Metal-induced malformations in early Palaeozoic plankton are harbingers of mass extinction

Glacial episodes have been linked to Ordovician–Silurian extinction events, but cooling itself may not be solely responsible for these extinctions. Teratological (malformed) assemblages of fossil plankton that correlate precisely with the extinction events can help identify alternate drivers of extinction. Here we show that metal poisoning may have caused these aberrant morphologies during a late Silurian (Pridoli) event. Malformations coincide with a dramatic increase of metals (Fe, Mo, Pb, Mn and As) in the fossils and their host rocks. Metallic toxins are known to cause a teratological response in modern organisms, which is now routinely used as a proxy to assess oceanic metal contamination. Similarly, our study identifies metal-induced teratology as a deep-time, palaeobiological monitor of palaeo-ocean chemistry. The redox-sensitive character of enriched metals supports emerging ‘oceanic anoxic event’ models. Our data suggest that spreading anoxia and redox cycling of harmful metals was a contributing kill mechanism during these devastating Ordovician–Silurian palaeobiological events

Upper Ordovician chronostratigraphic correlation between the Appalachian and Midcontinent basins

Study of a subsurface core (named F688) from northern Indiana provides integrated data sets linking Katian chronostratigraphic records of the Appalachian and Midcontinent basins. The F688 core shows a variety of shallow- and deep-water facies containing numerous, well-preserved and zonally significant fossil species and diagnostic chemostratigraphic patterns. The succession belonging to the Cincinnatian Regional Stage in the F688 core is 210 m thick. Detailed benchtop examination of the succession revealed several phosphatic intervals, rich brachiopod faunas, multiple graptolitic horizons, and at least two tephras. Elemental analysis was conducted at 60 cm spacing quantifying lithofacies composition. Based on these results, the succession was assigned to six previously defined lithostratigraphic units (Kope, Waynesville, Liberty, Whitewater, Elkhorn, and Fort Atkinson formations). This lithostratigraphic succession shares components with both the Appalachian and Midcontinent basins, suggesting deposition near their shared margin. Twenty samples yielded abundant, well-preserved, low-diversity conodont assemblages with long-ranging taxa that clearly demarcate the position of the OrdovicianâSilurian boundary at the top of the succession in the core. More than fifty palynologic samples, targeting graptolite-bearing intervals, were processed for chitinozoans and produced important new insights. The Kope Formation contains the chitinozoan species Belonechitina kjellstromi, Hercochitina downiei, and Clathrochitina sp. nov., co-occurring with a graptolite assemblage suggestive of the Geniculograptus pygmaeus Zone. Samples from the overlying Waynesville Formation produced graptolites indicative of the upper G. pygmaeus to Paraorthograptus manitoulinensis zones co-occurring with the long-ranging chitinozoan species Belonechitina micracantha and Plectochitina spongiosa as well as several new species of the genera Tanuchitina and Hercochitina. Higher in the core, the Liberty, Whitewater, Elkhorn, and Fort Atkinson formations yielded chitinozoan species characteristic of the upper Katian biozones of Anticosti Island and Nevada, such as Tanuchitina anticostiensis, Hercochitina longi, and Eisenackitina ripae. Results of δ13Ccarb analysis reveal partial preservation of the Kope, Waynesville, and Elkhorn excursions. A tephra in the rising limb of the Waynesville Excursion yielded needle-shaped clear zircons that will provide a high-precision U-Pb age. The Fort Atkinson Formation is overlain by the Brassfield Formation containing Silurian conodonts and δ13Ccarb values suggesting an Aeronian age. Chronostratigraphic data from our study of the F688 core resolves longstanding uncertainty about correlations between strata of Katian Age in the Appalachian and Midcontinent basins. Integration of core F688 with our other regional chronostratigraphic data in the Midcontinent Basin demonstrates that the Fort Atkinson Formation of the Indiana and Illinois subsurface is age equivalent to the Fernvale Formation of Tennessee, Arkansas, and Oklahoma. Across this area, the Fernvale is overlain by graptolitic shales of the uppermost P. manitoulinensis to basal Dicellograptus complanatus graptolite zones. By contrast, the type Fort Atkinson Formation of Iowa is interpreted to occur completely within the younger D. complanatus Zone. These regional correlations taken as a whole suggest that the uppermost Katian (all of Ka4) and all but the uppermost Hirnantian are missing throughout much of the Appalachian Basin. By contrast, the Midcontinent Basin contains a much more complete upper Katian and Hirnantian succession. Our comprehensive approach is correcting temporal miscorrelation and providing robust chronostratigraphic context for study of biogeochemical events, which will further enable us to disentangle proxy data and identify the processes that drove the Katian diversity peak and culminated in the Late Ordovician mass extinction

