Annual sulfur cycle in a warm monomictic lake with sub-millimolar sulfate concentrations.

We studied the annual variability of the concentration and isotopic composition of main sulfur species and sulfide oxidation intermediates in the water column of monomictic fresh-water Lake Kinneret. Sulfate concentrations in the lake are <1 mM and similar to concentrations that are proposed to have existed in the Paleoproterozoic ocean. The main goal of this research was to explore biogeochemical constrains of sulfur cycling in the modern low-sulfate fresh-water lake and to identify which processes may be responsible for the isotopic composition of sulfur species in the Precambrian sedimentary rocks. RESULTS: At the deepest point of the lake, the sulfate inventory decreases by more than 20% between March and December due to microbial sulfate reduction leading to the buildup of hydrogen sulfide. During the initial stages of stratification, sulfur isotope fractionation between sulfate and hydrogen sulfide is low (11.6 ‰) and sulfur oxyanions (e.g. thiosulfate and sulfite) are the main products of the incomplete oxidation of hydrogen sulfide. During the stratification and at the beginning of the lake mixing (July-December), the inventory of hydrogen sulfide as well as of sulfide oxidation intermediates in the water column increases and is accompanied by an increase in sulfur isotope fractionation to 30 ± 4 ‰ in October. During the period of erosion of the chemocline, zero-valent sulfur prevails over sulfur oxyanions. In the terminal period of the mixing of the water column (January), the concentration of hydrogen sulfide decreases, the inventory of sulfide oxidation intermediates increases, and sulfur isotope fractionation decreases to 20 ± 2 ‰. CONCLUSIONS: Sulfide oxidation intermediates are present in the water column of Lake Kinneret at all stages of stratification with significant increase during the mixing of the water column. Hydrogen sulfide inventory in the water column increases from March to December, and sharply decreases during the lake mixis in January. Sulfur isotope fractionation between sulfate and hydrogen sulfide as well as concentrations of sulfide oxidation intermediates can be explained either by microbial sulfate reduction alone or by microbial sulfate reduction combined with microbial disproportionation of sulfide oxidation intermediates. Our study of sulfur cycle in Lake Kinneret may be useful for understanding the range of biogeochemical processes in low sulfate oceans over Earth history

Calcium isotopes as a record of the marine calcium cycle versus carbonate diagenesis during the late Ediacaran

Calcium isotope ratios in ancient carbonate rocks can provide insight into the global marine calcium cycle as well as local conditions during carbonate mineral precipitation and diagenesis. We compare two extraction techniques for the separation of calcium from other ions before δ44Ca analysis, using an automated ion chromatograph and using manual gravity columns. The two techniques produce the same δ44Ca within error (2σ). We present 31 δ44Ca analyses of carbonate rocks from the Nama Group, Namibia, which record a negative shift in δ44Ca of 0.35‰ between ∼550 and ∼547 Ma, from −1.25‰ to −1.60‰, followed by persistently low δ44Ca (−1.48 ± 0.06‰) between ∼547 and 539 Ma. Very low δ44Ca (&lt;−1.5‰) are commonly interpreted to represent the preservation of local aragonite that has recrystallized to calcite under sediment-buffered conditions (where the composition of the diagenetic carbonate product is determined mainly by the original sediments). The shift in δ44Ca across the Nama Group could therefore represent a change from fluid-buffered diagenesis (where the composition of the diagenetic carbonate mineral is determined mainly by the fluid) to sediment-buffered diagenesis. However, this interpretation is not consistent with either potential geochemical indicators of diagenesis (e.g., δ18O), or changes in large-scale fluid-flow as predicted from sequence stratigraphy. We consider alternative interpretations for generating changes in the δ44Ca of ancient carbonate rocks including enhanced continental weathering, increases in evaporite deposition, and changes in the style of dolomitisation

Coupled measurements of δ18O and δD of hydration water and salinity of fluid inclusions in gypsum from the Messinian Yesares Member, Sorbas Basin (SE Spain)

