Assessing bulk carbonates as archives for seawater Li isotope ratios

Silicate weathering is a primary control on the carbon cycle and therefore long-term climate. Tracing silicate weathering in the geological record has been a challenge for decades, with a number of proxies proposed and their limits determined. Recently lithium isotopes in marine carbonates have emerged as a potential tracer. Bulk carbonates are increasingly being used as a Li isotope archive, though with limited tests thus far of the robustness of this approach in the modern ocean. As the bulk composition of marine pelagic carbonates has changed through time and geographically, assessing the fidelity of bulk carbonate as proxy carrier is fundamental. To address the impact of compositional variability in bulk carbonate on Li isotopes, we examine 27 Bahamian aragonitic bulk carbonates and 16 Atlantic largely calcitic core-top sediment samples. Two core-tops only have trace (<10 %) carbonate, and are analysed to test whether carbonates in such sections are still a viable archive. We selectively extract the exchangeable and carbonate fractions from the core-top samples. The exchangeable fraction contains ∼2 % of the total Li and has a fairly constant offset from seawater of 16.5 ± 0.8‰. When leaching silicate-containing carbonates, acetic acid buffered with sodium acetate appears a more robust method of solely attacking carbonates compared to dilute HCl, which may also liberate some silicate-bound Li. Carbonates from samples that do not contain aragonite have the isotopic fractionation of seawater of Δ7Liseawater-calcite = 6.1 ± 1.3‰ (2sd), which is not affected by latitude or the water depth the sample was deposited at. The pure aragonite bulk carbonates from the Bahamas have a fractionation of Δ7Liseawater-aragonite = 9.6 ± 0.6‰. A sediment sample from the Galician coast that mostly consists of quartz is highly offset from seawater by ∼20‰ and also has relatively high Li/Ca ratios. These high values are not due to leaching of silicate material directly (Al/Ca ratios are low). We interpret this addition via cation exchange of Li from silicate during recrystallisation. Overall bulk carbonates from the open ocean are a reliable archive of seawater δ7Li, but care must be taken with carbonate mineralogy and low-carbonate samples. Overall, therefore, any examination of the palaeo-seawater δ7Li record must be reproduced in different global settings (e.g. multiple global cores) before it can be considered robust

Publisher Correction: Enhanced clay formation key in sustaining the Middle Eocene Climatic Optimum (Nature Geoscience, (2023), 16, 8, (730-738), 10.1038/s41561-023-01234-y)

Correction to: Nature Geoscience, published online 31 July 2023. In the version of the article originally published, a reference was missing from the seventh paragraph of the “A global shift towards enhanced clay formation” section and the first paragraph of the “Further information on the successful model Scenario 8” section (in the latter instance, the reference is cited in the added text “although a global reorganisation of the silicon cycle may have also played a part”). The reference—Dunlea, A. G. et al. Cenozoic global cooling and increased seawater Mg/Ca via reduced reverse weathering. Nat. Commun. 8, 844 (2017)—has now been inserted as new ref. 54. In the “Data treatment and availability section”, the isotopic data, which can be found in the Figshare data repository at , were incorrectly said to be found in the PANGAEA data repository. These corrections have been made in the HTML and PDF versions of the article

Enhanced clay formation key in sustaining the Middle Eocene Climatic Optimum

The Middle Eocene Climatic Optimum (around 40 million years ago) was a roughly 400,000-year-long global warming phase associated with an increase in atmospheric CO2 concentrations and deep-ocean acidifcation that interrupted the Eocene’s long-term cooling trend. The unusually long duration, compared with early Eocene global warming phases, is puzzling as temperature-dependent silicate weathering should have provided a negative feedback, drawing down CO2 over this timescale. Here we investigate silicate weathering during this climate warming event by measuring lithium isotope ratios (reported as δ7 Li), which are a tracer for silicate weathering processes, from a suite of open-ocean carbonate-rich sediments. We fnd a positive δ7 Li excursion—the only one identifed for a warming event so far —of ~3‰. Box model simulations support this signal to refect a global shift from congruent weathering, with secondary mineral dissolution, to incongruent weathering, with secondary mineral formation. We surmise that, before the climatic optimum, there was considerable soil shielding of the continents. An increase in continental volcanism initiated the warming event, but it was sustained by an increase in clay formation, which sequestered carbonate-forming cations, short-circuiting the carbonate–silicate cycle. Clay mineral dynamics may play an important role in the carbon cycle for climatic events occurring over intermediate (i.e., 100,000 year) timeframes

