Widespread Black Shale Deposition Research Articles

Roller-coaster atmospheric-terrestrial-oceanic-climatic system during Ordovician-Silurian transition: Consequences of large igneous provinces

The Ordovician-Silurian transition (OST) hosted profound and frequent changes in the atmospheric-terrestrial-oceanic-climatic system (ATOCS). Previous studies have found contrasting stages for such changes, primarily based on hiatus-interrupted sections. However, the dominant driving factors and mechanisms reconciling such frequent changes remain controversial. Mercury isotopes, which undergo both mass-dependent and mass-independent fractionation, can provide critical insights into the deep-time ATOCSs, especially for those impacted by large igneous provinces (LIPs) events. Here, we build a high-resolution multi-proxy record of Hg (concentrations and isotopic compositions) combined with organic carbon isotopes (δ13Corg) and whole-rock geochemical data (including trace elements and phosphorus) from continuous cores in the Yangtze Platform, South China. Our data, combined with reported ones, indicate the occurrence of LIP eruptions against localized volcanism, and four successive, yet contrasting stages of ATOCSs during the OST. Moreover, we identified the coupling between two-pulse LIP magmatism and extreme ATOCSs, each with special pCO2, weathering rate, primary productivity, redox condition, climatic mode, and biotic evolution. For stage I, the first pulse of LIP magmatism triggered global warming, enhanced terrestrial weathering, oceanic acidification, eutrophication, anoxia, P recycling, and thereby widespread deposition of black shales. During stage II, the Hirnantian glaciation and oxygenation arose from the intense chemical weathering and black shale deposition of stage I; slashed terrestrial weathering and oceanic oxygenation facilitated CO2 accumulation. In stage III, another pulse of LIP magmatism triggered the de-glaciation, and the ATOCS was largely similar to that of stage I. This led to another round of oxygenation and positive δ13Corg excursion in stage IV. Compared with the environmental pressure by the peculiar ATOCS of each stage, their transitions might have been more devastating in triggering the prolonged Late Ordovician Mass Extinction (LOME). Moreover, limited biotic recovery was possible in the later portion of stages I and III. The multi-proxy study of continuous strata of the OST provides an excellent framework for better illuminating LIPs’ essential role in driving the “roller-coaster” behavior of the ATOCS and thus biotic crisis during the pivotal period of the OST.

Do spores herald the Toarcian Oceanic Anoxic Event?

The environmental perturbations of the Toarcian Oceanic Anoxic Event (T-OAE, ~183 Ma) were associated with the widespread deposition of black shales, such as the Posidonia Shale Formation in southwest Germany. We recently published a detailed palynological analysis of the deposits of the Posidonia Shale Formation at Dormettingen, investigating pollen, spores, and marine plankton. In addition to the comprehensive palynological analysis, we point out the occurrence of possible teratological features (i.e. unseparated spore tetrads and dark-coloured sporomorphs) before the T-OAE. These features have been tentatively linked to environmental changes, such as increased UV-B irradiation or heavy metal pollution associated with the large-scale volcanism of the Karoo Ferrar province (Galasso et al., 2022). Our interpretation has drawn criticism (Riding et al., 2022). Here we present a more substantiated discussion of why spore tetrads and darkened spores might not be sedimentological artefacts but indicators of aggravating environmental conditions prior to the T-OAE. The combined occurrence of several teratomorphic features (i.e. spore tetrads, dark sporomorph walls, and even polyploidy) during the earliest Toarcian (Tenuicostatum Zone) is interpreted as a signal of environmental stress in land plants, although for each individual morphological variation a much easier explanation exists.