Financial support was provided by Clare College Geological Research Fund to N.P. Evans. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013)/ERC Grant Agreement n. 339694 (Water Isotopes of Hydrated Minerals) to D.A. Hodell.We studied one cycle (Cycle 6) of gypsum-marl deposition from the Messinian Yesares Member in Sorbas Basin, Spain. The objective was to reconstruct the changing environment of deposition and its relation to astronomically-forced climate change. The δ18O and δD of gypsum hydration water (CaSO4 • 2H2O) and salinity of fluid inclusions were measured in the same samples to test if they record the composition of the mother fluid from which gypsum was precipitated. Water isotopes are highly correlated with fluid inclusion salinity suggesting the hydration water has not exchanged after formation. The relatively low water isotope values and fluid inclusion salinities indicate a significant influence of meteoric water, whereas δ34S, δ18OSO4 and 87Sr/86Sr support a dominant marine origin for the gypsum deposits. The discrepancy between water and elemental isotope signatures can be reconciled if meteoric water dissolved previously deposited marine sulfates supplying calcium and sulfate ions to the basin which maintained gypsum saturation. This recycling process accounts for the marine δ34S, δ18OSO4 and 87Sr/86Sr signatures, whereas the low δ18O and δD values of gypsum hydration water and fluid inclusion salinities reflect the influence of freshwater. The cyclic deposition of gypsum and marl in the Yesares Member has previously been interpreted to reflect changing climate related to Earth's precession cycle. We demonstrate that the δ18O, δD and salinity of the parent brine increased from low values at the base of the cycle to a maximum in the massive gypsum palisade, and decreased again to lower values in the supercones at the top of the cycle. This pattern, together with changes in mineralogy (calcite-dolomite-gypsum), is consistent with a precession-driven change in climate with wettest conditions (summer insolation maxima) associated with the base of the calcium carbonate marls and driest conditions (summer insolation minima) during formation of the gypsum palisade.Publisher PDFPeer reviewe

Archaeological Geophysical Prospection in Peatland Environments: case studies and suggestions for future practice

Peatland environments, in contrast to ‘dry-land’ sites, preserve organic material, including anthropogenic objects, because they are anaerobic, and are therefore of great importance to archaeology. Peat also preserves macro- and micro- paleoenvironmental evidence and is the primary resource for understanding past climates and ecology. Archaeological sites often lie within or at the base of wet, deep, homogenous peat rendering them invisible to surface observers. As a result, they most often c..

The calcium isotopic composition of carbonate hardground cements: A new record of changes in ocean chemistry?

Reconstructing changes in the calcium isotopic composition (δ44Ca) of the ocean over Earth history has been challenging. This difficulty is due to the large range of calcium isotope fractionation factors during mineral precipitation and the potential for overwriting the initial δ44Ca of minerals during shallow marine diagenesis. We present a new δ44Ca record measured in carbonate hardground cements, an inorganic carbonate-mineral precipitate that rapidly forms at or near the sediment-water interface. The range in the δ44Ca for any particular carbonate hardground cements is between 0.05 and 0.56‰. In some cases, the progressive increase in the δ44Ca during precipitation can be observed, consistent with precipitation in a ‘closed-system’. Our data show an average calcium isotope fractionation during carbonate hardground cement precipitation that is −0.57 ± 0.27‰, similar to the calcium isotope fractionation factor for inorganic calcite precipitates in previous laboratory and modelling studies, and closer to what is considered a kinetic end member calcium isotope fractionation than growth at equilibrium. This is consistent with the rapid carbonate mineral precipitation expected for carbonate hardground cements. Our δ44Ca record over the Phanerozoic is similar to other calcium-bearing mineral records over the same time interval, with average δ44Ca becoming lower going back in time by about 0.5 to 0.7‰. Our results add further support for the evolution of seawater δ44Ca over time, and we discuss the possible causes of these changes with suggestions for future studies

Two-billion-year-old evaporites capture Earth's great oxidation

Funding sources: Simons Foundation (SCOL 339006 to C.L.B.), European Research Council (ERC Horizon 2020 grant 678812 to M.C.), Research Council of Norway (RCN Centres of Excellence funding scheme project 223259 to K.P. and A.L.), Estonian Science Agency (PUT696 to K.K., A.L., K.P., T.K.).Major changes in atmospheric and ocean chemistry occurred in the Paleoproterozoic Era (2.5–1.6 billion years ago). Increasing oxidation dramatically changed Earth’s surface, but few quantitative constraints exist on this important transition. This study describes the sedimentology, mineralogy, and geochemistry of a remarkably preserved two-billion-year-old and ~800 meter-thick evaporite succession from the Onega Basin in Russian Karelia. The deposit consists of a basal unit dominated by halite (~100 m) followed by anhydrite-magnesite (~500 m) and dolomite-magnesite (~200 m) dominated units. The evaporite minerals robustly constraint marine sulfate concentrations to at least 10 millimoles per kilogram of water, representing an oxidant reservoir equivalent to over 20% of the modern ocean-atmosphere oxidizing capacity. These results show that substantial amounts of surface oxidant accumulated during this critical transition in Earth’s oxygenation.PostprintPeer reviewe

Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle.

Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2-540 pg alkanes per mL per day, which translates into a global ocean yield of ∼ 308-771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities

Physical weathering of carbonate host-rock by precipitation of soluble salts in caves: A case study in El Orón-Arco Cave (Region of Murcia, SE Spain)

The dissolution of carbonate host-rock by freshwater in phreatic or vadose conditions is the most common mechanism for the formation of caves; however, circulation of saline solutions through carbonate materials and precipitation of soluble salts may also play an important role. We studied the stable isotope composition (δ18O and δ34S of sulfate, δ18O and δD of structurally-bound gypsum hydration water and 87Sr/86Sr) and salinity of fluid inclusions in gypsum speleothems found in El Orón-Arco Cave (Cartagena, SE Spain). We suggest that physical weathering of carbonate host-rock was driven by precipitation of soluble sea-salts (mostly gypsum and halite), and this process controlled the recent geomorphological evolution of the cave. The Triassic carbonate host-rock shows clear evidence for salt weathering, including gypsum/halite infillings in cracks of the bedrock, mechanical spalling of the carbonate, and detachment of rock fragments that lead to the formation cave voids and in-situ accumulations of piles of unsorted rubble. Sulfur and oxygen isotopes of gypsum sulfate (3.0‰ < δ18O < 11.6‰ and 16.7‰ < δ34S < 20.7‰) are generally lower than modern seawater sulfate and suggest contributions from a 34S-depleted source (i.e. oxidation of pyrite). The δ18O and δD of gypsum hydration water are relatively low compared to expected values for the evaporation of pure seawater to gypsum saturation, suggesting that gypsum precipitation involved a secondary calcium-sulfate source or recycling of gypsum from previous stages, along with mixing of seawater and meteoric water seepage to the cave. The 87Sr/86Sr in gypsum shows intermediate values between modern seawater and Triassic carbonate values because of interaction between the solution and the bedrock. The salinities of the speleothem-forming solutions are relatively high (13.2 ± 3.2 wt% eq. NaCl) compared to gypsum formed from evaporated brackish solutions (i.e. ~4–8 wt% eq. NaCl) and indicate dissolution of earlier evaporites before secondary gypsum precipitation. This cave-forming mechanism, which is related to saline water circulation and precipitation of evaporitic minerals, may be common in other coastal caves

Hydrocarbon-related microbial processes in the deep sediments of the Eastern Mediterranean Levantine Basin

During the 2011 exploration season of the EV Nautilus in the Mediterranean Sea, we conducted a multidisciplinary study, aimed at exploring the microbial populations below the sediment–water interface (SWI) in the hydrocarbon-rich environments of the Levantine basin. Two c. 1000-m-deep locations were sampled: sediments fueled by methane seepage at the toe of the Palmachim disturbance and a patch of euxinic sediment with high sulfide and methane content offshore Acre, enriched by hydrocarbon from an unknown source. We describe the composition of the microbial population in the top 5 cm of the sediment with 1 cm resolution, accompanied by measurements of methane and sulfate concentrations, and the isotopic composition of this methane and sulfate (δ13CCH4, δ18OSO4, and δ34SSO4). Our geochemical and microbiological results indicate the presence of the anaerobic methane oxidation (AOM) coupled to bacterial sulfate reduction (BSR). We show that complex methane and sulfur metabolizing microbial populations are present in both locations, although their community structure and metabolic preferences differ due to potential variation in the hydrocarbon source

The Carbon-Sulfur Link in the Remineralization of Organic Carbon in Surface Sediments

Here we present the carbon isotopic composition of dissolved inorganic carbon (DIC) and the sulfur isotopic composition of sulfate, along with changes in sulfate concentrations, of the pore fluid collected from a series of sediment cores located along a depth transect on the Iberian Margin. We use these data to explore the coupling of microbial sulfate reduction (MSR) to organic carbon oxidation in the uppermost (up to nine meters) sediment. We argue that the combined use of the carbon and sulfur isotopic composition, of DIC and sulfate respectively, in sedimentary pore fluids, viewed through a δ13CDIC vs. δ34SSO4 cross plot, reveals significant insight into the nature of carbon-sulfur coupling in marine sedimentary pore fluids on continental margins. Our data show systemic changes in the carbon and sulfur isotopic composition of DIC and sulfate (respectively) where, at all sites, the carbon isotopic composition of the DIC decreases before the sulfur isotopic composition of sulfate increases. We compare our results to global data and show that this behavior persists over a range of sediment types, locations and water depths. We use a reactive-transport model to show how changes in the amount of DIC in seawater, the carbon isotopic composition of organic matter, the amount of organic carbon oxidation by early diagenetic reactions, and the presence and source of methane influence the carbon and sulfur isotopic composition of sedimentary pore fluids and the shape of the δ13CDIC vs. δ34SSO4 cross plot. The δ13C of the DIC released during sulfate reduction and sulfate-driven anaerobic oxidation of methane is a major control on the minimum δ13CDIC value in the δ13CDIC vs. δ34SSO4 cross plot, with the δ13C of the organic carbon being important during both MSR and combined sulfate reduction, sulfate-driven AOM and methanogenesis