Redox Proxies Research Articles

Organic Heterogeneities in Foraminiferal Calcite Traced Through the Distribution of N, S, and I Measured With NanoSIMS: A New Challenge for Element-Ratio-Based Paleoproxies?

Oceanic oxygen decline due to anthropogenic climate change is a matter of growing concern. A quantitative oxygen proxy is highly desirable in order to identify and monitor recent dynamics as well as to reconstruct pre-Anthropocene changes in amplitude and extension of oxygen depletion. Geochemical proxies like foraminiferal I/Ca ratios seem to be promising redox proxies. Nevertheless, recent studies on microanalyses of benthic foraminiferal I/Ca ratios at the Peruvian Oxygen Minimum Zone (OMZ) measured with Secondary-Ion-Mass-Spectrometry (SIMS) revealed a possible association of iodine with organic accumulations within the test. Here we present a new study on the micro-distribution of nitrogen, sulphur and iodine within the test-walls of Uvigerina striata from the Peruvian OMZ measured with Nano-SIMS. A quantification of the foraminiferal I/Ca ratios from our NanoSIMS study is in good agreement with quantitative results from a previous SIMS study. Additionally, we compared uncleaned specimens with specimens that have been treated with an oxidative cleaning procedure. Both nitrogen and sulfur, which are used as tracer for organic matter, show a patchy distribution within the test walls of the uncleaned specimens and a statistically significant correlation with the iodine distribution. This patchy organic rich phase has a different geochemical signature than the pristine calcitic parts of the test and another phase that shows a banding like structure and that is characterized by a strong sulfur enrichment. All three elements, sulfur, nitrogen and iodine, are strongly depleted in the cleaned specimens, even within the massive parts of the test walls that lack the connection with the test pores. These results indicate that the organic parts of the test walls are located inside a microporous framework within the foraminiferal calcite. This has to be considered in the interpretation of geochemical proxies on foraminiferal calcite, especially for microanalytical methods, since the chemical signature of these organic parts likely alters some element to Calcium ratios within the foraminiferal test.

Evaluation of high-frequency paleoenvironmental variation using an optimized cyclostratigraphic framework: Example for C-S-Fe analysis of Devonian-Mississippian black shales (Central Appalachian Basin, U.S.A.)

Stratigraphic successions are rarely sampled at sufficiently dense spacing to permit evaluation of paleoenvironmental variation at the shortest fundamental frequency operative in the depositional system of interest, often because that frequency remains undetermined. Here, we provide an example of a sampling strategy optimized for recovery of high-frequency paleoenvironmental signals, based on (1) full-core analysis using a continuous survey tool such as X-radiography, followed by (2) fine sampling of selected small-scale cycles that record significant short-term paleoenvironmental variation. We show that this strategy results in recovery of high-frequency paleoenvironmental signals that are completely missed by low-density sampling protocols, permitting key insights into depositional and early diagenetic processes that may otherwise by overlooked.The present case study is based on C-S-Fe systematics of the Cleveland and Sunbury shales, which belong to the Upper Devonian-lowermost Carboniferous black shale succession of the Central Appalachian Basin in eastern North America. In these units, the fundamental scale of paleoenvironmental variation is recorded by pervasive decimeter-scale (~5- to 20-cm-thick) compositional cycles that are readily visible in outcrop, in which high-organic layers weather out as resistant ledges. We identified these cycles in drillcores using X-radiography, which proved to be an effective proxy for compositional variation owing to control of bulk density primarily by total organic carbon (TOC) content. We then sampled selected dm-scale cycles (n = 21) at a centimeter spacing, generating short, high-resolution, multiproxy chemostratigraphic records including TOC, sulfur and Fe concentrations, Fepy/FeHR (a redox proxy), δ34Spyrite, and organic maceral content. This analysis yielded the novel insight that all proxies related to authigenic iron sulfides (e.g., Stotal and Spyrite, Fetotal and Fepyrite, Fepy/FeHR, and δ34Spyrite) covary negatively with TOC within the dm-scale cycles.We interpret the unusual pattern of negative TOC-pyrite covariation in the Cleveland and Sunbury shales to have resulted from differential distributions of labile organic matter (OM), which drove H2S production via microbial sulfate reduction (MSR), and reactive Fe, which controlled pyrite formation. Labile OM was concentrated in high-TOC layers whereas reactive Fe was concentrated in low-TOC layers (possibly as Fe-oxyhydroxide coatings on silt grains), as a consequence of which part of the H2S generated in the high-TOC layers diffused upward into the low-TOC layers before becoming fixed as pyrite. This process is evidenced by several contrasts between high-TOC and low-TOC layers: (1) higher Spyrite concentrations and Fepy/FeHR values in the latter, (2) concentration of pyrite in the lower part of low-TOC layers, immediately above high-TOC layers, and (3) higher δ34Spyrite values in the latter, reflecting late diagenetic formation of the H2S that diffused upward into the low-TOC layers. To our knowledge, this process has not been documented previously in ancient marine shales, probably owing to insufficiently high-resolution analysis in earlier studies.

