Oxygen Isotope Data Research Articles

Mechanisms of secondary carbonate precipitation on felsic, intermediate and mafic igneous rocks: a case study for NW Scotland

Silicate weathering is a natural regulator of atmospheric carbon dioxide (CO 2 ), where the majority of carbonate is stored in the oceans. In some instances, carbonates may form via bedrock weathering in terrestrial landscapes, but this is commonly noted in ultramafic rock owing to its desirable mineralogy. In NW Scotland, carbonate minerals surround felsic, intermediate and mafic igneous bedrock. Their abundance suggests that these rocks could potentially be targeted for carbonation, given the absence of other known cation sources nearby. We present geochemical and mineralogical data for bedrock samples and mineralogy and stable carbon and oxygen isotope data for the carbonate samples. Whole-rock geochemistry demonstrates that major abundances of CaO and MgO are present in the bedrock samples and would be sourced from plagioclase and pyroxene, which are target minerals for CO 2 mineralization. The stable carbon and oxygen isotope data demonstrate that there are probably mixed carbon sources (atmospheric and organic), and other environmental factors including temperature, CO 2 degassing or evaporation and nearby waters influence the isotopic composition. Results suggest that rocks traditionally overlooked in CO 2 mineralization studies have the potential to serve as a feedstock for carbonation, given the abundance of secondary carbonates found in NW Scotland.

A framework for reconstructing marine heatwaves from individual foraminifera in sedimentary archives

Marine heatwaves (MHWs) are warm sea surface temperature (SST) anomalies with substantial ecological and economic consequences. Observations of MHWs are based on relatively short instrumental records, which limit the ability to forecast these events on decadal and longer timescales. Paleoclimate reconstructions can extend the observational record and help to evaluate model performance under near future conditions, but paleo-MHW reconstructions have received little attention, primarily because marine sediments lack the temporal resolution to record short-lived events. Individual foraminifera analysis (IFA) of paleotemperature proxies presents an intriguing opportunity to reconstruct past MHW variability if strong relationships exist between SST distributions and MHW metrics. Here, we describe a method to test this idea by systematically evaluating relationships between MHW metrics and SST distributions that mimic IFA data using a 2000-member linear inverse model (LIM) ensemble. Our approach is adaptable and allows users to define MHWs based on multiple duration and intensity thresholds and to model seasonal biases in five different foraminifera species. It also allows uncertainty in MHW reconstructions to be calculated for a given number of IFA measurements. An example application of our method at 12 north Pacific locations suggests that the cumulative intensity of short-duration, low-intensity MHWs is the strongest target for reconstruction, but that the error on reconstructions will rely heavily on sedimentation rate and the number of foraminifera analyzed. This is evident when a robust transfer function is applied to new core-top oxygen isotope data from 37 individual Globigerina bulloides at a site with typical marine sedimentation rates. In this example application, paleo-MHW reconstructions have large uncertainties that hamper comparisons to observational data. However, additional tests demonstrate that our approach has considerable potential to reconstruct past MHW variability at high sedimentation rate sites where hundreds of foraminifera can be analyzed.

Highly enriched carbon and oxygen isotopes in carbonate-derived CO2 at Gale crater, Mars

Carbonate minerals are of particular interest in paleoenvironmental research as they are an integral part of the carbon and water cycles, both of which are relevant to habitability. Given that these cycles are less constrained on Mars than they are on Earth, the identification of carbonates has been a point of emphasis for rover missions. Here, we present carbon (δ13C) and oxygen (δ18O) isotope data from four carbonates encountered by the Curiosity rover within the Gale crater. The carbon isotope values range from 72 ± 2‰ to 110 ± 3‰ Vienna Pee Dee Belemnite while the oxygen isotope values span from 59 ± 4‰ to 91 ± 4‰ Vienna Standard Mean Ocean Water (1 SE uncertainties). Notably, these values are isotopically heavy (13C- and 18O-enriched) relative to nearly every other Martian material. The extreme isotopic difference between the carbonates and other carbon- and oxygen-rich reservoirs on Mars cannot be reconciled by standard equilibrium carbonate-CO2 fractionation, thus requiring an alternative process during or prior to carbonate formation. This paper explores two processes capable of contributing to the isotopic enrichments: 1) evaporative-driven Rayleigh distillation and 2) kinetic isotope effects related to cryogenic precipitation. In isolation, each process cannot reproduce the observed carbonate isotope values; however, a combination of these processes represents the most likely source for the extreme isotopic enrichments.

