Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Raman spectroscopy and biomarker analysis reveal multiple carbon inputs to a Precambrian glacial sediment

Extractable biomarkers can help elucidate the environment and biota of ancient glaciations, although the method must be applied with care, as glacial sediments have a potential for incorporation of older detrital carbon. In Phanerozoic glacial sediments, the distinct elemental, molecular and isotopic compositions of the terrestrial and marine biomass allow discrimination between primary marine and redeposited terrestrial organic matter. However, as the Proterozoic biosphere was largely microbial and marine, biomarker and isotopic analyses are insufficient for distinguishing primary organic matter from secondary reworked organic matter. Here, we report the combined application of Raman spectroscopy and biomarker analysis to Precambrian glacial sediments, which, together, allows discrimination between mixed pools of organic carbon and provides a promising new approach for rapidly screening Precambrian sediments for immature organic matter amenable to biomarker analysis.     

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ³⁴S_CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation.Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ³⁴S_CAS values near Miocene seawater sulfate (～+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ¹³C_carb (～?11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ³⁴S_CAS (up to ～+37‰), CAS concentrations of ～600 ppm, mildly depleted δ¹³C_carb (～?6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ¹³C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.     

The impact of horizontal resolution on moist processes in the ECMWF model

Summer and winter climates simulated with the ECMWF (cycle 33) model at spectral scales T21, T42, T63 and T106 are analyzed to determine the impact of changes in horizontal resolution on atmospheric water vapor, clouds, convection, and precipitation. Qualitative changes in many moist processes occur in the transition from T21 to T42, especially in the tropics; at higher resolutions mostly incremental variations from patterns established at T42 result. Large-scale tropical moist processes are simulated more realistically at T21 than at finer resolutions, possibly reflecting a mismatch between the finer-scale dynamics and the scales at which the underlying assumptions of the physical parameterizations apply. Global precipitation increases monotonically with resolution, as a consequence of increasing convection. Global cloud cover, however, decreases in the transition from T21 to T42 due to drying of the tropics, but then increases slightly at finer resolutions. These small global increases are an outcome of compensating changes in different regions: decreases in cloud cover due to drying of the atmosphere at low latitudes are offset by high-latitude increases resulting from enhanced relative humidity associated with an intensifying atmospheric cold bias at finer resolutions.     

Terrestrial laser scanning survey in support of unstable slopes analysis: the case of Vulcano Island (Italy)

Natural Hazards - The capability to measure at distance dense cloud of 3D point has improved the relevance of geomatic techniques to support risk assessment analysis related to slope instability....     

Environmental and diagenetic variations in carbonate associated sulfate: An investigation of CAS in the Lower Triassic of the western USA

An integrated stable isotope, elemental and petrographic analysis of Early Triassic (Spathian) carbonates and evaporites along a proximal to deep environmental transect reveals significant variations in δ³⁴S composition of carbonate associated sulfate (CAS). The variations in the δ³⁴S of CAS are strongly correlated with the Ca/Mg composition of carbonates, suggesting that the variations are driven by the degree of dolomitization. The δ³⁴S of dolostones and evaporites are similar to one another and exhibit lower δ³⁴S values than limestones from all localities.Three hypotheses may explain the differences in δ³⁴S between proximal dolostones/evaporites and inner/middle shelf limestones: (1) limestones experienced anaerobic sulfate reduction and subsequent incorporation of ³⁴S-enriched sulfate into CAS during diagenesis, while dolostones did not—this is unlikely because of the lack of correlation between δ³⁴S_CAS and TOC, as well as other indicators of diagenesis, (2) dolomitization controlled the δ³⁴S_CAS in proximal paleoenvironments, where the source of the ³⁴S depleted fluids was either continentally-derived or the result of Rayleigh distillation during evaporite formation, and (3) a δ³⁴S depth gradient existed during the Early Triassic such that limestones formed in distal waters are more enriched in ³⁴S versus evaporites and dolostones formed in proximal settings—we do not favor this hypothesis because the strong correlation between Ca/Mg and δ³⁴S_CAS implies that dolomitization controls the δ³⁴S_CAS in these samples. Results from subtidal, well-preserved (non-dolomitized) limestones suggest that the δ³⁴S of Spathian seawater sulfate may have been heavier than previously suggested from analyses of evaporite deposits alone.     

Carbonate-associated sulfate as a proxy for lake level fluctuations: a proof of concept for Walker Lake, Nevada

Closed-basin alkaline lakes record climate change particularly well because they generally contain a sedimentary record that is high in carbonate mineral content from which climate proxies can be determined. Various approaches are used to estimate paleo-lake level and volume (δ¹⁸O, dating of “shoreline” tufas, biotic proxies, etc.), yet all carry certain caveats that limit their usefulness. Ultimately, the relationship between the chemistry of the lake, the volume of the lake, and the response of the proxy will determine how well a proxy serves a paleolimnologic purpose. Here, we discuss the use of carbonate-associated sulfate (CAS), the sulfate contained within the lattice of carbonate minerals that precipitate in lake water, as a proxy for lake water chemistry and by extension, lake volume. Walker Lake, an alkaline closed-basin lake in western Nevada, has experienced a well-documented lake-level decline since 1880 and provides a test case for CAS as a lake-level proxy. By extracting the CAS from sedimentary carbonate and tufas that have been age dated, we can relate these values to lake sulfate content based on historical or other proxy data. We confirm that CAS tracks lake sulfate. Our study of sedimentary carbonates demonstrates that CAS is a linear function of lake sulfate through a range of 10–25 mM, which corresponds to a change in lake level of 30 m. As confirmation of the CAS technique, we analyzed a stromatolitic tufa dated using AMS ¹⁴C. The CAS trend in the stromatolite suggested that it grew during a lake-level decline, a result consistent with other proxy data. Finally, laboratory experiments were conducted that demonstrate CAS is monotonically correlated with sulfate concentration and that precipitation kinetics are not likely a major control on CAS in alkaline lakes, but that ionic strength of the solution exerts a strong control on CAS.