Pyrite oxidation in shales: Implications for palaeo-redox proxies based on geochemical and SEM-EDX evidence

Pyrite oxidation in marine shales during weathering has been widely studied, however, the effects of this process on geochemical proxies commonly used to reconstruct ocean redox conditions, or the details of pyrite oxidation at the mineral grain scale, have not received much scientific attention. We conducted a four-week laboratory experiment designed to stimulate pyrite oxidation at shale outcrops, and to assess effects on the chemical phase of iron and sulphur in the samples both in bulk sediments (useful for comparison to palaeo-environmental geochemistry) and at a finer scale (to gain a better understanding of the nature of these changes). Geochemical and scanning electron microscopy (SEM) techniques provide evidence for pyrite oxidation, carbonate dissolution, and iron (oxyhydr)oxide formation during the experiment. The net effect of the experiment on the ratio of highly reactive iron phases (FeHR) to total iron (FeT) is minimal (≪0.03% difference), suggesting that this redox proxy behaves relatively conservatively during weathering. The effect of weathering on the ratio of pyrite-bound iron to highly reactive iron (FePY/FeHR), used to investigate the availability of sulphur, in contrast, is pronounced (up to 32.5% difference) due to the oxidation of pyrite and the precipitation of iron (oxyhydr)oxides in the shale samples. Electron microscopy provides evidence that iron (oxyhydr)oxides precipitated in situ as rims around cores of pyrite particles, “passivating” and protecting them from further oxidation. The quantification of these partly oxidised pyrite particles is now possible using a novel automated particle analysis method coupled to chemical mapping, developed in this study. We conclude that this method can be of wide use, both to quantify pyrite oxidation, and assess the significance of FePY/FeHR at measured in shale outcrop samples.

Nitrogen isotope compositions of the Upper Triassic Chang 7 Shale, Ordos Basin, North China: Implications for depositional redox conditions

Nitrogen isotope (δ 15 N) analysis has been used to evaluate depositional redox conditions in well-preserved sedimentary systems; however, fewer N-isotope studies have been performed to reconstruct the redox conditions in lacustrine shales. In this paper, we report the δ 15 N data from the Upper Triassic Chang 7 Shale of the Ordos Basin, North China. Sedimentary δ 15 N values are significantly higher in the Chang 7 3 and the lower part of the Chang 7 2 submembers (Zone A; average = 9.4 ± 1.3‰) than in the upper part of the Chang 7 2 and the Chang 7 1 submembers (Zone B; average = 5.4 ± 1.5‰). Previous geochemical measurements (i.e., U and TOC/P) of both zones show wide redox variation, however, the average values of these redox proxies are relatively higher in Zone A than those of Zone B. Combined with lithological aspects of the Chang 7 Shale, our study suggest that Zone A was mainly deposited under suboxic bottom water conditions, whereas Zone B deposits accumulated within an oxygenated water column. Stable organic carbon isotopes (δ 13 C org ) and total nitrogen (TN) values of the two zones display little variation that could be attributed to changing organic matter sources and/or post-depositional alteration of δ 15 N. Thus, we suggest that variations in δ 15 N throughout the Chang 7 Shale primarily reflect differences in depositional redox conditions and δ 15 N values of the shale that can provide important details regarding the depositional history of unconventional resource plays. • Provide the first δ 15 N records of the Chang 7 Shale, Ordos Basin. • Differences in δ 15 N are primarily influenced by water column redox conditions. • Organic-rich intervals accumulated under suboxic conditions. • Tectonic events drove redox changes during deposition.

Productivity or preservation? The factors controlling the organic matter accumulation in the late Katian through Hirnantian Wufeng organic-rich shale, South China

The Wufeng organic-rich shale is widespread in the Upper Yangtze platform, and it is one of the most advantageous shale gas producers in China. Its deposition commenced with the onset of the Boda warming event in the late Katian and terminated at the Hirnantian glacial maximum. The depositional mechanism of the Wufeng Formation was poorly understood owing to its relatively thin thickness, being interpreted as the result of organic matter (OM) accumulation in a shelf setting under anoxic conditions. This study integrated detailed geochemical analyses based on the core samples from three boreholes which are located in the outer-, middle- and inner-shelf of the Upper Yangtze platform, in order to investigate the depositional environments during the deposition of the Wufeng Formation. Geochemical redox proxies (Mo-EF, U-EF, and V/Cr) and productivity proxies (P, Baxs, Sixs) indicate that the deposition of the Wufeng Formation was associated with four intervals (WF1 to WF4), each characterized by its unique geochemical features related to sea-level fluctuations. Black siliceous mudstones deposited during WF1 and WF2 are relatively organic-lean due to low productivity, less favorable preservation conditions, and terrestrial dilution. Whereas black siliceous mudstone deposited during WF3 and WF4 is organic-rich due to high paleoproductivity and conducive preservation conditions. The geochemical proxies (Cd/Mo, Co x Mn) associated with the modern upwelling settings were replicated in the Wufeng Formation, revealing that the outer-shelf of the Upper Yangtze platform was dominated by persistent upwelling. The upwelling-driven primary productivity is considered as the first-order control for the OM enrichment at the outer-shelf of the Upper Yangtze platform. Seasonal upwelling may influence the middle-shelf of the Upper Yangtze Platform, where both primary productivity and preservation played essential roles in the OM accumulation. In contrast, the OM accumulation at the inner-shelf was fundamentally driven by good preservation conditions.