Marine osmium isotope record during the Carnian “pluvial episode” (Late Triassic) in the pelagic Panthalassa Ocean

The Carnian Pluvial Episode (CPE) was a global environmental change and biotic crisis that occurred during the Carnian (Late Triassic). The climate during the CPE was characterized by a short-lived period of extreme rainfall, and an extinction of marine taxa is known to have occurred during the latest Julian (i.e. early Carnian). Although these events are considered to have been caused by the Wrangellia Flood Basalt (FB) volcanism, existing studies have found little direct evidence to support this. We investigated the temporal relationship between the eruption of Wrangellia FB and CPE using high-resolution microfossil biostratigraphy and paleo-seawater Os isotope data of an Upper Triassic bedded chert succession from an accretionary complex in Japan, which accumulated in a pelagic deep-sea environment in an equatorial region of the Panthalassa Ocean. Our biostratigraphic analysis, based on conodonts and radiolarians, and osmium isotope data show: (i) a continuous decline of initial Os isotope ratios (187Os/188Osi) in the early Julian; (ii) low 187Os/188Osi ratios during the late Julian; and (iii) an abrupt increase in 187Os/188Osi ratios at the end of the Julian. The decrease in 187Os/188Osi ratios throughout the Julian suggests an increased input of unradiogenic Os from the eruption of the Wrangellia FB into the ocean. Moreover, redox-sensitive elements, such as V and U, increased abruptly at the end of the Julian, which is the first evidence of reducing conditions during the CPE within the pelagic deep-sea Panthalassa Ocean. Marine anoxic event in the late Julian has been recognized from widespread deposition of black shales and organic-rich marls in intermediate to shallow water Tethyan sections. Thus, oxygen-depleted conditions occurred at the Tethyan shallow continental margin, as well as in the pelagic deep-sea Panthalassa Ocean, at the end of Wrangellia FB volcanism.

Enhanced Arctic-Tethys connectivity ended the Toarcian Oceanic Anoxic Event in NW Europe

AbstractThe Toarcian Oceanic Anoxic Event (T-OAE, c. 182 Ma) represents a major perturbation of the carbon cycle marked by widespread black shale deposition. Consequently, the onset of the T-OAE has been linked to the combined effects of global warming, high productivity, basin restriction and salinity stratification. However, the processes that led to termination of the event remain elusive. Here, we present palynological data from Arctic Siberia (Russia), the Viking Corridor (offshore Norway) and the Yorkshire Coast (UK), all spanning the upper Pliensbachian – upper Toarcian stages. Rather than a ‘dinoflagellate cyst black-out’, as recorded in T-OAE strata of NW Europe, both the Arctic and Viking Corridor records show high abundance and dinoflagellate diversity throughout the T-OAE interval as calibrated by C-isotope records. Significantly, in the Arctic Sea and Viking Corridor, numerous species of the Parvocysta and Phallocysta suites make their first appearance in the lower Toarcian Falciferum Zone much earlier than in Europe, where these key dinoflagellate species appeared suddenly during the Bifrons Zone. Our results indicate migrations of Arctic dinoflagellate species, driven by relative sea-level rise in the Viking Corridor and the establishment of a S-directed circulation from the Arctic Sea into the Tethys Ocean. The results support oceanographic models, but are at odds with some interpretations based on geochemical proxies. The migration of Arctic dinoflagellate species coincides with the end of the T-OAE and marks the arrival of oxygenated, low-salinity Arctic waters, triggering a regime change from persistent euxinia to more dynamic oxygen conditions.

Extreme sulfur isotope fractionation in the Late Devonian Dry Creek volcanogenic massive sulfide deposit, central Alaska

The Dry Creek Zn-Pb-Cu-Ag-Au volcanogenic massive sulfide (VMS) deposit, in east-central Alaska, occurs in a Late Devonian sequence of peralkaline rhyolite tuff, minor graphitic argillite, and local peralkaline quartz-porphyry rhyolite intrusions. Principal mineralized facies are semi-massive and massive sulfide in variably silicified and graphitic rhyolite tuff, massive sulfide in graphitic argillite, disseminated sulfides in graphitic and non-graphitic rhyolite tuff, and vein-hosted sulfides in a subvolcanic, peralkaline quartz-porphyry intrusion. In situ analysis of the sulfur isotope composition of sulfide minerals from all facies of the deposit shows a total range in δ34S values from −48.0 to 23.1‰. This remarkable 71.1‰ variation is more than twice the largest range known for sulfides in nearly all individual VMS deposits, both modern and ancient, which typically is <25‰. Based on results of geochemical reaction modeling presented here, extreme sulfur isotope systematics in the Dry Creek deposit is attributed to two main processes: low-temperature (<100 °C) kinetically controlled bacterial sulfate reduction (BSR) in anoxic to locally sulfidic bottom waters and pore fluids, and higher temperature (100–300 °C) hydrothermal sulfate reduction (HSR) of seawater sulfate during water-rock reactions. Deposition of organic-rich sediments prior to and during mineralization provided the key environment that promoted microbially mediated fractionations with Δ34Ssulfate-sulfide of up to 70‰. During BSR reaction progress modeling, residual sulfate evolved by Rayleigh distillation in pore water, producing δ34SSO4 values up to 58‰; normal Late Devonian seawater sulfate had δ34SSO4 = 22‰. BSR produced FeS precipitates with δ34S values from −50 to −15‰. Integrated textural and δ34S data also suggest that isotopically light H2S produced in pore fluids by BSR was incorporated into hydrothermal fluids and early disseminated sulfide minerals during the emplacement of peralkaline quartz-porphyry rhyolite intrusions in the shallow subsurface, broadly coeval with VMS mineralization. Modeling of moderate- to high-temperature (100–300 °C) hydrothermal sulfate reduction (HSR) of seawater-rock interaction predicts sulfide minerals with δ34S values from −8 to 19‰.High-precision CA-ID-TIMS U-Pb geochronology of zircons from a synvolcanic peralkaline quartz porphyry intrusion yields a weighted mean 206Pb/238U date of 363.02 ± 0.43 Ma (2σ total uncertainty). This date indicates that the formation of graphitic and sulfidic sediments at Dry Creek, and contemporaneous VMS mineralization, occurred at least 3.6 m.y. before, and hence are unrelated to, widespread black shale deposition during the Hangenberg Event at ca. 359 Ma.

Carbon cycle dynamics linked with Karoo-Ferrar volcanism and astronomical cycles during Pliensbachian-Toarcian (Early Jurassic)

Abstract One of the most profound environmental changes in the Mesozoic occurred during the Pliensbachian-Toarcian (Pl/To) time interval, including massive black shale deposition across Pl/To boundary and early Toarcian Oceanic Anoxic Event (T-OAE). These events are associated with negative carbon isotope excursions (CIEs), but their temporal link with 12C-rich carbon injection, possibly related with Karoo-Ferrar volcanisms and carbon cycle feedbacks, such as terrestrial methanogenesis and methane hydrate dissociation, is still debated. Here we present a new chemostratigraphy of the carbon isotopic ratio of organic matter (δ13Corg) from Pl/To deep-sea successions, in conjunction with bio-astrochronology. The deep-sea successions are located at the Katsuyama and Sakahogi outcrops in the Inuyama area, Japan, and contain two black bedded chert intervals named T-BBCs 1 and 2, which have astrochronologic ages of 183.25–183.01 ± 0.2 Ma and 183.55–182.80 ± 0.2 Ma. Negative CIEs of ~2‰ and ~5‰ are recognized across the base of T-BBCs 1 and 2, respectively, which are correlated with Pl/To boundary and classical T-OAE in shallow marine sections based on biostratigraphy. Astrochronologic ages of the onset of T-BBCs 1 and 2 are within the errors of the oldest high-precision U-Pb ages of Karoo and Ferrar LIPs, respectively. These temporal relations suggest a link between the 12C-rich carbon injection associated with Karoo and Ferrar volcanism, and CIEs associated with widespread black shale deposition across the Pl/To and T-OAE, respectively. Obliquity cycles in classic T-OAE CIE could have linked with terrestrial methanogenesis and methane hydrate dissociation in high-latitudes areas, whereas 405-kyr pacing of termination of T-CIE and T-BBCs deposition would be related with decreased chemical weathering and nutrient supply under weaker monsoon intensity, and possibly suppressed methane cycle across the termination of Pl/To and T-OAE periods.

