Clemens V. Ullmann

Onset of main Phanerozoic marine radiation sparked by emerging Mid Ordovician icehouse

The Great Ordovician Biodiversification Event (GOBE) was the most rapid and sustained increase in marine Phanerozoic biodiversity. What generated this biotic response across Palaeozoic seascapes is a matter of debate; several intrinsic and extrinsic drivers have been suggested. One is Ordovician climate, which in recent years has undergone a paradigm shift from a text-book example of an extended greenhouse to an interval with transient cooling intervals – at least during the Late Ordovician. Here, we show the first unambiguous evidence for a sudden Mid Ordovician icehouse, comparable in magnitude to the Quaternary glaciations. We further demonstrate the initiation of this icehouse to coincide with the onset of the GOBE. This finding is based on both abiotic and biotic proxies obtained from the most comprehensive geochemical and palaeobiological dataset yet collected through this interval. We argue that the icehouse conditions increased latitudinal and bathymetrical temperature and oxygen gradients initiating an Early Palaeozoic Great Ocean Conveyor Belt. This fuelled the GOBE, as upwelling zones created new ecospace for the primary producers. A subsequent rise in δ13C ratios known as the Middle Darriwilian Isotopic Carbon Excursion (MDICE) may reflect a global response to increased bioproductivity encouraged by the onset of the GOBE.

Effect of a Jurassic oceanic anoxic event on belemnite ecology and evolution

Significance The Toarcian oceanic anoxic event (OAE; ∼183 million y ago) is marked by one of the largest carbon cycle perturbations in Earth history, rapid climate change, widespread ocean oxygen deficiency, and strong changes in marine ecosystems. The temporal links between increasing atmospheric pCO2, changes in ocean oxygen availability, and marine biotic response during this event are still poorly understood. Here we use isotopic analyses of calcite and organic matter from belemnites, marine predators of that time, to address their response to bottom water anoxia during the OAE. We infer that some belemnite taxa showed resilience to a strong reduction in ocean oxygen availability and occupied ecological niches in the Cleveland Basin (United Kingdom), enabling a strong evolutionary diversification after the event. The Toarcian oceanic anoxic event (T-OAE; ∼183 million y ago) is possibly the most extreme episode of widespread ocean oxygen deficiency in the Phanerozoic, coinciding with rapid atmospheric pCO2 increase and significant loss of biodiversity in marine faunas. The event is a unique past tipping point in the Earth system, where rapid and massive release of isotopically light carbon led to a major perturbation in the global carbon cycle as recorded in organic and inorganic C isotope records. Modern marine ecosystems are projected to experience major loss in biodiversity in response to enhanced ocean anoxia driven by anthropogenic release of greenhouse gases. Potential consequences of this anthropogenic forcing can be approximated by studying analog environmental perturbations in the past such as the T-OAE. Here we present to our knowledge the first organic carbon isotope record derived from the organic matrix in the calcite rostra of early Toarcian belemnites. We combine both organic and calcite carbon isotope analyses of individual specimens of these marine predators to obtain a refined reconstruction of the early Toarcian global exogenic carbon cycle perturbation and belemnite paleoecology. The organic carbon isotope data combined with measurements of oxygen isotope values from the same specimens allow for a more robust interpretation of the interplay between the global carbon cycle perturbation, environmental change, and biotic response during the T-OAE. We infer that belemnites adapted to environmental change by shifting their habitat from cold bottom waters to warm surface waters in response to expanded seafloor anoxia.

Tectonic Forcing of Early to Middle Jurassic seawater Sr/Ca

The Jurassic Period (ca. 201–145 Ma) is marked by fundamental reorganizations of paleogeography, paleoceanography, ecosystems, and the progressive shift from aragonite to calcite as the favored marine biogenic carbonate polymorph. Sr/Ca ratios of well-preserved Jurassic oysters and belemnites from sections in the UK and Poland demonstrate that the Sr/Ca ratio of seawater varied systematically throughout the Early and Middle Jurassic in parallel with already documented seawater 87 Sr/ 86 Sr. The Sr flux from increased mid-ocean ridge activity in the Early Jurassic outbalanced the input of riverine Sr, leading to gradually lower seawater 87 Sr/ 86 Sr associated with the parallel and strong decrease in seawater Sr/Ca ratios. This downward trend was reversed by enhanced continental input in the Toarcian and Aalenian, but resumed in the Bajocian and continued to the Callovian. Parallel changes of seawater 87 Sr/ 86 Sr and Sr/Ca suggest a common cause for these long-term variations and are best explained by changes in the balance of continental weathering and hydrothermal fluxes. These findings underline the strong control of global tectonic processes on the evolution of biomineralization and downplay the role of biomineral evolution in influencing strontium chemistry of seawater in the mid-Mesozoic.

Interlaboratory comparison of magnesium isotopic compositions of 12 felsic to ultramafic igneous rock standards analyzed by MC-ICPMS

To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3‰ in 26Mg/24Mg, >4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.

Fungal decomposition of terrestrial organic matter accelerated Early Jurassic climate warming

Soils – constituting the largest terrestrial carbon pool - are vulnerable to climatic warming. Currently existing uncertainties regarding carbon fluxes within terrestrial systems can be addressed by studies of past carbon cycle dynamics and related climate change recorded in sedimentary successions. Here we show an example from the Early Jurassic (early Toarcian, c. 183 mya) marginal-marine strata from Poland, tracking the hinterland response to climatic changes through a super-greenhouse event. In contrast to anoxia-related enhanced carbon storage in coeval open marine environments, Total Organic Carbon (TOC) concentrations in the Polish successions are substantially reduced during this event. Increasing temperature favoured fungal-mediated decomposition of plant litter – specifically of normally resistant woody tissues. The associated injection of oxidized organic matter into the atmosphere corresponds to abrupt changes in standing vegetation and may have contributed significantly to the amplified greenhouse climate on Earth. The characteristic Toarcian signature of multiple warm pulses coinciding with rapidly decreasing carbon isotope ratios may in part be the result of a radical reduction of the terrestrial carbon pool as a response to climate change.

Subaerial speleothems and deep karst in central Sweden linked to Hirnantian glaciations

The limestones of the upper Katian Boda mud mounds (Ordovician) of the Siljan district in central Sweden are deeply fractured. The fissures were partly synsedimentary and are often lined with stromatolite-like crusts. These crusts thus far are the only known subaerial Ordovician speleothems. They reach depths of up to 30 m below the former mound top. Macroscopically the crusts form decimetre-sized, cone-shaped domal aggregates, stalactites and stalagmites. Microfabric and morphology identify them as microbially mediated speleothems in a dark environment. Combined Sr and C isotope values indicate a formation of the speleothems from meteoric waters without influence of a significant soil horizon. For the first time the age of the speleothems can be precisely constrained by δ13C whole-rock and brachiopod shell isotope data to the mid-Hirnantian. Repeated and/or prolonged subaerial exposure of the Boda mud mounds during the Hirnantian is evident from karst surfaces and early cements in the mound capping carbonates. The speleothems and the karst surfaces record an estimated sea-level fall in the range of 80–130 m within the time window of the Hirnantian Isotopic Carbon Excursion. This massive regression coincides with maximum ice sheet extent inferred from sections in West Gondwana. Supplementary material: 87Sr/86Sr isotope ratio of selected brachiopod shells and results of Energy-dispersive-X-ray spectroscopy are available from http://www.geolsoc.org.uk/SUP18809

Crystallographic control on lithium isotope fractionation in Archean to Cenozoic lithium-cesium-tantalum pegmatites

The age distribution of LCT pegmatites largely overlaps with major phases of collisional orogenic events and assembly of super-continents. Some of the largest known LCT pegmatite deposits formed in very short intervals, 2.7-2.5 and 1.9-1.8 billion years ago (Ga), corresponding to two major pulses of continental crust growth. However, the exact process of generation and segregation of large volumes of Li-bearing pegmatite liquids, perhaps involving disequilibrium fractional crystallization and leaving residual melts enriched in fluxing elements such as B, F, H2O, Li, and P, remains largely obscure. The new data on Li contents and isotope compositions in major mineral phases from temporally and geographically separated pegmatite bodies document extreme variations in d7Li values among individual large LCT pegmatites, in particular Archean occurrences. The observed >10‰ variations in d7Li values for the same mineral phases from different localities (i.e., beryl, petalite, spodumene, lepidolite, amblygonite, muscovite) contrast with globally homogeneous Li isotope systematics of major mineral phases from unmodified mantle rocks. Consistent Li isotope offsets between coexisting mineral phases are best explained by Li isotope fractionation as a function of the bond length between Li and neighboring ions (O, OH, F). We suggest that spatially distinct Li isotope patterns act as fingerprints for different pegmatites and can be explained by the pre-existing Li isotope differences of their crustal sources at the time of pegmatite formation owing to differences in crustal age and evolution. This would imply secular evolution of the continental crust over Earth history toward present-day globally broadly uniform crustal 7Li/6Li ratios (d7Li ~0‰). The differences among Archean occurrences could reflect possible Archean paleogeography and perhaps be linked with different thermal regimes of individual cratons as a consequence of variations in crustal thickness.

Permian strontium isotope stratigraphy

Abstract The secular evolution of the Permian seawater 87Sr/86Sr ratios carries information about global tectonic processes, palaeoclimate and palaeoenvironments, such as occurred during the Early Permian deglaciation, the formation of Pangaea and the Permian–Triassic (P–Tr) mass extinction. Besides this application for discovering geological aspects of Earth history, the marine 87Sr/86Sr curve can also be used for robust correlations when other bio-, litho- and/or chemostratigraphic markers are inadequate. The accuracy of marine 87Sr/86Sr reconstructions, however, depends on high-quality age control of the reference data, and on sample preservation, both of which generally deteriorate with the age of the studied interval. The first-order Permian seawater 87Sr/86Sr trend shows a monotonous decline from approximately 0.7080 in the earliest Permian (Asselian) to approximately 0.7069 in the latest Guadalupian (Capitanian), followed by a steepening increase from the latest Guadalupian towards the P–Tr boundary (c. 0.7071–0.7072) and into the Early Triassic. Various higher-order changes in slope of the Permian 87Sr/86Sr curve are indicated, but cannot currently be verified owing to a lack of sample coverage and significant disagreement of published 87Sr/86Sr records.

Geochemical signatures in Late Triassic brachiopods from New Caledonia

Brachiopod fossils from the sedimentary sequences of the Téremba Terrane (New Caledonia) provide a unique opportunity to study the environmental parameters of the Late Triassic. 87Sr/86Sr ratios, δ13C and δ18O values, and Sr/Ca, Mg/Ca and Mn/Ca ratios were measured on brachiopods from Oretian to Otapirian (Norian to Rhaetian) fossil localities of the Baie de St.-Vincent area. Post-depositional impacts on the geochemical proxies were investigated by analysing calcite cements and partly recrystallized shell material. Diagenetic fluids carried strontium with a low 87Sr/86Sr ratio of c. 0.7065, and light δ13C values of c. −20‰, suggesting major contributions by oxidized organic matter. Diagenetic equilibrium was reached at δ18O values of c. −12‰, very low Sr/Ca ratios of < 0.05 mmol/mol and locally variable Mn/Ca ratios of up to 5.9 mmol/mol. Results from the best-preserved samples suggest that calcification temperatures of Warepan and Otapirian brachiopods from New Caledonia were consistently ≥ 15 °C.

Coral-based climate records from tropical South Atlantic: 2009/2010 ENSO event in C and O isotopes from Porites corals (Rocas Atoll, Brazil)

Coral skeletons contain records of past environmental conditions due to their long life span and well calibrated geochemical signatures. C and O isotope records of corals are especially interesting, because they can highlight multidecadal variability of local climate conditions beyond the instrumental record, with high fidelity and sub-annual resolution. Although, in order to get an optimal geochemical signal in coral skeleton, sampling strategies must be followed. Here we report one of the first coral-based isotopic record from the Equatorial South Atlantic from two colonies of Porites astreoides from the Rocas Atoll (offshore Brazil), a new location for climate reconstruction. We present time series of isotopic variation from profiles along the corallite valley of one colony and the apex of the corallite fan of the other colony. Significant differences in the isotopic values between the two colonies are observed, yet both record the 2009/2010 El Niño event - a period of widespread coral bleaching - as anomalously negative δ18O values (up to -1 permil). δ13C is found to be measurably affected by the El Niño event in one colony, by more positive values (+0.39 ‰), and together with a bloom of endolithic algae, may indicate physiological alteration of this colony. Our findings indicate that corals from the Rocas Atoll can be used for monitoring climate oscillations in the tropical South Atlantic Ocean.