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Chromium (Cr) isotope fractionation is sensitive to redox changes and the Cr isotopic composition (δ53Cr) of sedimentary rocks has been used to reconstruct marine redox conditions and atmospheric oxygenation in the past. However, little is known about the behaviour of chromium isotopes across modern marine redox boundaries. We investigated Cr concentrations and δ53Cr variations in seawater and sediment across the Peruvian oxygen minimum zone (OMZ) to provide a better understanding of Cr cycling in the ocean. We found that seawater δ53Cr values ranged from 0.02 ± 0.16‰ to 0.59 ± 0.11‰ (2SD) and sediment values from 0.31 ± 0.07 to 0.92 ± 0.12‰. Neither Cr concentrations nor δ53Cr values in the water column revealed significant shifts across the oxic-anoxic boundaries. Instead, processes that operate at a local scale, such as Cr scavenging by Fe-rich particles and Cr release from reducing sediments, are identified as the main controls on Cr concentrations and isotope compositions in the water column. The δ53Cr values of sediments deposited in permanently anoxic waters (0.77 ± 0.19‰, n = 5) are significantly different from the δ53Cr values of sediments deposited in oxic bottom waters (0.46 ± 0.19‰, n = 4). This suggests that sediment Cr concentrations and δ53Cr values are to some extent influenced by water column redox (e.g. reductive dissolution and transport of Fe oxides) and/or early diagenetic (e.g. redistribution of Cr during phosphogenesis) processes as well as biologic activity. Our data demonstrate that local scale water column redox gradients and sediment exchange can lead to a large range of δ53Cr values in sediments, comparable to the range found in the entire geologic record to date. Given the increasing prominence of Cr isotope measurements in constraining atmospheric oxygenation in deep time, we argue that the processes influencing Cr cycling under different conditions and from the water column to the sediment need to be better resolved to verify the utili

Fossil microbiotas are rare in the early rock record, limiting the type of ecological information extractable from ancient microbialites. In the absence of body fossils, emphasis may instead be given to microbially derived features, such as microbialite growth patterns, microbial mat morphologies, and the presence of fossilized gas bubbles in lithified mats. The metabolic affinity of micro-organisms associated with phosphatization may reveal important clues to the nature and accretion of apatite-rich microbialites. Stromatolites from the 1.6Ga Chitrakoot Formation (Semri Group, Vindhyan Supergroup) in central India contain abundant fossilized bubbles interspersed within fine-grained in situ-precipitated apatite mats with average C-13(org) indicative of carbon fixation by the Calvin cycle. In addition, the mats hold a synsedimentary fossil biota characteristic of cyanobacterial and rhodophyte morphotypes. Phosphatic oncoid cone-like stromatolites from the Paleoproterozoic Aravalli Supergroup (Jhamarkotra Formation) comprise abundant mineralized bubbles enmeshed within tufted filamentous mat fabrics. Construction of these tufts is considered to be the result of filamentous bacteria gliding within microbial mats, and as fossilized bubbles within pristine mat laminae can be used as a proxy for oxygenic phototrophy, this provides a strong indication for cyanobacterial activity in the Aravalli mounds. We suggest that the activity of oxygenic phototrophs may have been significant for the formation of apatite in both Vindhyan and Aravalli stromatolites, mainly by concentrating phosphate and creating steep diurnal redox gradients within mat pore spaces, promoting apatite precipitation. The presence in the Indian stromatolites of alternating apatite-carbonate lamina may result from local variations in pH and oxygen levels caused by photosynthesis-respiration in the mats. Altogether, this study presents new insights into the ecology of ancient phosphatic stromatolites and warr

The geochemical behavior of molybdenum (Mo) in the oceans is closely linked to the presence of sulfide species in anoxic environments, where Fe availability may play a key role in the Mo scavenging. Here, we show that Mo(VI) is reduced in the presence of particulate organic matter (represented by sulfate-reducing bacteria). Molybdenum was immobilized at the surface of both living cells and dead/lysed cells, but not in cell-free control experiments. Experiments were carried out at four different Mo concentrations (0.1 to 2 mm) to yield cell-associated Mo precipitates with little or no Fe, consisting of mainly Mo(IV)-sulfide compounds with molecular structures similar to Mo enzymes and to those found in natural euxinic sediments. Therefore, we propose that Mo removal in natural sulfidic waters can proceed via a non-Fe-assisted pathway that requires particulate organic matter (dead or living sulfate-reducing bacteria). This pathway has implications for global marine Mo cycling and the current use of Mo-based proxies for paleo-environmental investigations.

Nitrogen cycling is normally thought to dominate the biogeochemistry and microbial ecology of oxygen-minimum zones in marine environments. Through a combination of molecular techniques and process rate measurements, we showed that both sulfate reduction and sulfide oxidation contribute to energy flux and elemental cycling in oxygen-free waters off the coast of northern Chile. These processes may have been overlooked because in nature, the sulfide produced by sulfate reduction immediately oxidizes back to sulfate. This cryptic sulfur cycle is linked to anammox and other nitrogen cycling processes, suggesting that it may influence biogeochemical cycling in the global ocean.

Animal burrowing and sediment-mixing (bioturbation) began during the run up to the Ediacaran/Cambrian boundary1,2,3, initiating a transition4,5 between the stratified Precambrian6 and more well-mixed Phanerozoic7 sedimentary records, against the backdrop of a variable8,9 global oxygen reservoir probably smaller in size than present10,11. Phosphorus is the long-term12 limiting nutrient for oxygen production via burial of organic carbon13, and its retention (relative to carbon) within organic matter in marine sediments is enhanced by bioturbation14,15,16,17,18. Here we explore the biogeochemical implications of a bioturbation-induced organic phosphorus sink in a simple model. We show that increased bioturbation robustly triggers a net decrease in the size of the global oxygen reservoir—the magnitude of which is contingent upon the prescribed difference in carbon to phosphorus ratios between bioturbated and laminated sediments. Bioturbation also reduces steady-state marine phosphate levels, but this effect is offset by the decline in iron-adsorbed phosphate burial that results from a decrease in oxygen concentrations. The introduction of oxygen-sensitive bioturbation to dynamical model runs is sufficient to trigger a negative feedback loop: the intensity of bioturbation is limited by the oxygen decrease it initially causes. The onset of this feedback is consistent with redox variations observed during the early Cambrian rise of bioturbation, leading us to suggest that bioturbation helped to regulate early oxygen and phosphorus cycles.

The Neoproterozoic recorded super-continent breakup, extensive glaciations and the first oxygenation of the deep ocean with a shift from sulfidic/ferruginous conditions to more oxic conditions, accompanied by the expansion of the first animals. Set within this tableau were enigmatic large-amplitude fluctuations in the isotopic composition of marine carbonate carbon (d13CIC ) and oxygen (d18O) and more subdued changes in the isotope composition of marine organic carbon. Normally, carbon isotope changes are considered to reflect the burial history of inorganic and organic carbon into sediments, while the oxygen isotope record is considered to be more sensitive to post depositional diagenesis. The Neoproterozoic d13CIC record, however, reveals prolonged excursions to less than mantle values that cannot be explained by our normal understanding of the carbon cycle. We present a quantitative model of the Shurum-Wonoka anomaly; the largest, and most challenging to understand isotope event. Stratigraphic sections display the following common features: 1) d13CIC minimums of ~-8 ‰, 2) a general correlation between d13CIC and d18O within the anomaly and 3) lower carbon isotope fractionation between carbonate and organic carbon at lower values of d13CIC, with a cross-plot slope of about 1. This unit slope seems to be unique to the Neoproterozoic in Earth history and not easily explained. In our model, the carbon isotope excursions were driven by methane from sediment-hosted clathrate hydrate deposits. Being a powerful greenhouse gas, methane increased temperature and melted icecaps. These combined to produce a negative 18O anomaly, while the higher temperatures also accelerated the weathering of continental rocks, drawing down atmospheric CO2. Lower CO2, in turn, reduced the isotope fractionation between DIC and organic carbon during primary production. This cause and effect chain of events is qualitatively consistent with all observations. Earlier, others