The late Katian Elkhorn event: precursor to the Late Ordovician mass extinction

The late Katian Elkhorn event is a biogeochemical perturbation preceding the Late Ordovician mass extinction (LOME) with an exceptional record in the United States (U.S.). Results of our recent studies in this interval allow revised temporal ordering to strata across multiple basins providing insights into the magnitude of environmental disturbance and associated processes and feedbacks. The record of the Elkhorn event spans portions of the Appalachian and Midcontinent basins in the eastern U.S. and the Williston Basin and Cordilleran margin in the west. Our work focuses heavily on the Midcontinent Basin in particular, as it shares many characteristics of size, tectonic setting, and lithofacies with the Baltic Basin, providing the potential for resolving global signatures of the event. In its type-area, the Cincinnatian Series ends with the Elkhorn event. The succession is marked by shallowing from subtidal to marginal marine facies, capped by a karstic sequence boundary. Our new conodont data demonstrate that an overlying white to pink crinoidal grainstone package, previously assigned to the basal Silurian âwhiteâ Brassfield Formation near the Ohio-Indiana state line, is in fact Upper Ordovician. Further, δ13Ccarb values in this unit are elevated, in line with later phases of the Elkhorn event (2â° more positive than reported Rhuddanian values). These findings support a correlation of the grainstone interval with the Fernvale Formation of central Tennessee. To the east, much of the northern Appalachian Basin was overfilled with widespread marginal marine to terrestrial red beds by the onset of the Elkhorn event, while the Midcontinent Basin to the west remained relatively sediment starved. In the southern Midcontinent, the mid-Elkhorn event sequence boundary was onlapped by ironstone deposition (lower Fernvale Formation). The ironstones are overlain by sparry and hematitic grainstones with localized bioherms. In Arkansas, where the Fernvale is thickest (>30 m), the sparry phase gives way upward to manganese carbonates and bioherms. Across the region, the Fernvale is, in turn, cut by a sequence boundary, suggesting a yet higher Katian sequence, and is perforated by paleokarst pockets that are filled and overlain by upper Katian (Ka4) sediments. This sequence boundary is onlapped by black shales and the thickest (>10 m) phosphorite of the Ordovician at the end of the Elkhorn event. Previous studies have suggested age equivalence of the Elkhorn and Paroveja δ13Ccarb excursions in Laurentia and Baltica. Despite the attraction of aligning the latest Richmondian and Pirgu regional stages, our data sets demonstrate that this is a miscorrelation. Critical to this revision are new integrated biostratigraphic and chemostratigraphic data sets in a transect from the margin of the Appalachian Basin into the Midcontinent Basin. The new data reveal that the Elkhorn Shale and Fernvale Formation are overlain by the Brainard and laterally equivalent Sylvan, and Mannie shales. These shale successions contain graptolites of the complanatusand pacificus zones. Thus, the Elkhorn event occurred in the latest manitoulinensis Zone, suggesting correlation with the Baltic Moe δ13Ccarb excursion. Our extensive new data sets provide regional chronostratigraphic correlation of strata deposited during the Elkhorn event. When temporally ordered, these records provide evidence for high amplitude sea level oscillations, major redox fluctuations, and reef pulses that demonstrate the waxing and waning of continental ice sheets on Gondwana and the spread of oceanic anoxia only a few million years before the LOME. These findings further call into question traditional models of rapid glaciation during a long-lived greenhouse state as the sole driver of the LOME and emphasize the need for new integrated Upper Ordovician research initiatives to better characterize Katian events

