Search

[The manuscript presents the first attempt to define the diagenetic conditions (burial and related paleo‐temperatures) for sulfur formation in relationship with the deposits generated by the Messinian salinit crisis. ​, Abstract Recent studies on the genesis of sedimentary native sulfur deposits indicate diagenetic mid‐low temperature Bacterial Sulfate Reduction (BSR) as the main process, involving organic compounds (kerogen/hydrocarbons), bacterial colonies and gypsiferous rocks. In the peri‐Mediterranean area (Southern Spain, Sicily, Northern Apennines, Israel), the main sulfur accumulations are always associated with late Miocene sulfates and organic‐rich successions encompassing the Messinian salinity crisis (MSC). In particular, the Messinian successions of the Apennine‐Adriatic foreland basin system, due to a large amount of high‐resolution stratigraphic data, represent a perfect case study for understanding the diagenetic conditions controlling the development of the BSR process during sedimentary basin evolution. In this work, thermal models performed in three sub‐basins in a sector of the Northern Apennines comprised of the Sillaro and Marecchia rivers (Italy), calibrated by means of organic and inorganic geothermometers, indicate a general thermal immaturity of the studied successions attained as a result of a constant heat flow similar to the present day one (ca. 40 mW/m2) since Late Tortonian and lithostatic loads between 615 and 1,710 m depending on different sub‐basins. These results suggest that the MSC deposits experienced maximum temperatures between about 39°C and 65°C. Temperatures derived from thermal models have been used to constraint occurrence of the diagenetic BSR associated with evaporitic deposits providing thermal constraints in sulfur genesis as well as new useful thermal‐constraints for basin analysis studies.]

Thermochemical sulfate reduction (TSR) commonly occurred in the dolostone reservoirs of the Upper Permian Changxing Formation (P3c) in the Yuanba (YB) gas field, Sichuan Basin, yet controversy remains regarding the source of sulfate required for TSR. To trace the source of the sulfate, sulfur and strontium isotopic compositions were measured for three diagenetic celestite (SrSO4) samples found in the P3c dolostone reservoirs in the YB gas field. In addition, the sulfur isotopic compositions of Carbonate-associated sulfates (CAS) from the P3c carbonates and spheroidal pyrites in dolomicrites from the P/T boundary (PTB) in the YB gas field were measured for comparative studies. The results show that the sulfur isotopic compositions of celestites are significantly heavier than those of the contemporaneous seawater, and these celestites have strontium isotopic values consistent with those of the host dolostones and contemporaneous seawater. The −33.68‰ fractionation in average δ34S values between pyrites and celestites indicated that their formation was likely to be related to bacterial sulfate reduction (BSR). During the P/T extinction event that accompanied the end-Permian regression, the reflux of brine directly precipitated 34S-rich celestites in the fractures and vugs of the dolostone reservoirs due to the BSR and the evaporation of seawater. These 34S-rich celesites and associated pore fluids provide a new explanation for the source of sulfate required for the late TSR.

Sulfur isotope in sulfides from the Paleoarchean and the Neoarchean sedimentary rocks evidence microbial sulfur metabolism in Archean sulfur cycle. However, sulfur metabolism for the Mesoarchean interval is less obvious since evidence for a large range in sulfur isotope values has not yet been observed in Mesoarchean samples. We report the results of multiple sulfur isotope measurements for sulfide minerals from ~2.8 Ga sedimentary rocks in the southeastern part of the Karelian Craton. In situ isotope analysis of sulfide grains have been performed using a femtosecond laser-ablation fluorination method. Sulfide samples studied here yielded Δ33S values between −0.3 and +2.7‰ and δ34S values between −10 and +33‰. The Δ33S dataset was interpreted to indicate the incorporation of sulfur from two coexisting sulfur pools, photolytic sulfate and photolytically derived elemental sulfur. We suggest that the relative contributions of these Δ33S different pools to the pyritic sulfur could be controlled by the metabolic activity of coexisting sulfate-reducing and sulfur-disproportionating bacteria during pyrite formation. We therefore suggest the operation of different metabolic pathways of sulfur in Mesoarchean sedimentary environments.

This study investigates how glacially delivered reactive iron (oxyhydr) oxide and manganese oxide phases influence the biogeochemical cycling of sulfur in sediments of three Arctic fjords and how the biogeochemical signatures of these processes are preserved. Results reveal differences in the concentrations of dissolved iron and manganese in pore-waters and the concentration of solid-phase sulfur species within individual fjords and amongst the three fjords, likely controlled by the varying input of reactive iron (oxyhydr) oxides to the sediment. Broadly, the stations can be divided into three categories based on their biogeochemical signals. Stations in the first category, located in Smeerenburgfjorden, are characterized by relatively low concentrations of (easily) reducible particulate iron phases, increasing concentrations of iron monosulfides, pyrite, and elemental sulfur with depth, and low pore-water dissolved iron and manganese concentrations. Biogeochemical processes at these stations are primarily driven by organoclastic sulfate reduction, sulfur disproportionation and the subsequent reaction and sequestration of sulfide in the sediment as iron monosulfide and pyrite. Sulfur and oxygen isotope values of sulfate display progressive enrichment in heavy isotopes with depth at these stations. In contrast, concentrations of (easily) reducible particulate iron phases and pore-water dissolved iron (up to 850 mu M) and manganese (up to 650 mu M) are very high at stations of the second and third category, located in Kongsfjorden and Van Mijenfjorden, while iron monosulfide and pyrite contents are extremely low. The amount of pyrite and its isotope values in conjunction with organic sulfur compounds provide evidence for a detrital origin of a fraction of these sulfur compounds. At the Kongsfjorden and Van Mijenfjorden stations, oxidative pathways of the sedimentary sulfur cycle, controlled by the high availability of reducible particulate iron phases, play an important role, leading to the effective recycling of sulfide to sulfate through sulfur intermediates and concomitant resupply of the sulfate reservoir with S-32. In both fjords, elemental sulfur was only detected at the outer fjord stations grouped into the third category. Our study provides a framework for interpreting the Fe-S-C geochemistry of similar continental shelf areas in modern settings and ultimately for identifying these environments in the rock record.

Copyright © 2016, SEPM (Society for Sedimentary Geology). The mechanisms by which soft-bodied organisms were preserved in late Ediacaran deep-marine environments are revealed by petrographic and geochemical investigation of fossil-bearing surfaces from the Conception and St. John's groups (Newfoundland, Canada). Framboidal pyrite veneers are documented on fossilbearing horizons at multiple localities. The pyrite is interpreted to have formed via microbial processes in the hours to weeks following burial of benthic communities. This finding extends the 'death mask' model for Ediacaran soft-tissue preservation to deep-marine settings. Remineralization of pyrite to iron oxides and oxyhydroxides is recognized to result from recent oxidation by meteoric fluids in the shallow subsurface. Consideration of other global Ediacaran macrofossil occurrences reveals that pyrite is observed in association with Ediacaran macrofossils preserved in all four previously described styles of moldic preservation (Flinders-, Conception-, Fermeuse- and Nama-type). This suggests that replication of external morphology by framboidal pyrite was a widespread mechanism by which softbodied organisms and associated organic surfaces were preserved, in multiple facies and depositional environments, 580-541 million years ago. The extensive global burial of pyrite in medium- to coarse-grained clastics and carbonates is a previously unrecognized yet potentially significant geological sink of iron and sulfur, and may have contributed to rising atmospheric and marine oxygen concentrations across the late Ediacaran interval.

The Mazatán barite deposits, Sonora, NW Mexico, represent an outstanding example of Paleozoic bedded barite, a poorly understood type of mineral deposit of major economic interest. The deposits of this type commonly occur hosted by shales and are characterized by the lack of base-metal sulfide mineralization, in contrast to classic sedimentary-exhalative (or SEDEX) deposits. A throughout study of the Mazatán barite deposits, based on petrography, fluid inclusions analyses and isotope geochemistry, confirmed the link between bedded barite and fossil hydrocarbon seeps, thereby leaving hydrothermal vent-related processes ruled out. Hence, modern cold seeps in continental margins would account for the geological setting and genetic aspects of this type of deposit.The largest barite bodies of Mazatán are hosted within an Upper Carboniferous flysch succession, which formed part of an accretionary wedge related to the subduction of the Rheic Ocean beneath Gondwana. As well, a few barite occurrences are hosted in Upper Devonian, pre-orogenic turbidites. A variety of mineralized structures is displayed by barite, including: septaria nodules, enterolitic structures, rosettes and debris-flow conglomerates. Barite is accompanied by chalcedony, pyrite (framboids) and berthierine. Gas-rich fluid inclusions in barite were analyzed by micro-Raman spectroscopy and methane was identified, suggesting the occurrence of light hydrocarbons in the environment within which barite precipitated. 13C-depleted carbonates (δ13C: -24.3 to -18.7‰) were found in the barite deposits; they likely formed through anaerobic oxidation of methane coupled to sulfate reduction. Besides, these carbonates yield negative δ18O values (-11.9 to -5.2‰) reflecting the isotopic composition of Devonian-Carboniferous seawater; alternatively, this 18O-depletion could reflect late diagenetic processes. Methane-derived carbonates occur at modern hydrocarbon seeps and have been reported from Mesozoic, Cenozoic and even Paleozoic seep sediments, but they have never before been described in Paleozoic bedded barite deposits. δ34S values of barite vary from +17.6 to +64.1‰, with the lowest values overlapping the range for coeval seawater sulfate; this distribution indicates a process of sulfate reduction. Barite precipitation can be explained by mixing methane- and barium-rich fluids with pore-water (seawater) containing sulfate residual from microbial reduction. Two analyses from barite gave an 87Sr/86Sr within and slightly above the range for seawater at the time of deposition, with 0.708130 and 0.708588, which would preclude the involvement of hydrothermal fluids in the mineralization process. © 2013 Elsevier B.V., Funding was provided by the projects IN103211 (PAPIIT, UNAM) and 2009SGR-00444 (AGAUR, Generalitat de Catalunya).

The Xilitla section of central Mexico (western margin of the proto-North Atlantic) is characterized by pelagic sediments enriched in marine organic matter. Using biostratigraphic and radiometric data, it was dated at the latest Cenomanian–earliest Turonian transition. We identified an interval coeval with the faunal turnover associated with the Oceanic Anoxic Event 2 (OAE 2), recording the Heterohelix shift and the “filament event” for the first time in Mexico. An integral analysis of sedimentary facies, pyrite and geochemical proxies reveals vertically variable redox conditions, with prevailing anoxic to dysoxic bottom waters. Along with phosphorous and manganese depletion, the highest content of total organic carbon and of certain redox-sensitive trace elements (RSTEs) is found during part of the anoxic event, confirming more uniform and constant oxygen-depleted conditions. This interval is also characterized by a significant enrichment in biogenic barium and elevated TOC/NTOT ratios, suggesting a link between productivity and anoxia. Sulfur isotope fractionation has a maximum value within the anoxic event, favored by the increase in the flux of organic matter and intensified through sulfur recycling. Highly bioturbated beds representing short-lived episodes of oxic conditions are intermittent within the OAE 2 and become more frequent in the early Turonian. This study proposes a model similar to that of modern upwelling regions. High marine productivity controlled organic matter burial and oxygenation at the seafloor, varying between anoxic (laminated facies with small pyrite framboids) and dysoxic conditions (bedding-parallel bioturbated facies with inoceramid bivalves and large pyrite framboids), interrupted by short-term well-oxygenated episodes (thoroughly bioturbated facies with common benthic foraminifera). General low-oxygen conditions led to the formation of glauconite and pyrite (bacterially mediated); the enrichment of redox-sensitive trace elements in sediments (Cd, Zn, V and Cr scavenged by organic matter and Ni, Mo, Pb, Co and Re by pyrite) and resulted in Mn and P depletion.

El artículo original ha sido publicado por Ore Geology Reviews, de la Editorial Elsevier, disponible en: http://www.sciencedirect.com/science/article/pii/S0169136813001443 El enlace vía DOI es: http://dx.doi.org/10.1016/j.oregeorev.2013.06.013, Chilean manto-type (CMT) Cu(-Ag) hydrothermal deposits share a characteristic association of volcano-sedimentary Jurassic to Lower Cretaceous host rocks, style of mineralization, ore and associated mineralogy and geochemistry, with ore grades typically >1%Cu, that make this family of deposits significant and interesting, both academically and economically. Although often stratabound, geological evidence supports an epigenetic origin for these deposits. We present a detailed stable isotope study of La Serena and Melipilla-Naltahua Lower Cretaceous deposits, central Chile, which reveals extremely negative δ34S values, to -50‰, which are among the lowest values found in any ore deposit. In addition, the range of δ34S values from sulfides in the two areas is very wide: -38.3 to -6.9‰ in La Serena, and -50.4 to -0.6‰ in Melipilla-Naltahua. These new data significantly extended the reported range of δ34S data for CMT deposits. Co-existing sulfates range from 7.9 to 14.3‰, and are exclusive to La Serena deposit. The wide sulfide isotopic range occurs at deposit and hand specimen scale, and suggests a polygenic sulfur source for these deposits, where bacteriogenic sulfide dominates. While sulfur isotope data for the bulk of Jurassic CMT deposits, northern Chile, suggests a predominant magmatic source in their origin (mean = -2.7 ± 1.9‰, 1σ), contributions of a magmatic component is only likely to be involved at Melipilla-Naltahua deposit. The δ13C values obtained for calcites associated with the mineralization range from -20.1 to 0.2‰ also suggesting polygenic carbon sources, with the likely strong involvement of degradation of organic matter and leaching of limestone. Two different genetic models, with involvement of hydrocarbon, are proposed for both areas. For Melipilla-Naltahua, a two-step model can be developed as follows: 1) Framboidal pyrite growth, with very low δ34S, formed by bacterial sulfate reduction in an open system, and with diagenetic degradation of oil-related brines, leaving pyrobitumen. 2) Cu-bearing stage, replacing of framboidal pyrite, inheriting depleted sulfur as low as -50.4‰, together with sulfides directly precipitated from a hydrothermal fluid with δ34S close to 0‰. For La Serena, a single step model fits best, without framboidal pyrite generation. Cu-bearing sulfides were precipitated mainly in veins where Cu plus base metal-bearing hydrothermal fluids mixed with H2S generated by bacterial sulfate reduction in the host rocks. Isotopic evidence clearly illustrates that bacterial activity, perhaps enhanced by hydrothermal activity, was fed by hydrocarbon brines and sulfate remobilized from continental evaporites. It is possible that variable ecological conditions led to different extents of isotopic fractionation, adding to the typical sulfur isotopic heterogeneity of such bacterial systems. For both areas, the Cu-bearing stage occurred during the peak to waning stages of the very low-grade metamorphism that affected the Lower Cretaceous sequence., Departamento de Didáctica de las Ciencias Experimentales (Universidad de Granada), Departamento de Mineralogía y Petrología (Universidad de Granada), Instituto Andaluz de Ciencias de la Tierra (CSIC-Universidad de Granada), Scottish Universities Environmental Research Centre, SUERC, Departamento de Geología, (Universidad de Chile), Andean Geothermal Center of Excellence CEGA-FONDAP (Universidad de Chile), School of Ocean and Earth Science, National Oceanography Centre (University of Southampton)

Shallow gas accumulates in coastal marine sediments when the burial rate of reactive organic matter beneath the sulfate zone is sufficiently high and the methanogenic zone is sufficiently deep. We investigated the controls on methane production and free methane gas accumulation along a 400 m seismo-acoustic transect across a sharp transition from gas-free into gas-bearing sediment in Aarhus Bay (Denmark). Twelve gravity cores were taken, in which the pore water was analyzed for inorganic solutes while rates of organic carbon mineralization were measured experimentally by (SO42-)-S-35 radiotracer method. The thickness of organic-rich Holocene mud increased from 5 to 10 m along the transect concomitant with a shallowing of the depth of the sulfate-methane transition from >4 m to 2.5 m. In spite of drastic differences in the distribution of methane and sulfate in the sediment along the transect, there were only small differences in total mineralization, and methanogenesis was only equivalent to about 1% of sulfate reduction. Shallow gas appeared where the mud thickness exceeded 8-9 m. Rates of methanogenesis increased along the transect as did the upward diffusive flux of methane. Interestingly, the increase in the sedimentation rate and Holocene mud thickness had only a modest direct effect on methanogenesis rates in deep sediments. This increase in methane flux, however, triggered a shallowing of the sulfate-methane transition which resulted in a large increase in methanogenesis at the top of the methanogenic zone. Thus, our results demonstrate a positive feedback mechanism that causes a strong enhancement of methanogenesis and explains the apparently abrupt appearance of gas when a threshold thickness of organic-rich mud is exceeded. (C) 2016 Elsevier Ltd. All rights reserved.