Investigating Ocean Deoxygenation During the PETM Through the Cr Isotopic Signature of Foraminifera

AbstractOver the past several decades, oxygen minimum zones have rapidly expanded due to rising temperatures raising concerns about the impacts of future climate change. One way to better understand the drivers behind this expansion is to evaluate the links between climate and seawater deoxygenation in the past especially in times of geologically abrupt climate change such as the Palaeocene‐Eocene Thermal Maximum (PETM), a well‐characterized period of rapid warming ~56 Ma. We have developed and applied the novel redox proxies of foraminiferal Cr isotopes (δ53Cr) and Ce anomalies (Ce/Ce*) to assess changes in paleoredox conditions arising from changes in oxygen availability. Both δ53Cr and Cr concentrations decrease notably over the PETM at intermediate to upper abyssal water depths, indicative of widespread reductions in dissolved oxygen concentrations. An apparent correlation between the sizes of δ53Cr and benthic δ18O excursions during the PETM suggests temperature is one of the main controlling factors of deoxygenation in the open ocean. Ocean Drilling Program Sites 1210 in the Pacific and 1263 in the Southeast Atlantic suggest that deoxygenation is associated with warming and circulation changes, as supported by Ce/Ce* data. Our geochemical data are supported by simulations from an intermediate complexity climate model (cGENIE), which show that during the PETM anoxia was mostly restricted to the Tethys Sea, while hypoxia was more widespread as a result of increasing atmospheric CO2 (from 1 to 6 times preindustrial values).

Depositional processes of microbially colonized manganese crusts, Sambe hot spring, Japan

Abstract Relative contribution of microbially mediated and purely abiotic processes during Mn(II) oxidation is evaluated by investigating microbially colonized manganese deposits at the Sambe hot spring in Japan. Microscopic observations and DNA analyses suggest that manganese-oxidizing bacteria are present in the deposits at all of the sites investigated, while thick microbial mats, which consist mainly of phototrophic microorganisms, are developed at only one site. Microelectrode measurements (pH, O2 concentration, and Mn(II) concentration) near the deposit surface indicate that microbially mediated processes are dominant at all sites. These microbially mediated processes exceed the purely abiotic process by more than 2–24 times. At sites without abundant phototrophs, the major microbially mediated process that is occurring is light-independent oxidation (e.g., direct/indirect oxidation via manganese-oxidizing bacteria/fungi). In contrast, the site with abundant phototrophs is characterized by the occurrence of light-independent oxidation (mostly indirect oxidation by oxygenic phototrophs), and the contribution of light-independent oxidation is subordinate. Chemical gradients, which are established within a diffusive boundary layer and microbial mat, drive indirect oxidation by oxygenic phototrophs, and the O2 concentration gradient is particularly important when the concentration of dissolved inorganic carbon is higher than ca. 3 mM. X-ray diffraction and X-ray absorption fine-structure spectrometry analyses indicate that microbially mediated processes yield poorly-crystalline birnessite (i.e., vernadite) regardless of their relative contribution. The observations of this study imply that (1) photosynthetic increases in the O2 concentration drive indirect oxidation by oxygenic phototrophs at high concentrations of dissolved inorganic carbon like the Precambrian ocean, and that (2) the contribution of indirect oxidation by oxygenic phototrophs to ancient manganese oxides can be evaluated via geochemical redox proxies.

Diagenesis and iron paleo-redox proxies: New perspectives from magnetic and iron speciation analyses in the Santa Barbara Basin

Sedimentary redox proxies are usually employed to reconstruct the paleo-redox conditions of bottom water environments, assuming that porewater and bottom water dissolved oxygen concentrations are similar. Using a combination of geochemical and magnetic techniques, we investigate the relationship between iron speciation and mineralogy in recent (~1760–2009 CE) sediments retrieved from the Santa Barbara Basin (SBB) – a modern silled basin with low-oxygen (dissolved O2 < 10 μmol/kg) and sporadically anoxic (no O2 detected) bottom waters. Magnetic analyses reveal that biogenic magnetite is preserved in SBB sulfidic porewaters on at least decadal to centennial time scales. Highly-reactive Fe (oxyhydr)oxides remain preserved despite observed sulfidic porewaters, indicating incomplete pyrite conversion, and producing low Fepy [pyrite Fe]/FeHR ratios. We attribute this observation to restricted porewater reaction kinetics under high sedimentation rates. Our results also reveal non-steady state diagenesis caused by instantaneous depositional events (e.g., turbidites and flood layers). The most reducing water column suggested by Fe speciation coincided with the Macoma layer, where in situ colonization of hypoxia-intolerant bivalve shells argues for the most oxygenated bottom water in the 250 year record. A turbidite potentially introduced fresh unsulfidized FeHR that buffered upward-diffusing sulfide from underlying sediments. Subsequent pyrite precipitation following re-establishment of sulfidic porewaters could have facilitated a “false positive” interpretation. In comparison, redox-sensitive metal enrichments (MoEF, UEF, and ReEF) were not obscured by post-depositional diagenesis and appear to accurately record redox geochemistry at the sediment-water interface.