The origin and composition of carbonatite-derived carbonate-bearing fluorapatite deposits

Carbonate-bearing fluorapatite rocks occur at over 30 globally distributed carbonatite complexes and represent a substantial potential supply of phosphorus for the fertiliser industry. However, the process(es) involved in forming carbonate-bearing fluorapatite at some carbonatites remain equivocal, with both hydrothermal and weathering mechanisms inferred. In this contribution, we compare the paragenesis and trace element contents of carbonate-bearing fluorapatite rocks from the Kovdor, Sokli, Bukusu, Catalão I and Glenover carbonatites in order to further understand their origin, as well as to comment upon the concentration of elements that may be deleterious to fertiliser production. The paragenesis of apatite from each deposit is broadly equivalent, comprising residual magmatic grains overgrown by several different stages of carbonate-bearing fluorapatite. The first forms epitactic overgrowths on residual magmatic grains, followed by the formation of massive apatite which, in turn, is cross-cut by late euhedral and colloform apatite generations. Compositionally, the paragenetic sequence corresponds to a substantial decrease in the concentration of rare earth elements (REE), Sr, Na and Th, with an increase in U and Cd. The carbonate-bearing fluorapatite exhibits a negative Ce anomaly, attributed to oxic conditions in a surficial environment and, in combination with the textural and compositional commonality, supports a weathering origin for these rocks. Carbonate-bearing fluorapatite has Th contents which are several orders of magnitude lower than magmatic apatite grains, potentially making such apatite a more environmentally attractive feedstock for the fertiliser industry. Uranium and cadmium contents are higher in carbonate-bearing fluorapatite than magmatic carbonatite apatite, but are much lower than most marine phosphorites

Composition and source of salinity of ore-bearing fluids in Cu-Au systems of the Carajás Mineral Province, Brazil

The composition and Cl/Br – Na/Cl ratios of highly saline aqueous fluid inclusions from large tonnage (> 100 t) IOCG deposits (Sossego, Alvo 118, and Igarapé Bahia) and a Paleoproterozoic intrusion-related Cu-Au- (Mo-W-Bi-Sn) deposit (Breves; < 50 Mt)) in the Carajás Mineral Province have been analysed by LA-ICP-MS and ion chromatography. In both Cu-Au systems, brine inclusions are Ca-dominated (5 to 10 times more than in porphyry Cu-Au fluids), and contain percent level concentrations of Na and K. IOCG inclusion fluids, however, contain higher Sr, Ba, Pb, and Zn\ud concentrations, but significantly less Bi, than inclusions\ud from the intrusion-related Breves deposit. Cu is consistently below detection limits in brine inclusions from\ud the IOCG and intrusion-related systems, with Fe not detected in the latter. Cl/Br and Na/Cl ratios of the IOCG\ud inclusion fluids range from entirely evaporative brines\ud (bittern fluids; e.g. Igarapé Bahia and Alvo 118) to values\ud that indicate mixing with magma-derived brines. Cl/Br and Na/Cl ratios of the Breves inclusion fluids strongly suggest the involvement of magmatic brines, but possibly\ud also incorporated bittern fluids. Collectively, these data\ud demonstrate that residual evaporative and magmatic brines were important components of the fluid regime involved in the formation of Cu-Au systems in the Carajás Mineral Province

Fluid inclusion insights into the origins of fluids and metals in porphyry copper deposits