Multiple sulfur-isotopic evidence for a shallowly stratified ocean following the Triassic-Jurassic boundary mass extinction

The cause of the Triassic-Jurassic (Tr-J) boundary biotic crisis, one of the ‘Big Five’ mass extinctions of the Phanerozoic, remains controversial. In this study, we analyzed multiple sulfur-isotope compositions (δ33S, δ34S and δ36S) of pyrite and Spy/TOC ratios in two Tr-J successions (Mariental, Mingolsheim) from the European Epicontinental Seaway (EES) in order to better document ocean-redox variations during the Tr-J transition. Our results show that upper Rhaetian strata are characterized by 34S-enriched pyrite, low Spy/TOC ratios, and values of Δ33Spy (i.e., the deviation from the mass-dependent array) lower than that estimated for contemporaneous seawater sulfate, suggesting an oxic-suboxic depositional environment punctuated by brief anoxic events. The overlying Hettangian strata exhibit relatively 34S-depleted pyrite, high Δ33Spy, and Spy/TOC values, and the presence of green sulfur bacterial biomarkers indicate a shift toward to euxinic conditions. The local development of intense marine anoxia thus postdated the Tr-J mass extinction, which does not provide support for the hypothesis that euxinia was the main killing agent at the Tr-J transition. Sulfur and organic carbon isotopic records that reveal a water-depth gradient (i.e., more 34S-, 13C-depleted with depth) in combination with Spy/TOC data suggest that the earliest Jurassic EES was strongly stratified, with a chemocline located at shallow depths just below storm wave base. Shallow oceanic stratification may have been a factor for widespread deposition of black shales, a large positive shift in carbonate δ13C values, and a delay in the recovery of marine ecosystems following the Tr-J boundary crisis.

Redox variations and organic matter accumulation on the Yangtze carbonate platform during Late Ediacaran–Early Cambrian: Constraints from petrology and geochemistry

In order to understand redox variations and organic matter accumulation on the Yangtze carbonate platform during the Late Ediacaran–Early Cambrian, petrological and geochemical studies of several wells were carried out in this work. Our data suggest that depositional environments were dominated by oxidizing bottom water conditions during the late Ediacaran, and evolved to anoxic conditions, triggered by blooms of microbial organisms in surface waters during the earliest Cambrian. Subsequently, massive release of H2S derived from both anaerobic recycling of organic matter and, probably, hydrothermal venting promoted a sulfidic ocean. The discovery of a Ni-Mo sulfide ore layer in the basal Cambrian implies that such a sulfidic condition spread onto the Yangtze carbonate platform interior during the late Cambrian Stage 2. Further, transgressive flooding led to widespread black shale deposition and persistently anoxic conditions, as indicated by geochemical proxies. During the late Ediacaran to earliest Cambrian, local and widespread phosphogenesis indicates that organic matter accumulation was intimately associated with microbial (especially cyanobacterial) blooms driven by phosphorus cycling. The organic matter accumulations in early Cambrian black shales, however, were in connection with anoxic bottom water conditions and intermittent replenishment of recycled organic phosphorus to surface waters.

The global Hangenberg Crisis (Devonian–Carboniferous transition): review of a first-order mass extinction

Abstract The global Hangenberg Crisis near the Devonian–Carboniferous boundary (DCB) represents a mass extinction that is of the same scale as the so-called ‘Big Five’ first-order Phanerozoic events. It played an important role in the evolution of many faunal groups and destroyed complete ecosystems but affected marine and terrestrial environments at slightly different times within a short time span of c. 100–300 kyr. The lower crisis interval in the uppermost Famennian started as a prelude with a minor eustatic sea-level fall, followed rather abruptly by pantropically widespread black shale deposition (Hangenberg Black Shale and equivalents). This transgressive and hypoxic/anoxic phase coincided with a global carbonate crisis and perturbation of the global carbon cycle as evidenced by a distinctive positive carbon isotope excursion, probably as a consequence of climate/salinity-driven oceanic overturns and outer-shelf eutrophication. It is the main extinction level for marine biota, especially for ammonoids, trilobites, conodonts, stromatoporoids, corals, some sharks, and deeper-water ostracodes, but probably also for placoderms, chitinozoans and early tetrapods. Extinction rates were lower for brachiopods, neritic ostracodes, bryozoans and echinoderms. Extinction patterns were similar in widely separate basins of the western and eastern Prototethys, while a contemporaneous marine macrofauna record from high latitudes is missing altogether. The middle crisis interval is characterized by a gradual but major eustatic sea-level fall, probably in the scale of more than 100 m, that caused the progradation of shallow-water siliciclastics (Hangenberg Sandstone and equivalents) and produced widespread unconformities due to reworking and non-deposition. The glacio-eustatic origin of this global regression is proven by miospore correlation with widespread diamictites of South America and South and North Africa, and by the evidence for significant tropical mountain glaciers in eastern North America. This isolated and short-lived plunge from global greenhouse into icehouse conditions may follow the significant drawdown of atmospheric CO 2 levels due to the prior massive burial of organic carbon during the global deposition of black shales. Increased carbon recycling by intensified terrestrial erosion in combination with the arrested burial of carbonates may have led to a gradual rise of CO 2 levels, re-warming, and a parallel increase in the influx of land-derived nutrients. The upper crisis interval in the uppermost Famennian is characterized by initial post-glacial transgression and a second global carbon isotope spike, as well as by opportunistic faunal blooms and the early re-radiation of several fossil groups. Minor reworking events and unconformities give evidence for continuing smaller-scale oscillations of sea-level and palaeoclimate. These may explain the terrestrial floral change near the Famennian–Tournaisian boundary and contemporaneous, evolutionarily highly significant extinctions of survivors of the main crisis. Still poorly understood small-scale events wiped out the last clymeniid ammonoids, phacopid trilobites, placoderms and some widespread brachiopod and foraminiferan groups. The post-crisis interval in the lower Tournaisian is marked by continuing eustatic rise (e.g. flooding of the Old Red Continent), and significant radiations in a renewed greenhouse time. But the recovery had not yet reached the pre-crisis level when it was suddenly interrupted by the global, second-order Lower Alum Shale Event at the base of the middle Tournaisian.