Post-depositional overprinting of chromium in foraminifera

Present-day ocean deoxygenation has major implications for marine ecosystems and biogeochemical cycling in the oceans. Chromium isotopes are used as a proxy to infer changes in past oceanic redox state. Chromium isotopes in carbonates, including the prime proxy carrier foraminifera, were initially thought to record the seawater composition during crystallisation. However, the uptake of Cr into foraminiferal tests and carbonates is still poorly understood and recent studies question this assumption. We assess whether Cr in foraminiferal calcite is taken up during biomineralisation, has a post-depositional origin or is a combination of the two. Laser Ablation-MC-ICP-MS analyses and NanoSIMS imaging of individual tests were used to characterise the distribution of Cr in both planktic and benthic foraminifera. Foraminifera in sediment core-top samples have up to two orders of magnitude more Cr than sediment trap, plankton net, and culture samples. In cultured specimens, Cr is incorporated in foraminiferal tests at low concentrations (0.04–0.13 ppm) with a distribution coefficient of ∼250 ± 43 (2SE) which is an upper estimate due to substantial loss of dissolved Cr during the experiment. Part of the Cr signal in sedimentary foraminifera may be primary, but this primary signal is likely often overprinted by the uptake of Cr from bottom and pore waters. In sediment samples, there is no significant isotopic offset between individual species and bulk foraminiferal calcite from the same size fraction. The >500 μm fraction has a heavier isotopic composition than the smaller 250–500 μm fraction with an offset of −0.3 to −0.5‰ due to an increase in surface area to volume. We propose that Cr in foraminifera is predominantly post-depositional and records bottom/pore water signals. This is contrary to current interpretations of the foraminiferal Cr isotope proxy as a surface seawater redox proxy.

Effects of pH on redox proxies in a Jurassic rift lake: Implications for interpreting environmental records in deep time

Abstract It is widely agreed that the Earth’s atmosphere and oceans have undergone major redox changes over the last 2.5 billion years. However, the magnitude of these shifts remains a point of debate because it is difficult to reconstruct concentrations of dissolved O2 from indirect proxies in sedimentary archives. In this study, we show that an additional complicating factor that is rarely considered may be the pH of the water column. We analyzed rock samples from the early Jurassic Towaco Formation in the Newark basin (eastern USA), comprising deposits of a rift lake that became temporarily redox stratified. New biomarker evidence points to increasingly saline aquatic conditions during the second half of the lake’s history. Salinity stratification likely induced redox stratification, consistent with the disappearance of macrofauna at this time. Distinctive lipid biomarker assemblages and stable nitrogen isotope data support previous mineralogical indications that the lake was alkaline (pH ≥ 9) during its saline episode. Despite the biomarker and macrofaunal evidence for anoxia, ratios of Fe/Al and FeHR/FeT show only small to no enrichments in the anoxic horizon compared to oxic facies in the same section – counter to what is commonly observed in anoxic marine settings. Molybdenum, As, V, U and to some degree Cd show enrichments in the anoxic interval, whereas Co, Ni, Cu, Zn and Cr do not. These patterns are most parsimoniously explained by differential pH effects on the solubility of these elements. Extrapolating from these observations in lacustrine strata, we speculate that a secular increase in seawater pH over Earth’s history as recently proposed may have helped modulate the magnitude of trace metal enrichments in marine shales, although other factors such as atmospheric and oceanic redox likely dominated the observed enrichment patterns. Further, a decrease in the solubility of ferrous iron, a major O2 sink, with increasing pH may have contributed to ocean oxygenation. In summary, our results highlight the potential importance of pH in influencing global biogeochemical cycles for multiple elements, including the ancient nitrogen isotope record.