Enhanced clay formation key in sustaining the Middle Eocene Climatic Optimum

The Middle Eocene Climatic Optimum (around 40 million years ago) was a roughly 400,000-year-long global warming phase associated with an increase in atmospheric CO2 concentrations and deep-ocean acidification that interrupted the Eocene’s long-term cooling trend. The unusually long duration, compared with early Eocene global warming phases, is puzzling as temperature-dependent silicate weathering should have provided a negative feedback, drawing down CO2 over this timescale. Here we investigate silicate weathering during this climate warming event by measuring lithium isotope ratios (reported as δ7Li), which are a tracer for silicate weathering processes, from a suite of open-ocean carbonate-rich sediments. We find a positive δ7Li excursion—the only one identified for a warming event so far —of ~3‰. Box model simulations support this signal to reflect a global shift from congruent weathering, with secondary mineral dissolution, to incongruent weathering, with secondary mineral formation. We surmise that, before the climatic optimum, there was considerable soil shielding of the continents. An increase in continental volcanism initiated the warming event, but it was sustained by an increase in clay formation, which sequestered carbonate-forming cations, short-circuiting the carbonate–silicate cycle. Clay mineral dynamics may play an important role in the carbon cycle for climatic events occurring over intermediate (i.e., 100,000 year) timeframes

Lithium-isotope evidence for enhanced silicate weathering during OAE 1a (Early Aptian Selli event)

An abrupt rise in temperature, forced by a massive input of CO2 into the atmosphere, is commonly invoked as the main trigger for Oceanic Anoxic Events (OAEs). Global warming initiated a cascade of palaeoenvironmental perturbations starting with increased continental weathering and an accelerated hydrological cycle that delivered higher loads of nutrients to coastal areas, stimulating biological productivity. The end-result was widespread anoxia and deposition of black shales: the hallmarks of OAEs. In order to assess the role of weathering as both an OAE initiator and terminator (via CO2 sequestration) during the Early Aptian OAE 1a (Selli Event, ∼120 Ma) the isotopic ratio of lithium isotopes was analysed in three sections of shallow-marine carbonates from the Pacific and Tethyan realms and one basinal pelagic section from the Tethyan domain. Because the isotopic composition of lithium in seawater is largely controlled by continental silicate weathering and high- and low-temperature alteration of basaltic material, a shift to lighter δ7Li values is expected to characterize OAEs. The studied sections illustrate this phenomenon: δ7Li values decrease to a minimum coincident with the negative carbon-isotope excursion that effectively records the onset of OAE 1a. A second negative δ7Li excursion occurs coeval with the minimum in strontium isotopes after the event. The striking similarity to the strontium-isotope record argues for a common driver. The formation and destruction (weathering) of an oceanic LIP could account for the parallel trend in both isotope systems. The double-spike in lithium isotopes is probably related to a change in weathering congruencies. Such a chemostratigraphy is consistent with the hypothesis that an increase in silicate weathering, in conjunction with organic-carbon burial, led to drawdown of atmospheric CO2 during the early Aptian OAE 1a