Models of the evolution of the hydrothermal systems that form porphyry Cu (Mo-Au) deposits are compromised because aqueous magma-derived fluids in the ore zones of most deposits have changed from their original magmatic compositions as a result of cooling, depressurising, mineral precipitation, brine-vapour unmixing and fluid-rock\ud reactions. However, in deep quartz-rich, sulfide-poor veins from numerous porphyry type deposits, we have identified parental fluids trapped in inclusions at near magmatic\ud temperatures and pressures above the brine-vapour unmixing solvus. We have analysed these inclusions for bulk salinity, density, solute chemistry, helium isotopic ratios and elemental composition, These parental inclusions contain 35 - 70 volume per cent bubble, are low to moderate salinity, contain up to ten mol per cent CO2, and commonly contain a chalcopyrite daughter crystal. Our results indicate that these Cu-rich fluids transport Cu from a plutonic complex below upward into a hydrothermal system, where decompression, cooling, unmixing and water-rock\ud reaction drive ore-mineral precipitation. Na/CI ratios greater than one indicate that in addition to chlorine, sulfur and/or carbonate must play a key role in Cu transportation. Helium isotope ratios indicate that between - 15 and 100 per cent of helium in these fluids is mantle-derived. We suggest that in addition to He, volatiles from mafic magmas in the mantle are also likely to supply CO2 Cu and S to the fluids that form porphyry copper deposits

Precipitation of lead-zinc ores in the Mississipi Valley-type deposit at Trèves, Cévennes region of southern France

International audienceThe Trèves zinc-lead deposit is one of several Mississippi Valley-type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ34S values determined for the minerals in the deposit (12.2-19.2‰ for barite, 3.8-13.8‰ for sphalerite and galena, and 8.7 to −21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur-rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore-forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault-controlled and mineralogically similar MVT deposits in the Cévennes region

Can facies act as a chronostratigraphical tool?

Recent advances in chronostratigraphy are enabling global correlation of Silurian strata at a temporal resolution of 10-100 k.y. Comparative analysis of disparate localities at this resolution is yielding surprisingly similar peculiarities of facies. Facies analysis has been traditionally regarded as a tool to investigate local paleoenvironmental conditions and reconstruct past paleoecological settings. Less frequently are aspects of facies recognized as long-distance time-correlative markers. The concept of time-specific facies, originally proposed by Walliser (1986) and recently revised by Brett et al. (2012), challenges the \u201cstrictly local\u201d facies paradigm by emphasizing that some aspects of facies are signatures of broader oceanic-climatic processes. Their synchronous occurrence, spanning major portions of sedimentary basins to globally, represents the key distinctive factor of time-specific facies. This aspect is combined with the significance of the ecostratigraphic analysis as a tool to identify bioevents and, therefore, for improving biostratigraphic subdivisions (e.g., Boucot, 1986). Marine ironstones represent a prime example of time-specific facies. Silurian ironstones retaining microbial signatures are documented by Ferretti et al. (2012) in forms of Fe-rich oolitic horizons and ferruginous laminated structures for the Llandovery-Wenlock boundary interval (mid-late Telychian, Pt. celloni Superzone-Pt. a. amorphognathoides Zone and Sheinwoodian, Oz. s. rhenana Zone) in the Carnic Alps (Austria). Age-equivalent ironstones also occur in the Appalachian Basin of eastern North America (McLaughlin et al., 2012). Appalachian Basin ironstones collected from the New Point Stone quarry (Napoleon, Indiana) and Dawes Quarry Creek (Clinton, New York) were recently analyzed through combined analytical techniques (i.e., confocal laser Raman microscopy, X-ray diffraction, ESEM-EDX, and optical microscopy) for a geobiological characterization. Results demonstrate that the Appalachian ironstones seem to reflect the same microbially-mediated iron mineralization already documented in the Carnic Alps. Combined evidence of iron geochemistry and microbial interactions include i) the formation of planar laminated ironstones (late Telychian); ii) coeval ooidal pack- to grain-ironstones; iii) a wealth of other microbial-related morphostructures and mineralogies. The synchroneity of iron microbe activity on opposite ends of the Iapetus Ocean during the late Telychian and Sheinwoodian is inferred as a time-specific sea water redox signature associated with the Ireviken Event