Mobilization and isotope fractionation of chromium during water-rock interaction in presence of siderophores

Chromium mobilization and isotope fractionation during water-rock interaction in presence of the biogenic siderophore desferrioxamine B (DFOB) was studied with batch leaching experiments on chromitite and other igneous oxide and silicate rocks. Siderophores are a group of organic ligands synthesized and excreted by bacteria, fungi and plants to enhance the bioavailability of key nutrients like Fe. However, the DFOB siderophore also has a strong affinity for complexation with other metals such as Cr, U and rare earth elements. Here we show that leaching of rocks in the presence of the hydroxamate siderophore DFOB significantly increased the mobilization of Cr from all investigated rocks and caused an enrichment of the heavier 53Cr isotope in leachates from chromitite (δ53Crleach = +0.15 ± 0.087‰ to +2.14 ± 0.042‰) and from altered silicate rock (δ53Crleach = +0.48 ± 0.07‰). In contrast, stable isotope fractionation of Cr was not observed in DFOB leachates of pristine silicate and low-Cr oxide rocks. Leaching in the presence of citric acid significantly enhanced Cr mobility, but did not result in fractionation of Cr isotopes. Chromium isotope fractionation is used in geochemistry as a quantitative proxy for oxidative weathering, because Cr(III) is oxidized to Cr(VI) in presence of MnO2 and the associated Cr isotope fractionation is commonly linked to the presence of oxygen in the atmosphere. Our findings indicate that the presence of specific biogenic ligands with a high affinity for Cr may also cause Cr isotope fractionation. The presence of biomolecules like siderophores during weathering, hydrothermal alteration or during mineral precipitation, therefore, may put constraints on the applicability of certain trace metals and their isotopes as redox proxies in modern and past environments. The results of our study also suggest that siderophores may have a high potential for (bio)remediation of Cr-contaminated sites and detoxification of contaminated natural waters.

Absence of biomarker evidence for early eukaryotic life from the Mesoproterozoic Roper Group: Searching across a marine redox gradient in mid-Proterozoic habitability.

By about 2.0 billion years ago (Ga), there is evidence for a period best known for its extended, apparent geochemical stability expressed famously in the carbonate-carbon isotope data. Despite the first appearance and early innovation among eukaryotic organisms, this period is also known for a rarity of eukaryotic fossils and an absence of organic biomarker fingerprints for those organisms, suggesting low diversity and relatively small populations compared to the Neoproterozoic era. Nevertheless, the search for diagnostic biomarkers has not been performed with guidance from paleoenvironmental redox constrains from inorganic geochemistry that should reveal the facies that were most likely hospitable to these organisms. Siltstones and shales obtained from drill core of the ca. 1.3-1.4Ga Roper Group from the McArthur Basin of northern Australia provide one of our best windows into the mid-Proterozoic redox landscape. The group is well dated and minimally metamorphosed (of oil window maturity), and previous geochemical data suggest a relatively strong connection to the open ocean compared to other mid-Proterozoic records. Here, we present one of the first integrated investigations of Mesoproterozoic biomarker records performed in parallel with established inorganic redox proxy indicators. Results reveal a temporally variable paleoredox structure through the Velkerri Formation as gauged from iron mineral speciation and trace-metal geochemistry, vacillating between oxic and anoxic. Our combined lipid biomarker and inorganic geochemical records indicate at least episodic euxinic conditions sustained predominantly below the photic zone during the deposition of organic-rich shales found in the middle Velkerri Formation. The most striking result is an absence of eukaryotic steranes (4-desmethylsteranes) and only traces of gammacerane in some samples-despite our search across oxic, as well as anoxic, facies that should favor eukaryotic habitability and in low maturity rocks that allow the preservation of biomarker alkanes. The dearth of Mesoproterozoic eukaryotic sterane biomarkers, even within the more oxic facies, is somewhat surprising but suggests that controls such as the long-term nutrient balance and other environmental factors may have throttled the abundances and diversity of early eukaryotic life relative to bacteria within marine microbial communities. Given that molecular clocks predict that sterol synthesis evolved early in eukaryotic history, and (bacterial) fossil steroids have been found previously in 1.64Ga rocks, then a very low environmental abundance of eukaryotes relative to bacteria is our preferred explanation for the lack of regular steranes and only traces of gammacerane in a few samples. It is also possible that early eukaryotes adapted to Mesoproterozoic marine environments did not make abundant steroid lipids or tetrahymanol in their cell membranes.

Is seawater geochemical composition recorded in marine carbonate? Evidence from iron and manganese contents in Late Devonian carbonate rocks

Iron and manganese are the important redox-sensitive elements in the ocean. Previous studies have established a series of paleo-depositional redox proxies based on the form and content of iron in sedimentary rocks (e.g., degree of pyritization, FeHR/FeT, Fe/Al). These proxies were developed and applied on siliciclastic-rich marine sediments. Although marine carbonate rocks are generally considered to preserve the geochemical signals of ancient seawater, neither Fe nor Mn content in marine carbonate rocks (Fecarb, Mncarb) has been independently used as a proxy to quantify environmental cues in paleo-oceans. Both Fe and Mn are insoluble in oxic conditions (Fe2O3, Fe(OH)3, MnO2), while their reduced forms (Fe2+ and Mn2+) are soluble. Therefore, oxic seawater should have low concentrations of dissolved Fe2+ and Mn2+, and accordingly carbonate rocks precipitated from oxic seawater should have low Fecarb and Mncarb, and vice versa. To evaluate whether Fecarb and Mncarb can be used to quantify oxygen fugacity in seawater, we measured Fecarb and Mncarb of Upper Devonian marine carbonate rocks collected from nine sections in South China. Fecarb of intraplatform basin samples was significantly higher than that of shelf samples, while shelf and basin samples had comparable Mncarb. The modeling result indicates that the dramatic difference in Fecarb cannot be explained by variation in oxygen fugacity between the shelf and basin seawater. Instead, both Fecarb and Mncarb appear to be more sensitive to benthic flux from sediment porewater that is enriched in Fe2+ and Mn2+. Porewater Fe2+ and Mn2+ derive from bacterial iron and manganese reduction; flux was controlled by sedimentation rate and the depth of the Fe(Mn) reduction zone in sediments, the latter of which is determined by oxygen fugacity at the water–sediment interface. Thus, high Fecarb of the basin samples might be attributed to low sedimentation rate and/or low oxygen fugacity at the seafloor. However, invariant Mncarb of the shelf and basin samples might be the consequence of complete reduction of Mn in sediments. Our study indicates that marine carbonate rocks may not necessarily record seawater composition, particularly for benthic carbonate rocks. The influence of benthic flux might cause carbonate rocks’ geochemical signals to deviate significantly from seawater values. Our study suggests that interpretation of geochemical data from carbonate rocks, including carbonate carbon isotopes, should consider the process of carbonate formation.

Cr isotope systematics in the Connecticut River estuary

Stable chromium (Cr) isotopes (expressed in δ53Cr as the deviation of 53Cr/52Cr in samples from the international standard NIST SRM 979) are an emerging paleoredox proxy that has been used to track Earth's redox evolution over a range of timescales. There have been several major advances in our understanding of the Cr isotope system, but we are still developing a basic knowledge of the global Cr isotope mass balance and there are key Cr fluxes with poorly constrained isotopic compositions. The Cr isotope behavior in estuaries is one such poorly constrained aspect of the modern Cr cycle. Therefore, we collected water and suspended particulate samples from the estuary of the Connecticut River, and present the first Cr isotope dataset from a salinity gradient. As pH and salinity increases from brackish to salt water, dissolved Cr increases from 118.1 ± 25.7 ng/kg (1σ, n = 6) to 225.1 ± 26.0 ng/kg (1σ, n = 8), while particulate Cr decreases from 341.3 ± 319.8 ng/kg (1σ, n = 6) to 208.4 ± 364.5 ng/kg (1σ, n = 8); dissolved δ53Cr decreases from 1.30 ± 0.27‰ (1σ, n = 6) to 0.64 ± 0.16‰ (1σ, n = 8), whereas particulate δ53Cr remained stable at 0.11 ± 0.07‰ (1σ, n = 9). These data suggest that Cr is lost from particles to solution when transitioning from brackish to salt water in the Connecticut River estuary. If these observations can be confirmed in other estuaries, estuary systems can potentially enhance riverine dissolved Cr fluxes and thus lower the Cr oceanic residence time, which has important implications for the Cr isotope system as a paleoceanographic redox proxy. There is a clear inverse correlation between dissolved Cr and δ53Cr in the Connecticut River estuary, which yields a Cr isotope fractionation factor of ~0.89‰ that is indistinguishable from previous estimates based on open seawater samples. Large δ53Cr variation in oxygenated open and estuary seawater suggests that marine δ53Cr variations need not necessarily be exclusively tied to Cr(VI) reduction in low oxygen zones. Therefore, interpreting δ53Cr in the sedimentary record requires taking multiple processes into consideration.

Geochemical and petrographic characteristics of Wufeng-Longmaxi shales, Jiaoshiba area, southwest China: Implications for organic matter differential accumulation

Abstract The organic matter-rich shales in Wufeng-Longmaxi Formation have been considered to be a high-quality source rock and a main shale-gas producer in southern China. As the material basis of shale gas, the organic matter content in shales exhibits a notable vertical difference in the Jiaoshiba area of Fulin shale gas field. This study integrated detailed geochemical analysis and sedimentary observations to investigate organic matter enrichment and depletion mechanism. Three intervals are identified by organic matter contents and their according variations. Six major lithofacies are identified based on mineral composition X-ray diffraction (XRD) analyses, microscopic observations and Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) data. Geochemical redox proxies (Mo-EF, U-EF, V/Cr and Corg/P) indicate that organic matter-rich shales of Wufeng and bottom Longmaxi formation are deposited in anoxic conditions, whereas organic matter-lean shales of the middle to top Longmaxi formation are deposited in oxic environment. This pattern is influenced by both worldwide marine transgression and regional tectonic movement. The productivity proxies (P/Al, Cu/Al, Ni/Al, SiO2-bio) indicate that the organic matter-rich Wufeng-Longmaxi shales were deposited under moderate to high surficial primary productivity. Increasing terrigenous influxes dominated organic matter dilution and may have been promoted by regional tectonic uplift. The organic matter enrichment or depletion mechanisms in each unit are controlled by different geological events. Enrichment was controlled by multiple reasons, including both global and regional factors, whereas depletion was mainly dominated by regional tectonic uplift. Additionally, the sequence stratigraphic boundaries coincide with organic matter shifting interfaces, indicating that high-resolution sequence stratigraphy of fine-grained sediments may have a certain effect on optimal reservoir predication. Conversely, boundaries of TOC and geochemical proxies may also help to subdivide sequence boundaries.

High-frequency redox variations of the Eocene cyclic lacustrine sediments in the Yingxi area, western Qaidam Basin, China

The mineral assemblages of lacustrine mixed sediments have vital significance for reconstructing paleo-lake environments, and typical lacustrine mixed sediments deposited during the Eocene are distributed throughout the Yingxi area in the western Qaidam Basin. Accordingly, the framboid size distributions and sulfur isotope (δ34Spy) characteristics of pyrite in addition to the carbon isotope (δ13Ccarb) characteristics and redox-sensitive element ratios (Th/U, V/(V + Ni) and V/Cr) of authigenic carbonates were investigated to reconstruct the high-frequency redox variations in cyclic lacustrine sediments.Corresponding to different redox conditions, three types of mixed sediments developed during transgression and regression stages within the saline basin in the Yingxi area during the Eocene: mixed terrigenous clasts formed in oxic-dysoxic water column conditions during lake transgression, mixed carbonates formed in anoxic water column conditions during early-stages lake regression, and mixed evaporites formed in anoxic-sulfidic water column conditions during middle-late-stage lake regression. The redox proxies correlate well with the water salinity, exhibit little or no correlation with the water temperature, and show an incongruity with the water depth, suggesting that the redox conditions were predominantly controlled by the water salinity rather than the water depth or temperature. Therefore, based on the water redox condition variations and the salinity, three dynamic formation models of the high-frequency sedimentary cycles in a saline basin are established: a deep-water, low-salinity, oxic-dysoxic model (Model I), a medium-water, medium-salinity, anoxic model (Model II) and a shallow-water, high-salinity, anoxic-sulfidic model (Model III). Because the climate gradually turned dry and hot from lake transgression to regression, the continued closure of the basin enhanced evaporation and salinization. In addition, mixed terrigenous clasts, mixed carbonates and mixed evaporites deposited successively. Correspondingly, salinity stratification gradually developed within the lake water, increasing the extent of bacterial sulfate reduction in the bottom water.

An integrated approach to understanding the depositional environment and organic matter enrichment factor in Carboniferous source rocks, Junggar Basin, NW China

Multiple indicators (trace fossils, trace metals, and δ13Corg) are used to assess the depositional environments and controls on organic carbon accumulation in the Lower Carboniferous Nanmingshui Formation, Junggar Basin, NW China. The majority of trace fossils belong to the Nereites ichnofacies, representing low energy, oxygen‐poor, and relatively quiet bottom water environments. However, the shallow water trace fossil Planolites also appears in the strata, possibly reflecting variations in the bottom water oxygen contents of the turbidite succession. Redox proxies Th/U, V/Sc, and V/(V + Ni) reveal variable redox conditions; most of the samples are in the range from suboxic to anoxic depositional conditions. Ni and Cu show a positive correlation with TOC, but U and V have no correlation with TOC, also suggesting the redox conditions were mainly suboxic. The P/Al and Cu/Al ratios of all samples are higher than those of Post‐Archean Australian Shales (PAAS), and about two‐thirds of the samples' Ba/Al and Ni/Al ratios are close to or higher than PAAS, suggesting the Early Carboniferous Junggar Basin had relatively high palaeo‐productivity levels. δ13Corg values average − 23.75‰, reflecting a mixture of terrestrial organic and marine organic matter. The indexes of Ba/Al, Cu/Al, Ni/Al, and δ13Corg show good positive correlations with TOC, indicating the palaeo‐productivity played an important role for the organic matter accumulation. On the other hand, the TOC correlates inversely with redox proxies (Th/U, V/Sc, and V/(V + Ni)), suggesting the preservation conditions (anoxia) are not the control factor of organic matters accumulation. Using these multiple approaches, our results indicate that productivity was the primary factor controlling organic matter accumulation.

Rare Earth Elements in early-diagenetic foraminifer ‘coatings’: Pore-water controls and potential palaeoceanographic applications

Rare Earth Element (REE) distributions in the ocean bear the fingerprints of several key environmental processes, including vertical particle/organic carbon fluxes, water column/pore-water oxygenation and ocean transports. The use of ‘fossil’ REE analyses in the service of palaeoceanography as redox, water transport or nutrient cycling ‘proxies’ has long been a tantalizing possibility. Here we demonstrate the application of a novel laser-ablation microanalysis approach for the rapid and accurate measurement of the REE composition of early diagenetic ‘coatings’ on fossil foraminifera. By applying this new method to a range of core-top and multi-core samples, we show that ‘authigenic’ REE enrichments on planktonic foraminifer surfaces (REEfs) reflect a primary seawater signature that becomes overprinted during sediment burial due to early diagenetic processes that control the flux of REEs to pore-fluids. Thus ‘light’ REEs (LREEs), and eventually ‘middle’ REEs (MREEs) are generally enriched in foraminifer 'coatings' relative to seawater, while Ce-anomalies (Ce/Ce*) recorded in surface sediments are typically more positive than local seawater values and are further ‘eroded’ during burial with the onset of anoxic conditions in the sediment. Similar patterns have previously been observed in pore-fluid measurements. Indeed, we show that Mn and Fe concentrations measured in foraminifer ‘coatings’ track the availability of these elements in pore-water, indicating that they are not associated with a secondary oxide phase. We propose that these elements, along with REEs are instead adsorbed directly from pore-fluids. In contrast, U in authigenic coatings tracks the removal of this element from solution under sub-oxic conditions, supporting the use of U/Ca in foraminifer coatings as a redox proxy. Although our results confirm a significant early diagenetic influence on REEfs, we also demonstrate the potential utility of ‘Ce-enrichment’ relative to expected seawater values as a palaeo-oxygenation proxy. We support this proposal with down-core measurements of U/Ca and Ce-enrichment spanning the last deglaciation in the sub-Antarctic Atlantic, as well as a global array of LGM measurements, which are found to co-vary with parallel estimates of radiocarbon ventilation age, consistent with a widespread drop in oxygen suggesting an increase in the efficiency of the biological pump. Our results suggest that laser-ablation REEfs measurements may hold some promise for palaeoceanographic reconstruction, in particular through a shift in emphasis away from the reconstruction of primary seawater signals to the analysis of diagenetic impacts that are sensitive to changing hydrographic conditions.

Estimation of original kerogen type and hydrogen index using inorganic geochemical proxies: Implications for assessing shale gas potential in the Devonian Horn River Formation of western Canada

Considerable attention has been directed to the Devonian Horn River Formation in western Canada with respect to geochemical evaluation of gas-generation and storage potential. Because organic geochemical analyses are not always useful for characterizing the type and amount of original organic matter, we surmise the original kerogen type and original hydrogen index (HIo) and subsequently estimate a reliable original total organic carbon (TOCo) based on a combination of inorganic and organic geochemical data. Productivity (SiO2 and Ba) and terrestrial input (Al2O3, Hf, Nb, and Zr) proxies are used to estimate original kerogen types, which suggest that the Evie and Muskwa Members formed under conditions of high productivity and minor terrestrial input. These members also formed under reducing conditions, as indicated by the redox proxies (Mo, U, and Th/U). Under such conditions, primarily type II kerogen was preserved. By considering the fraction of biogenic silica, the estimated HIo values (400–500 mg hydrocarbon/g total organic carbon [TOC]) for the middle Otter Park Member are lower than that for Evie and Muskwa Members and higher than the upper and lower Otter Park Member. The stronger correlation between TOCo and trace elements suggests that HIo is useful for reconstructing the coherent variation in TOCo. Based on the original kerogen type and TOCo, the gas-generation and storage potentials of the Evie, middle Otter Park, and Muskwa Members are higher than those of other members. The source-rock potential is excellent for the Evie Member with an approximately 75% difference between TOCo and measured present-day TOC.

Foraminiferal assemblages, 14C ages, and compositional variations in two sediment cores in the western Gulf of Mexico

Foraminifera species distribution, 14C ages, and geochemistry data of sediment cores GM33 and GM34 recovered from the southwestern Gulf of Mexico were investigated to infer the age, sedimentation rate, provenance, heavy metal contamination, and depositional environment. Core GM34 (490 cm interval) reached an age of 34,346 ± 280 cal Yrs. BP and the average sedimentation rate was calculated as 0.014 cm/yr. The weathering indices like Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), and Plagioclase Index of Alteration (PIA) revealed a moderate intensity of weathering in the source area. The trace elemental ratios and rare earth element (REE) patterns indicated the derivation of sediments from intermediate rocks like andesite. The trace element based bivariate (La/Sc and Co/Th) and ternary (NiThV) diagrams revealed that the sediments were derived mostly from andesite located along the Gulf of Mexico coastal areas. The enrichment factor and geo-accumulation index suggested the absence of heavy metal contamination in sediment cores. The redox proxy trace elemental ratios like V/Cr, Ni/Co, Cu/Zn, and (Cu + Mo)Zn suggested an oxic depositional condition. The benthic foraminiferal assemblages, Mn and Mo concentrations indicated that the late Pleistocene abyssal waters in the Gulf of Mexico were more oxygenated than the present. An absence of significant compositional variations between the core sediments revealed that the depositional condition in the southwestern Gulf of Mexico was probably similar for the last 34,346 cal Yrs. BP.