The dissolution of olivine added to soil: Implications for enhanced weathering

Chemical weathering of silicate minerals consumes atmospheric CO2 and is a fundamental component of geochemical cycles and of the climate system on long timescales. Artificial acceleration of such weathering (“enhanced weathering”) has recently been proposed as a method of mitigating anthropogenic climate change, by adding fine-grained silicate materials to continental surfaces. The efficacy of such intervention in the carbon cycle strongly depends on the mineral dissolution rates that occur, but these rates remain uncertain. Dissolution rates determined from catchment scale investigations are generally several orders of magnitude slower than those predicted from kinetic information derived from laboratory studies. Here we present results from laboratory flow-through dissolution experiments which seek to bridge this observational discrepancy by using columns of soil returned to the laboratory from a field site. We constrain the dissolution rate of olivine added to the top of one of these columns, while maintaining much of the complexity inherent in the soil environment. Continual addition of water to the top of the soil columns, and analysis of elemental composition of waters exiting at the base was conducted for a period of five months, and the solid and leachable composition of the soils was also assessed before and after the experiments. Chemical results indicate clear release of Mg2+ from the dissolution of olivine and, by comparison with a control case, allow the rate of olivine dissolution to be estimated between 10−16.4 and 10−15.5 moles(Mg) cm−2 s−1. Measurements also allow secondary mineral formation in the soil to be assessed, and suggest that no significant secondary uptake of Mg2+ has occurred. The olivine dissolution rates are intermediate between those of pure laboratory and field studies and provide a useful constraint on weathering processes in natural environments, such as during soil profile deepening or the addition of mineral dust or volcanic ash to soils surfaces. The dissolution rates also provide critical information for the assessment of enhanced weathering including the expected surface-area and energy requirements

Evidence for weathering and volcanism during the PETM from Arctic Ocean and Peri-Tethys osmium isotope records

Sudden global warming during the Paleocene–Eocene Thermal Maximum (PETM, 55.9 Ma) occurred because of the rapid release of several thousand gigatonnes of isotopically light carbon into the oceans and atmosphere; however, the cause of this release is not well understood. Some studies have linked carbon injection to volcanic activity associated with the North Atlantic Igneous Province (NAIP), while others have emphasised carbon cycle feedbacks associated with orbital forcing. This study presents the osmium isotope compositions of mudrocks that were deposited during the PETM at four locations (one from the Arctic Ocean, and three from the Peri-Tethys). The Os-isotope records all exhibit a shift of similar magnitude towards relatively radiogenic values across the PETM. This observation confirms that there was a transient, global increase in the flux of radiogenic Os from the weathering of continental rocks in response to elevated temperatures at that time. The tectonic effects of NAIP volcanic emplacement near the onset of the PETM is recorded by anomalously radiogenic Os-isotope compositions of PETM-age Arctic Ocean samples, which indicate an interval of hydrographic restriction that can be linked tectonic uplift due to hotspot volcanism in the North Atlantic seaway. The Peri-Tethys data also document a transient, higher flux of unradiogenic osmium into the ocean near the beginning of the PETM, most likely from the weathering of young mafic rocks associated with the NAIP. These observations support the hypothesis that volcanism played a major role in triggering the cascade of environmental changes during the PETM, and highlight the influence of paleogeography on the Os isotope characteristics of marine water masses

Structure of the human activating natural cytotoxicity receptor NKp30 bound to its tumor cell ligand B7-H6

As revealed by the first crystal structure of a natural cytotoxicity receptor bound to its ligand, NKp30 engages B7-H6 in a manner structurally distinct from that of other CD28 family members

A genome-wide association study of Hodgkin Lymphoma identifies new susceptibility loci at 2p16.1 (REL), 8q24.21, and 10p14 (GATA3)

To identify predisposition loci for classical Hodgkin Lymphoma (cHL) we conducted a genome-wide association study of 589 cHL cases and 5,199 controls with validation in 4 independent samples totaling 2,057 cases and 3,416 controls. We identified three new susceptibility loci at 2p16.1 (rs1432295, REL; odds ratio [OR]=1.22, Pcombined=1.91×10−8), 8q24.21 (rs2019960, PVT1; OR=1.33, Pcombined=1.26×10−13) and 10p14 (rs501764, GATA3; OR=1.25, Pcombined=7.05×10−8). Furthermore, we confirmed the role of the MHC in disease etiology by revealing a strong HLA association (rs6903608; OR=1.70, Pcombined=2.84×10−50). These data provide new insight into the pathogenesis of cHL

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates – Relation between textural control on effective element fluxes and resulting carbonate phase

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure