Seth A. Young

Geochemical evidence for widespread euxinia in the Later Cambrian ocean

Widespread anoxia in the ocean is frequently invoked as a primary driver of mass extinction as well as a long-term inhibitor of evolutionary radiation on early Earth. In recent biogeochemical studies it has been hypothesized that oxygen deficiency was widespread in subsurface water masses of later Cambrian oceans, possibly influencing evolutionary events during this time. Physical evidence of widespread anoxia in Cambrian oceans has remained elusive and thus its potential relationship to the palaeontological record remains largely unexplored. Here we present sulphur isotope records from six globally distributed stratigraphic sections of later Cambrian marine rocks (about 499 million years old). We find a positive sulphur isotope excursion in phase with the Steptoean Positive Carbon Isotope Excursion (SPICE), a large and rapid excursion in the marine carbon isotope record, which is thought to be indicative of a global carbon cycle perturbation. Numerical box modelling of the paired carbon sulphur isotope data indicates that these isotope shifts reflect transient increases in the burial of organic carbon and pyrite sulphur in sediments deposited under large-scale anoxic and sulphidic (euxinic) conditions. Independently, molybdenum abundances in a coeval black shale point convincingly to the transient spread of anoxia. These results identify the SPICE interval as the best characterized ocean anoxic event in the pre-Mesozoic ocean and an extreme example of oxygen deficiency in the later Cambrian ocean. Thus, a redox structure similar to those in Proterozoic oceans may have persisted or returned in the oceans of the early Phanerozoic eon. Indeed, the environmental challenges presented by widespread anoxia may have been a prevalent if not dominant influence on animal evolution in Cambrian oceans.

Long-lived glaciation in the Late Ordovician? Isotopic and sequence-stratigraphic evidence from western Laurentia

The timing and causes of the transition to an icehouse climate in the Late Ordovician are controversial. Results of an integrated δ13C and sequence stratigraphic analysis in Nevada show that in the Late Ordovician Chatfieldian Stage (mid-Caradoc) a positive δ13C excursion in the upper part of the Copenhagen Formation was closely followed by a regressive event evidenced within the prominent Eureka Quartzite. The Chatfieldian δ13C excursion is known globally and interpreted to record enhanced organic carbon burial, which lowered atmospheric p CO2 to levels near the threshold for ice buildup in the Ordovician greenhouse climate. The subsequent regressive event in central Nevada, previously interpreted as part of a regional tectonic adjustment, is here attributed in part to sea-level drawdown from the initiation of continental glaciation on Gondwana. This drop in sea level—which may have contributed to further cooling through a reduction in poleward heat transport and a lowering of p CO2 by suppressing shelf-carbonate production—signals the transition to a Late Ordovician icehouse climate ∼10 m.y. before the widespread Hirnantian glacial maximum at the end of the Ordovician.

Microbial life at −13 °C in the brine of an ice-sealed Antarctic lake

The permanent ice cover of Lake Vida (Antarctica) encapsulates an extreme cryogenic brine ecosystem (−13 °C; salinity, 200). This aphotic ecosystem is anoxic and consists of a slightly acidic (pH 6.2) sodium chloride-dominated brine. Expeditions in 2005 and 2010 were conducted to investigate the biogeochemistry of Lake Vida’s brine system. A phylogenetically diverse and metabolically active Bacteria dominated microbial assemblage was observed in the brine. These bacteria live under very high levels of reduced metals, ammonia, molecular hydrogen (H2), and dissolved organic carbon, as well as high concentrations of oxidized species of nitrogen (i.e., supersaturated nitrous oxide and ∼1 mmol⋅L−1 nitrate) and sulfur (as sulfate). The existence of this system, with active biota, and a suite of reduced as well as oxidized compounds, is unusual given the millennial scale of its isolation from external sources of energy. The geochemistry of the brine suggests that abiotic brine-rock reactions may occur in this system and that the rich sources of dissolved electron acceptors prevent sulfate reduction and methanogenesis from being energetically favorable. The discovery of this ecosystem and the in situ biotic and abiotic processes occurring at low temperature provides a tractable system to study habitability of isolated terrestrial cryoenvironments (e.g., permafrost cryopegs and subglacial ecosystems), and is a potential analog for habitats on other icy worlds where water-rock reactions may cooccur with saline deposits and subsurface oceans.

Pulse of atmospheric oxygen during the late Cambrian

A rise in atmospheric O2 has been linked to the Cambrian explosion of life. For the plankton and animal radiation that began some 40 million yr later and continued through much of the Ordovician (Great Ordovician Biodiversification Event), the search for an environmental trigger(s) has remained elusive. Here we present a carbon and sulfur isotope mass balance model for the latest Cambrian time interval spanning the globally recognized Steptoean Positive Carbon Isotope Excursion (SPICE) that indicates a major increase in atmospheric O2. We estimate that this organic carbon and pyrite burial event added approximately 19 × 1018 moles of O2 to the atmosphere (i.e., equal to change from an initial starting point for O2 between 10–18% to a peak of 20–28% O2) beginning at approximately 500 million years. We further report on new paired carbon isotope results from carbonate and organic matter through the SPICE in North America, Australia, and China that reveal an approximately 2‰ increase in biological fractionation, also consistent with a major increase in atmospheric O2. The SPICE is followed by an increase in plankton diversity that may relate to changes in macro- and micronutrient abundances in increasingly oxic marine environments, representing a critical initial step in the trophic chain. Ecologically diverse plankton groups could provide new food sources for an animal biota expanding into progressively more ventilated marine habitats during the Ordovician, ultimately establishing complex ecosystems that are a hallmark of the Great Ordovician Biodiversification Event.

A major drop in seawater 87Sr/86Sr during the Middle Ordovician (Darriwilian): Links to volcanism and climate?

A large drop in seawater 87 Sr/ 86 Sr during the Middle Ordovician was among the most rapid in the entire Phanerozoic. New 87 Sr/ 86 Sr measurements from Nevada indicate that the rapid shift began in the Pygodus serra conodont zone of the upper Darriwilian Stage. We use a numerical model to explore the hypothesis that volcanic weathering provided the flux of nonradiogenic Sr to the oceans. A close balance between volcanic outgassing and CO 2 consumption from weathering produced steady p CO 2 levels and climate through the middle Katian, consistent with recent Ordovician paleotemperature estimates. In the late Katian, outgassing was reduced while volcanic weathering continued, and resulted in a cooling episode leading into the well-known end-Ordovician glaciation.

Hirnantian (latest Ordovician) delta C-13 chemostratigraphy in southern Sweden and globally: a refined integration with the graptolite and conodont zone successions

The δ13Corg chemostratigraphy of the Hirnantian and lower Rhuddanian in the biostratigraphically well-controlled Röstånga-1 drillcore from west-central Scania is used for an improved integration of the Hirnantian Isotope Carbon Excursion (HICE) with the standard graptolite zonation. In this drillcore succession, the end of the HICE corresponds to the top of the range of Metabolograptus persculptus. Baseline δ13Corg values occur in the uppermost Hirnantian Avitograptus avitus Faunal Interval as well as in the Rhuddanian Akidograptus ascensus Zone, and the isotope curve is also tied to the Swedish uppermost Katian and Hirnantian trilobite zonation. Chemostratigraphic data from sections in Västergötland confirm that the beginning of the HICE is at, or very close to, the base of the Skultorp Member of the Loka Formation. The biostratigraphically less precisely controlled end of the HICE is at least locally in the Upper Member of the same formation. The graptolite biostratigraphy in the Mt. Kinnekulle succession indicates that the lowermost Kallholn Formation, which has long been known as the Leonaspis (formerly Acidaspis) Shale, is of Hirnantian rather than earliest Silurian age which is consistent with the age of the lowermost Kallholn Formation in the Röstånga-1 drillcore. Comparisons with Hirnantian sections in the United Kingdom, North America and China make it possible to improve the calibration of the HICE with conodont and graptolite biostratigraphy and confirm the usefulness of δ13Corg chemostratigraphy for detailed correlations. The upper Katian carbon chemostratigraphy in key sections in North America and eastern Baltoscandia indicates that the Elkhorn and Paroveja excursions are the same. Available data are used for a new Hirnantian eustasy-climate-faunal evolution model.

Lower Katian (Upper Ordovician) delta(13)C chemostratigraphy, global correlation and sea-level changes in Baltoscandia

A long-standing problem in the Ordovician stratigraphy of south-eastern Norway has been to the relations between the Mjøsa Formation in the Lake Mjøsa region and coeval strata in the Oslo region. The recent discovery of the globally distributed Guttenberg δ13C excursion (Guttenberg Isotopic Carbon Excursion) in the Mjøsa region provided the impetus to search for this excellent chemostratigraphic marker in the classical Oslo region succession, where it was found in the Frognerkilen Formation. Another positive δ13C excursion, which we identify as the Kope excursion, was discovered in the Solvang Formation. The new data show that the lower Katian δ13C chemostratigraphy in the Oslo region is closely similar to that from south-eastern and southern Estonia. This permits detailed correlations across Baltoscandia, which are useful for recognising the Baltic stage boundaries in the Oslo region succession. Both the Lake Mjøsa and Oslo regions study successions can be chemostratigraphically correlated with those in North America and eastern Asia. The newly established stratigraphic relations in the Oslo region are also used for a re-assessment of lower Katian local and eustatic sea-level changes.

Strontium isotope (87Sr/86Sr) stratigraphy of Ordovician bulk carbonate: Implications for preservation of primary seawater values

The present study on bulk carbonate 87 Sr/ 86 Sr stratigraphy represents a companion work to earlier research that presented a conodont apatite-based Ordovician seawater 87 Sr/ 86 Sr curve for the Tremadocian–Katian Stages (485–445 Ma). Here, we directly compare the curve based on conodont apatite (including some new data not published in earlier work) with a new curve based on 87 Sr/ 86 Sr results from bulk carbonate from the Tremadocian–Sandbian Stages. We sampled eight Lower to Upper Ordovician carbonate successions in North America to assess the reliability of bulk carbonate to preserve seawater 87 Sr/ 86 Sr and its utility for 87 Sr/ 86 Sr chemostratigraphy. A high-resolution 87 Sr/ 86 Sr curve based on 137 measurements of bulk conodont apatite is used as a proxy for seawater 87 Sr/ 86 Sr ( 87 Sr/ 86 Sr seawater ). In total, 230 bulk carbonate samples that are paired to conodont samples were measured for 87 Sr/ 86 Sr in order to determine the conditions under which 87 Sr/ 86 Sr seawater is preserved in bulk carbonate. Results indicate that well-preserved bulk carbonate can faithfully record the 87 Sr/ 86 Sr seawater trend, but that its 87 Sr/ 86 Sr values are commonly more variable than those of conodont apatite. On average, bulk carbonate samples of the same age vary by 10–20 × 10 −5 , compared to 5–10 × 10 −5 for conodont apatite. The amount of isotopic alteration of bulk carbonate from seawater 87 Sr/ 86 Sr (Δ 87 Sr/ 86 Sr) was determined by taking the difference between 87 Sr/ 86 Sr values of bulk carbonate and the approximated seawater trend based on the least radiogenic conodont 87 Sr/ 86 Sr values. Cross plots comparing Δ 87 Sr/ 86 Sr values to bulk carbonate Sr concentration ([Sr]) and conodont color alteration indices (CAI; an estimate of the thermal history of a rock body) indicate that bulk carbonate is most likely to preserve 87 Sr/ 86 Sr seawater (minimally altered) when either: (1) bulk carbonate [Sr] is greater than 300 ppm, or (2) carbonate rocks experienced minimal thermal alteration, with burial temperatures less than ~150 °C. Carbonates with intermediate [Sr] (e.g., between 130 and 300 ppm) can also yield 87 Sr/ 86 Sr seawater values, but results are less predictable, and local diagenetic conditions may play a greater role. Modeling results support the argument that seawater 87 Sr/ 86 Sr can be preserved in bulk carbonates with low [Sr] if pore water:rock ratios are low ( 87 Sr/ 86 Sr is similar to the seawater 87 Sr/ 86 Sr value preserved in limestone. Bulk carbonate samples that meet these criteria can be useful for high-resolution measurements of 87 Sr/ 86 Sr seawater , with a sample variation on par with fossil materials ( −5 ), particularly for successions where well-preserved fossil material (i.e., conodonts or brachiopods) is not available, such as Precambrian strata, sequences recording mass extinction events, or otherwise fossil-barren facies. These criteria and model predictions based on bulk carbonate [Sr] must be considered in the context of whether a limestone accumulated under calcite seas (e.g., Ordovician), with relatively high seawater Sr/Ca, or aragonite seas, in which case the diagenetic transformation of aragonite to calcite may result in incorporation of non-seawater Sr.

Conodont biostratigraphy, and delta C-13 and delta S-34 isotope chemostratigraphy, of the uppermost Ordovician and Lower Silurian at Osmundsberget, Dalarna, Sweden

The previously established graptolite and chitinozoan Hirnanian-Telychian biostratigraphy in the unique Osmundsberget North outcrop in the Siljan region, south-central Sweden, is integrated with new conodont biostratigraphy and δ13Corg, δ13Ccarb and δ34Spyr chemostratigraphy. At this locality, the middle Hirnantian (latest Ordovician) topmost part of the Boda Limestone is overlain by the latest Hirnantian Glisstjärn Formation, and the late Aeronian–early Telychian (Llandovery) Kallholn Formation rests unconformably on the Glisstjärn Formation. Previous conodont work showed that the Glisstjärn Formation belongs to the lower Ozarkodina hassi Zone. New samples from calcareous interbeds in the dominantly shaly Kallholn Formation, some of which contain hundreds of condont elements, yielded Distomodus staurognathoides, Aspelundia fluegeli and other taxa indicating the D. staurognathoides Zone. In the East Baltic succession, the coeval interval, which is in the uppermost Raikküla–lowermost Adavere stages just below the geographically widespread Osmundsberg K-bentonite, has yielded a conodont fauna similar to that of the lower Kallholn Formation. A regional review of the D. staurognathoides Zone shows that there are possible equivalents to our study interval also in Norway and the Welsh Borderland, but equivalent strata are missing in large parts of North America, or have not produced diagnostic conodonts. The δ13Corg values from the study section are relatively uniform (mostly ranging between − 29‰ and − 30‰), and the late Aeronian and Valgu positive excursions have not been recognized.

Iron cycling in the anoxic cryo-ecosystem of Antarctic Lake Vida

Iron redox cycling in metal-rich, hypersaline, anoxic brines plays a central role in the biogeochemical evolution of life on Earth, and similar brines with the potential to harbor life are thought to exist elsewhere in the solar system. To investigate iron biogeochemical cycling in a terrestrial analog we determined the iron redox chemistry and isotopic signatures in the cryoencapsulated liquid brines found in frozen Lake Vida, East Antarctica. We used both in situ voltammetry and the spectrophotometric ferrozine method to determine iron speciation in Lake Vida brine (LVBr). Our results show that iron speciation in the anoxic LVBr was, unexpectedly, not free Fe(II). Iron isotope analysis revealed highly depleted values of −2.5‰ for the ferric iron of LVBr that are similar to iron isotopic signatures of Fe(II) produced by dissimilatory iron reduction. The presence of Fe(III) in LVBr therefore indicates dynamic iron redox cycling beyond iron reduction. Furthermore, extremely low δ18O–SO42− values (−9.7‰) support microbial iron-sulfur cycling reactions. In combination with evidence for chemodenitrification resulting in iron oxidation, we conclude that coupled abiotic and biotic redox reactions are driving the iron cycle in Lake Vida brine. Our findings challenge the current state of knowledge of anoxic brine chemistry and may serve as an analogue for icy brines found in the outer reaches of the solar system.