted with a reaction-transport model. The model suggests that the inflow of Mediterranean seawater impacted the rain rate and reactivity of organic matter reaching the sediments, which shifted the sedimentary redox regimes throughout the Holocene that now are reflected on different lithology units. Organic matter in the sapropel layer is apparently the main source of modern-day accumulations of DOC and acetate, both of which probably sustained subsurface microbial activity throughout the post-glacial period. The ratio between DOC and dissolved inorganic carbon (DIC) flux to the bottom water decreased from ∼40% before the inflow of Mediterranean water to ∼2% at the present day. We suggest that the coexistence of methanogenesis and sulfate reduction was associated with sulfate-reducing bacteria and methanogens sharing common substrates of acetate and lactate and utilizing non-competitive substrates such as methylated compounds in the sapropel layer and in the bottom of modern marine deposits. Intense sulfur and iron cycling mainly took place in the organic-poor freshwater deposits, today characterized by high concentrations of dissolved iron and methane. In contrast to previous studies in similar environments, anaerobic oxidation of methane coupled to the reduction of ferric iron was negligible. The results have broad implications for coastal environments that are currently experiencing deoxygenation and seawater intrusion and also for understanding the role of DOC in the sedimentary carbon cycle. [ABSTRACT FROM AUTHOR]

• Constraining sources of core and intact archaeal lipids with stable C isotopic ratios. • No evidence for sedimentary sources of IPL crenarchaeol. • Evidence of sedimentary production of IPL caldarchaeol and BDGT-0. • Higher organic matter content promotes higher activity of sedimentary archaea. • Archaeol is a sensitive indicator of sedimentary archaea. Archaea occupy an important niche in the global carbon cycle and their lipids are widely used as indicators of environmental conditions in both paleoenvironmental and modern biogeochemical studies. The principal sources of archaeal lipids in marine sediments are benthic archaea, fossil remnants of planktonic archaea, and allochthonous sources such as soils. However, the relative contributions of these sources to the sedimentary lipid pool have not been comprehensively constrained, complicating a mechanistic understanding of archaeal lipid proxies. In order to provide insights into the relative contributions of these sources and identify signals derived from sedimentary activity, we performed a systematic survey of stable carbon isotopic compositions (δ13C) of both core and intact archaeal lipids via analyses of their phytanyl (Phy) and biphytanyl (BP) moieties in diverse marine sediments. The sample set consisted of 44 sediment horizons from the Mediterranean and adjacent basins and represented diverse sources of organic matter and depositional conditions. Complementary geochemical data enabled the comparison of lipid distributions and carbon isotopic signatures with prevailing redox conditions. The δ13C of tricyclic BP (BPcren) from the core and intact forms of crenarchaeol ranged from −19.1 to −28.6‰ and −18.1 to −27.4‰, respectively. δ13C values of core and intact BPcren did not differ, suggesting that intact crenarchaeol is either a fossil relic from planktonic archaea or a product of lipid recycling by benthic archaea, as opposed to being synthesized de novo by sedimentary archaea. δ13C values of BP0 derived from core and intact forms of glycerol and butanetriol dibiphytanyl glycerol tetraethers (GDGTs and BGDTs, respectively), but predominantly from caldarchaeol (GDGT-0), ranged from −19.4 to −32.0‰ and −20.9 to −37.0‰, respectively. In contrast to BPcren, intact-lipid derived BP0 was often 13C-depleted relative to its core counterpart, consistent with in situ production by sedimentary archaea. This relative depletion was most pronounced in sulfate reduction zones, likely due to heterotrophic activity. Core and intact archaeol exhibited the largest ranges in δ13C values, from −21.6 to −42.1‰ and −22.7 to −58.9‰, respectively. This strong 13C-depletion relative to both total organic carbon and dissolved inorganic carbon is consistent with mixtures of functional sources of sedimentary chemolithoautotrophic, methanotrophic, methanogenic and heterotrophic archaea. Based on the substantial 13C-depletion of BPcren and BP0 in samples in the vicinity of the Rhône River delta relative to a distal marine reference site, we infer that the terrestrial soil contribution of archaeal lipids to these sediments is as high as 43%. Hence, terrestrial input of archaeal lipids, including their intact forms, can be substantial and suggests caution when using existing molecular proxies aimed at constraining riverine input. In summary, our comparative isotopic analysis of sedimentary core versus intact archaeal lipids improves the apportionment of their diverse sources and confidence in distinguishing in situ lipid production by sedimentary archaea. [ABSTRACT FROM AUTHOR]

• Thallium (Tl) is more redox sensitive compared to other metals (Mo, U, and Re). • Beach pore waters and incubation experiments suggest fast reaction kinetics of Tl. • Seasonally changing redox conditions affect Tl, Mo, U, and Re fluxes. • Beach sediments are a net sink for Tl, U and Re, but temporary release those. Pore water data of thallium (Tl) in marine environments are scarce. It has been suggested that anoxic sediments are a sink for dissolved Tl likely due to its incorporation into Fe sulfides. However, recent studies indicated that Tl is removed from solution prior to the onset of sulfidic conditions and that Tl is involved in biological cycles in coastal seawater. To assess the Tl behavior in marine sediments, pore waters of a high energy beach (Spiekeroog Island, Germany) were sampled during different seasons and on different spatial scales. The study site provides a perfect set of samples to assess trace metal behavior under various redox conditions. Samples were analyzed for the dissolved trace metals Tl, molybdenum (Mo), uranium (U), and rhenium (Re). Additionally, sediments were incubated to monitor trace metal removal or release under controlled conditions. On-site redox conditions were characterized using dissolved oxygen (O 2), manganese (Mn), and iron (Fe) concentrations. Our results indicated high enrichments of Tl in pore waters concurrently to aerobic organic matter (OM) degradation, exceeding seawater concentrations up to 6-fold. In contrast, Tl was completely removed in weakly reducing pore water characterized by more than 1 µM Mn or Fe. The spatial Tl distribution in intertidal pore waters responded to the present dissolved Mn and Fe level, which varied in space and with season. We suggest, Tl release to be attributed to OM degradation, particle desorption, or reoxidation, whereas Tl removal is likely related to the presence of trace amounts of dissolved sulfide. In conclusion, the fast reaction kinetics of Tl led to fast and complete removal in comparison to Mo, U, and Re and we suggest the following order of removal: Tl > Re > U > Mo. The removal behavior as well as the high enrichments of Tl in pore waters implicate that sinks and sources in the marine environment are not yet fully understood. Although the intertidal sediments form an overall sink for Tl (U and Re), especially under mostly anoxic conditions in summer, sediments turn into a Tl net source in winter, when sediments are more oxic. For global marine Tl balances, Tl fluxes have been estimated based on pore water Tl/Mn ratios. Contrastingly, Tl removal from pore waters at low threshold concentrations of Mn at our site indicated that these Tl flux estimations may not be applicable in permeable sandy beach sediments and in many other types of sediments, which host mildly sulfidic conditions. [ABSTRACT FROM AUTHOR]