Redox‐controlled preservation of organic matter during “OAE 3” within the Western Interior Seaway

AbstractDuring the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events—the Coniacian to Santonian OAE 3—resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high‐resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon‐rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in δ13C indicate that redox‐controlled early diagenesis can also significantly alter δ13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, δ18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.

Black shales – from coolhouse to greenhouse (early Aptian)

Approximately 120 Ma major volcanic outgassing on the Ontong Java Plateau resulted in perturbations of the global carbon cycle, in a change from cool to greenhouse climate conditions and in major changes in oceanography leading to widespread deposition of black shales during the early Aptian Oceanic Anoxic Event 1a (OAE1a). However, onset of black-shale deposition was diachronous and prior to OAE1a occurred under specific paleogeographic and paleoceanographic conditions. The goal of this study is to identify paleoceanographic constraints during coolhouse conditions that resulted in pre-OAE1a black-shale deposition and to investigate if and to what extent the short-term orbitally induced climate changes are also recorded in the sedimentary archive. We compared four lower Aptian pelagic sections from the former southern and northern continental margins of the Alpine Tethys Ocean and traced the evolution of carbon isotopes, carbonate and organic carbon content as well as palynofacies before and at the onset of OAE1a. Throughout the studied interval, the sections record frequent precession-controlled changes in carbonate content, which are reflected by limestone-marlstone alternations in the shallowest and most proximal Cismon core and by limestone-black-shale couplets in the deepest Pusiano section. Depth controlled sub-/anoxia is also suggested by the prominent OAE1a black shales, which occurred first in the deeper Pie del Dosso and Roter Sattel sections and only subsequently in the shallower Cismon core. However, contrary to expectations, the deepest Pusiano section exhibits – instead of an earliest onset of prominent OAE1a black shales – only a minor increase in TOC and a decrease in carbonate content. This suggests that the orbitally driven climate changes most strongly influenced water stratification and hence are most prominently expressed in the deepest sections. Conversely, the volcanically induced long-term climate changes seemed to more strongly affect organic matter production, the extension of the oxygen minimum zone and hence had the strongest impact on sections at intermediate depth.

High‐precision U–Pb age and duration of the latest Devonian (Famennian) Hangenberg event, and its implications

AbstractPrecise U–Pb zircon dates from three volcanic ash beds that bracket the Hangenberg Shale in the Holy Cross Mountains, Poland, constrain the age and duration of one of the most significant palaeobiological events of the Palaeozoic Era, the Hangenberg Event. It is linked to a terminal Devonian global shift from greenhouse to icehouse climate conditions, a global transgression, and widespread black shale deposition. Our results constrain the Hangenberg Event to between 358.97 ± 0.11 Ma and 358.89 ± 0.20 Ma, with a calculated duration of 0.05 +0.14/−0.05 Ma. A third, underlying ash bed yielded a distinctly older age of 359.97 ± 0.46 Ma. The duration of ~50–100 ka. for the event is comparable to those of Quaternary glaciations, and is consistent with both a glacio‐eustatic origin for the eustatic fluctuations and changes in ocean chemistry that led to this major reorganization of the biosphere.

Altered Primary Production During Mass-Extinction Events

The Big Five mass-extinction events are characterized by dramatic changes in primary producers. Initial disturbance to primary producers is usually followed by a succession of pioneers that represent qualitative and quantitative changes in standing crops of land plants and/or phytoplankton. On land, a transient collapse of arborescent (tree-bearing) vegetation and the rapid spread of a pioneer vegetation dominated by ferns and fern allies characterizes the Permian/Triassic (P/T), Triassic/Jurassic (T/J), and Cretaceous/Paleogene (K/Pg) mass-extinction events. The availability of low-quality food, such as herbaceous low-growing plants, likely played a role in triggering secondary extinctions of herbivores (reptiles, insects). Furthermore, malformation of acritarchs, pollen, and spores during the end-Ordovician, end-Devonian, P/T and T/J extinctions also suggests primary producers were of lesser quality. More importantly, changes in vegetation drove important increases in weathering and erosion leading to elevated nutrient transfer from the continents to the oceans. In the marine realm, the end-Ordovician, end-Devonian, end-Permian, and end-Triassic extinction events are all followed by periods of high primary production, which is reflected in the widespread deposition of black shales. Due to their small size, low nutritional quality, and possible toxicity, the abundance of picoplankton, such as prasinophytes, acritarchs, as well as bacterioplankton (cyanobacteria and green sulfur bacteria) may have been additional factors in delaying ecosystem recovery.

Paleoceanographic Indicators for Early Cambrian Black Shales from the Yangtze Platform, South China: Evidence from Biomarkers and Carbon Isotopes

AbstractThe lower Cambrian Niutitang Formation, a widespread black shale deposition, is of geological interest because of its polymetallic beds, Cambrian explosion, depositional ages, dramatic environmental changes and so on. Previous study focused mainly on inorganic geochemistry and few studies have investigated the organic fractions of upper Neoproterozoic‐lower Cambrian strata in South China. Here we report a study of biomarkers plus organic carbon isotopes for black shales from Ganziping, Hunan Province (China). All the saturated hydrocarbon fractions have a unimodal distribution of n‐alkanes, a high content of short‐chain alkanes and maximize at C19 or C20 (C23 for sample Gzh00–1). The C27/C29 sterane ratio ranges from 0.77 to 1.20 and 4‐methylsteranes are in low abundance. These parameters indicate that algae and bacteria are the important primary producers. Furthermore, biomarker maturity proxies show the samples to be higher maturity. The low Pr/Ph values (&lt;0.7) suggest that the samples were deposited under anoxic conditions and, likely, under stratified water columns. In addition, 25‐norhopanes and gammacerane are present as diagnostic indicators of normal marine salinity and dysoxic to anoxic conditions. During the Early Tommotian, known to coincide with a transgression event, small shelly fossils increased in abundance and diversity. Moreover, positive δ13Corg excursions close to 1.4‰ occur at the base of the Tommotian stage. In summary, the Early Cambrian black shales were deposited under dramatic paleoenvironmental changes, including oceanic anoxia, higher primary productivity and sea‐level rise.

The Chachil Limestone (Pliensbachian–earliest Toarcian) Neuquén Basin, Argentina: U–Pb age calibration and its significance on the Early Jurassic evolution of southwestern Gondwana

New radiometric U–Pb ages obtained on zircon crystals from Early Jurassic ash layers found within beds of the Chachil Limestone at its type locality in the Chachil depocentre (southern Neuquén Basin) confirm a Pliensbachian age (186.0 ± 0.4 Ma). Additionally, two ash layers found in limestone beds in Chacay Melehue at the Cordillera del Viento depocentre (central Neuquén Basin) gave Early Pliensbachian (185.7 ± 0.4 Ma) and earliest Toarcian (182.3 ± 0.4 Ma) U–Pb zircon ages. Based on these new datings and regional geological observations, we propose that the limestones cropping out at Chacay Melehue are correlatable with the Chachil Limestone. Recent data by other authors from limestones at Serrucho creek in the upper Puesto Araya Formation (Valenciana depocentre, southern Mendoza) reveal ages of 182.16 ± 0.6 Ma. Based on these new evidences, we consider the Chachil Limestone an important Early Jurassic stratigraphic marker, representing an almost instantaneous widespread flooding episode in western Gondwana. The unit marks the initiation in the Neuquén Basin of the Cuyo Group, followed by widespread black shale deposition. Accordingly, these limestones can be regarded as the natural seal of the Late Triassic –earliest Jurassic Precuyano Cycle, which represents the infill of halfgrabens and/or grabens related to a strong extensional regime. Paleontological evidence supports that during Pliensbachian–earliest Toarcian times these limestones were deposited in western Gondwana in marine warm water environments.

A carbon isotopic and sedimentological record of the latest Devonian (Famennian) from the Western U.S. and Germany

New carbon isotopic data from upper Famennian deposits in the western United States reveal two previously unrecognized major positive isotopic excursions. The first is an abrupt ~ 3‰ positive excursion, herein referred to as ALFIE (A Late Famennian Isotopic Excursion), recorded in two sections of the Pinyon Peak Limestone of north-central Utah. Integration of detailed chemostratigraphic and biostratigraphic data suggests that ALFIE is the Laurentian record of the Dasberg Event, which has been linked to transgression in Europe and Morocco. Sedimentological data from the Chaffee Group of western Colorado also record transgression at a similar biostratigraphic position, with a shift from restricted to open-marine lithofacies. ALFIE is not evident in chemostratigraphic data from age-equivalent strata in Germany studied herein and in southern Europe, either because it is a uniquely North American phenomenon, or because the German sections are too condensed relative to those in Laurentia. A second positive carbon isotopic excursion from the upper Chaffee Group of Colorado is recorded in transgressive strata deposited directly above a previously unrecognized paleokarst interval. The age of this excursion, and the duration of the associated paleokarst hiatus, are not well constrained, although the events occurred sometime after the Late Famennian Middle expansa Zone. The high positive values recorded in this excursion are consistent with those associated with the youngest Famennian Middle to Late praesulcata Hangenberg Isotopic Excursion in Europe, the isotopic expression of the Hangenberg Event, which included mass extinction, widespread black shale deposition, and a glacio-eustatic fall and rise. If correct, this would considerably revise the age of the Upper Chaffee Group strata of western Colorado.

Geochemical evidence for major environmental change at the Devonian–Carboniferous boundary in the Carnic Alps and the Rhenish Massif

A positive carbon isotope excursion is reported for the global Hangenberg Event near the Devonian–Carboniferous boundary, one of the most significant Phanerozoic mass extinction events. The δ 13C excursion occurs both in micritic limestones and in sedimentary organic matter of black shales and limestones from different palaeogeographical regions, which were precisely correlated by conodont biostratigraphy. The excursion indicates global change in the isotopic composition of marine dissolved inorganic carbon and atmospheric CO 2. This resulted from the increased burial of organic matter by globally widespread deposition of black shales. The δ 18O values of conodont apatite indicate that globally widespread black shale deposition was preceded by increasing temperature, probably with a thermal gradient between equatorial and higher latitudes (∼ 20 °S). The main regressive interval of the event, correlated previously with a short-lived glacial episode in Gondwana, yielded no material for geochemical analyses, but low temperatures are recorded in overlying beds and increase again during the terminal Devonian. Early Carboniferous sea-surface temperatures were similar to those of the Late Devonian. This pattern of increased organic carbon burial, and changes in climate and sea level, is similar to that of several other extinction events of the Phanerozoic. It supports the hypothesis that increased organic carbon burial and oceanic anoxia can trigger mass extinctions, glaciations and eustatic sea-level change.

Late-Middle Ordovician Environmental Change: Molecular and Isotopic Evidence from North America

We recently reported inorganic and organic carbonisotope records for Caradocian units that crop out in central Pennsylvania (Patzkowsky et al., 1997). These data reveal a positive 3 %o excursion in the 13C content of micrites (~13CcARB) sampled across the P. undatus-P, tenuis boundary in Pennsylvania, and show the same magnitude of change observed in micrites by Ludvigson et al. (1996) in coeval core samples from Iowa. These findings confirm that the isotopic excursion extended across the North America, in both the Appalachian Basin and the midcontinental region. Both regions also record a positive excursion in the carbon-isotope composition of total organic matter (*13Cxoc). Data from the Iowa section show a +6 %0 excursion during this time (Hatch et al., 1987; Pancost, 1998), whereas ~13Cxo c data from our Pennsylvania samples show only +3.5 %0 change (Patzkowsky et al., 1997). We suggested these results indicate major changes in the carbon cycle accompanied by the lithologic changes noted above. In particular, the similarity in the timing and magnitude of the inorganic isotope excursions observed at both locations indicate an increase in organic carbon burial, possibly due to the widespread deposition of black shales in the foreland basin of the Taconic orogeny and elsewhere. The increased burial of organic matter during this time could have been accompanied by a marked decrease in the concentration of carbon dioxide in the ancient atmosphere. If so, it would have led to a decrease in the isotopic fractionation by marine algae, recorded by a decrease in the isotopic difference between inorganic and total organic carbon (A)13C = ~13CcARB-~13CToc). In both sections, values for A13C decrease beginning at the base of the P. tenuis zone (Patzkowsky et al., 1997), but the extent of change differs between the two locations. Specficially, the Iowa section records a slightly larger change (c. 4%o than in Pennsylvania (3%o). Thus A13C data suggest isotopic fractionation decreased at both sections, consistent with a drop in global atmospheric CO2 levels. However, the regional variation in the magnitude of change, and the coincident lithologic changes suggest the shift in A13C records that fractionation was driven, at least in part, by increased availability of nutrients (Laws et aL, 1995) and/or possible changes in the dominant phytoplankton taxa due to the pronounced change in oceanographic conditions. In this work, we examined biomarker distributions in the Iowa section, as well as an addition set of core samples from Ontario. Our specific goals were to determine if the inorganic and organic excursions are also recorded in the Canadian site to evaluate better the geographic extent of these signals. We hoped to use molecular evidence to evaluate if changes in either productivity or in the dominant phytoplankters can account for the regional differences in A13C. Further, we expected that biomarker distributions could reveal changes in mechanisms underlying the preservation and/or production of organic matter and possibly enhance our understanding of North American Caradocian palaeoceanography.

Models for the deposition of Mesozoic-Cenozoic fine-grained organic-carbon-rich sediment in the deep sea

Summary The widespread occurrence of organic-carbon-rich strata (‘black shales’) in certain portions of Jurassic, Cretaceous and Cenozoic sequences has been well-documented from Deep Sea Drilling Project sites in the Atlantic and Pacific Oceans and from sequences, now exposed on land, originally deposited in the Tethyan ocean. These ancient black shales usually have been explained by analogy with examples of modern deep-sea sediments in which organic matter locally is preserved by (1) increasing the supply of organic matter, (2) increasing the rate of sedimentation, and/or (3) decreasing the oxygen content of the bottom water. However, detailed examination of many black shales reveals characteristics that cannot be explained by simple local models, including: their approximate coincidence in time globally; their occurrence in a variety of different environments, including open oxygenated oceans, restricted basins, deep and shallow water; their interbedding with organic-carbonpoor strata which often dominate a so-called black shale sequence; their deposition by pelagic, hemipelagic, turbiditic and other processes; and the variations in type and amount of organic matter that occur even within the same sequence. A more complex model for the origin of black shales therefore appears most appropriate, in which the cyclic preservation of organic matter depends on the interplay of the three main variables, namely supply of organic matter, sedimentation rate, and deep-water oxygenation, each of which varies independently to some extent. The variation and relative importance of these parameters in individual basins and widespread black shale deposition in general are linked globally and temporally by changes in global sea-level, climate and related changes in oceanic circulation. An important and often overlooked factor for the supply of organic matter to deep-basin sediments is the frequency and magnitude of redepositional processes. The interplay of these variables is discussed in relation to the middle Cretaceous and Cenozoic organic-carbon-rich strata, in particular, which show marked differences in the relative importance of the different variables.