Assessment of seawater intrusion based on geochemical and isotopic data in Makassar coastal area, South Sulawesi, Indonesia

Makassar coastal area has experienced rapid development and has shown various negative impacts from groundwater overexploitation, such as seawater intrusion. This study aimed to assess seawater intrusion based on geochemical and isotopic data in the Makassar coastal area. The research was carried out by field measurement and taking the groundwater samples to the laboratory for geochemical and isotope tests. Geochemical analysis of seawater intrusion was based on TDS, EC, Cl-, Simpson ratio, Ca enrichment, BEX, Na/Cl ratio, and the piper trilinear diagram typer of water. Isotope analysis of seawater intrusion is based on comparing oxygen and deuterium isotopic data from groundwater samples with seawater, river, and rainwater. The results showed that some areas near the sea indicated seawater intrusion in both the semi-unconfined and unconfined aquifers. The indicated seawater intrusion spread in the north Tallo, Mamajang, and Tamalate subdistricts.

South American monsoon intensification during the last millennium driven by joint Pacific and Atlantic forcing

The South American summer monsoon (SASM) profoundly influences tropical South America’s climate, yet understanding its low-frequency variability has been challenging. Climate models and oxygen isotope data have been used to examine the SASM variability over the last millennium (LM) but have, at times, provided conflicting findings, especially regarding its mean-state change from the Medieval Climate Anomaly to the Little Ice Age. Here, we use a paleoclimate data assimilation (DA) method, combining model results and δ 18 O observations, to produce a δ 18 O-enabled, dynamically coherent, and spatiotemporally complete austral summer hydroclimate reconstruction over the LM for tropical South America at 5-year resolution. This reconstruction aligns with independent hydroclimate and δ 18 O records withheld from the DA, revealing a centennial-scale SASM intensification during the MCA-LIA transition period, associated with the southward shift of the Atlantic Intertropical Convergence Zone and the strengthening Pacific Walker circulation (PWC). This highlights the necessity of accurately representing the PWC in climate models to predict future SASM changes.

High resolution stable isotope ratios in modern African land snails: Testing inferred environmental conditions

High-resolution sub-annual stable oxygen isotope data were measured in modern land snail shells collected from different climatic zones in Africa to search for patterns in seasonal δ18O cycles associated with specific hydroclimates, keyed to flora/biozones. Thirty-three recently dead shells were collected between 1995 and 2012, and collection localities were divided into five climate types: tropical forest, woodland savannah, bushland savannah, woodland monsoon, and arid/semi-arid. Thirteen genera are represented in the collection. Sampling covered at least one year in the life of the land snails, often multiple years. A comparison of measured data to predicted δ18O values, using local temperature and rain δ18O value, shows that predictions tend to be lower than measured values, suggesting that surface waters or snail body waters have undergone some evaporation. Predictions based on night-time temperatures (average monthly minimum T) are closer to, but still underestimate, measured values compared to day-time (maximum) temperatures in a majority of cases. The largest range in δ18O values for individual shells occurs in the bushland savannah and woodland monsoon biomes. Longer seasonal intervals of dry conditions lead to greater δ18O ranges in shells, although if the dry interval approaches 10 months in the year the amplitude is again reduced. This is in agreement with other oxygen isotope studies of high-resolution land snail shell samples, which show very high δ18O variance in strong monsoon climates.

Taxonomic and stable isotope analyses of mammal remains from the Lateglacial site of Grotta Polesini (central Italy): Paleoenviromental implications

ABSTRACTGrotta Polesini is one of the most famous paleontological and archaeological sites of central Italy, which testifies to its human occupation during the Lateglacial. The site comprises a cave system where systematic excavation campaigns have been carried out since the 1950s. In 1974, 656 mammal remains were collected but never studied. This fossil collection is here described for the first time through taxonomic and stable isotope analyses of the enamel of selected mammal teeth. The aim is to reconstruct the paleoenvironmental and climatic conditions of the site and to offer new information on terrestrial ecosystems during the Lateglacial in central Italy. The faunal assemblage studied herein, in addition to other species reported in previous works, suggests cold climate conditions. We also describe a right radius of an adult individual of Homo sapiens, increasing the human fossil record of the site. Carbon isotope data point to a scenario dominated by C3 plants in open and dry habitats, such as grasslands and steppes, in accordance with the pollen data from central Italy. The oxygen isotope data suggest the use of water resources with a local origin, i.e. local precipitation and surface waters with a provenance from the nearby Apennine chain. The ecology of the taxa influenced the oxygen isotope values, especially in the case of semi‐obligate to non‐obligate drinker species.

Nutritional status of the reservoir tributary backwater area and implications for nutrient control

Understanding the spatial and temporal distribution and driving factors of the nutritional status in the backwater area of typical tributaries in the Three Gorges Reservoir Region (TGRR) is important for the prevention and control measures. In this study, the Environmental Fluid Dynamics Code (EFDC) was used to extend in situ monitoring data, followed by the application of hydrogen and oxygen isotope data and scoring methods to predict the nutritional status in the backwater area of the Daning River. The results indicated that the nutritional status-sensitive period mainly ranged from May-October and was distributed at the end of the backwater area and tributary bay. The water temperature and intermediate density flow were identified as the key factors inducing deterioration in the nutritional status at the end of the backwater area and tributary bay, respectively. Nutrient reduction in the mainstream and tributary areas significantly affected the nutritional status in the backwater area. Notably, hydrodynamic adjustment under reservoir objectives is indispensable for improving the water environment in tributary bay after reaching the water quality standard. Our findings highlight the necessity of focusing on the upper reaches of the tributaries and reservoir for nutrient control and emphasize the importance of combining reservoir operation strategies to mitigate the deterioration in the nutritional status.

Seasonal Variations and Controls on Triple Oxygen and Hydrogen Isotopes in Precipitation—A Case Study From Monitoring in Southwest China

AbstractPrecipitation δ18O has offered valuable insights into the evolution of the Asian monsoon. Recent researches focusing on precipitation Δ′17O has enhanced our understanding by offering new perspectives beyond those of δ18O, revealing insights into vapor sources and continental recycling. Nevertheless, there remains a lack of interannual triple oxygen isotope data, particularly in the Asian monsoon region. In this study, we analyzed the triple oxygen isotopes and hydrogen isotopes in monthly precipitation samples collected from Chongqing in Southwest China between 2019 and 2022 A.D. Seasonal variations in δD, δ18O, δ17O, and d‐excess values were observed, with lower values during the rainy season and higher values during the dry season, highlighting the impact of changes in moisture sources and local meteorological conditions on seasonal shifts in δD, δ18O, and δ17O. While, mean Δ′17O values were higher in rainy season and lower in dry season. Notably, during rainy season, there is a negative correlation between monthly Δ′17O values and the RH of the vapor source area, as well as a positive correlation with d‐excess. Recalculated Δ′17O values based on RH of oceanic moisture source, are higher than the measured values for this period, indicating the contribution of terrigenous moisture to precipitation in SW China. Precipitation Δ′17O values provide a more precise reflection of changes in moisture source, continental recycling, and evapotranspiration processes that drive water cycling compared Integrating modeling works in future will facilitate the use of precipitation Δ′17O values to quantify the impact of different moisture source on precipitation.

The vertical calcification mode of planktonic foraminifera in the Western Pacific Warm Pool

A thorough knowledge of the ecology of planktonic foraminifera throughout the water column is necessary for a reliable reconstruction of the paleooceanographic environment of the upper-middle water column. However, little is known about the planktonic foraminifera in the Western Pacific Warm Pool (WPWP), especially for the deep dwelling species. Here we present the stable oxygen isotope (δ18O) data of eight species collected from vertically stratified plankton tows across 0–500 m water depth from 5 sites in the WPWP during autumn, the vertical mode of foraminiferal calcification is explored. Vertical plankton tows provide more detailed information than other materials, it indicates a wider depth range of foraminiferal calcification than the other sample types. All the species exhibit a complex vertical calcification process that the majority of specimens precipitate their tests out of the depth at which they were obtained. It could be connected to the intricate hydrological conditions in the WPWP and/or the foraminiferal ontogenetic trajectory. Calcification depth range of the investigated species is substantially smaller than their living depth, and most of them prefer to calcify inside the abundant layers. Additionally, we found no clear correlation between foraminiferal test size and shell δ18O for any of the species that were studied at any of the locations.

Tracking palaeotemperatures in Coniacian–Maastrichtian seas

In this study the stable isotopes of belemnites, are presented from the Coniacian–Maastrichtian interval (∼76–66 Ma) derived from the chalks of Yorkshire and Norfolk, UK, deposited on the western North Atlantic shelf. Cathodoluminescence and elemental geochemistry of the belemnites reveals that most of the rostra were well preserved. If interpreted in terms of temperature, our oxygen isotope record reveals that during the Coniacian (at ∼43 °N) the climate was relatively warm, with maximum mean temperatures of ∼26 °C, followed by cooling to <∼21 °C during the Campanian and Maastrichtian. This overall stratigraphic trend is similar to other records, suggesting that the cooling pattern was not a regional trend and, therefore, driven predominantly by global mechanisms. Within our belemnite data, we also observe a decline in δ13C at the Campanian- Maastrichtian boundary, again consistent with other records. This trend has been interpreted as a result of an increased ratio of organic to inorganic carbon introduced into the oceans, driven by increased weathering and reworking of organic-rich sediments exposed on continental shelves during a sea-level fall. The latter related to a build-up of polar ice. Although our oxygen isotope data point to a cooling this was not necessarily linked to polar ice formation.

Paleoaltimetry and paleotectonic reconstruction using triple oxygen and hydrogen isotopes: Depleted δ18O and δD values in ignimbrites of Verkhneavachinskaya caldera record collisional uplift during Miocene arc accretion to Kamchatka

Here we use δ18O and δD values as tools to investigate the paleo-altitude and the origin of large-volume (120 km3, 10 × 12 km) ignimbrites of Verkhneavachinskaya caldera (cf. Verkhne-Avachinskaya) (VC) in eastern Kamchatka, formed the in Late Miocene 5.8 Ma. The basaltic-andesitic intracaldera ignimbrite deposit exhibits low δ18O values, reaching −5.03‰, and δD values of −182‰ across a 1.2 km depth range in several sampled sections. The results support a massive meteoric-hydrothermal system throughout the cooling history of the thick intracaldera ignimbrite deposit. Using triple oxygen isotope data we estimate that the δ18O values of altering meteoric water are as low as −19‰ to −23‰, much lower than modern precipitation of −14‰, or − 16‰ estimated for the 2–3 °C warmer Kamchatka climate of the late Miocene. Therefore, the VC meteoric-hydrothermal system depended on high-altitude precipitation and glaciers, and altitudinal isotopic lapse rates suggest a paleo-altitude of 3.5 km at 5.8 Ma during caldera formation. These elevations exceed the modern by 1.5 km and provide a unique snapshot into an evolving landscape and paleo-environment of eastern Kamchatka at 6–5 Ma as the dynamic outcomes of accretion of the Kronotski arc. In particular, the existence of such a high plateau is in line with contemporary accretionary tectonics: accretion of the Shipunsky peninsula of this accreting arc terrain, ∼120 km to the east of the VC, and evidence of contemporaneous exhumation of high-grade Ganal amphibolites to the west. We conclude that the eruption of large-volume mafic ignimbrites that formed VC caldera was syncollisional or intracollisional in nature, likely requiring delamination of thickened crust to account for both uplift and magmatism.

A record of magmatic differentiation in plutonic xenoliths from Santorini (Greece)

Plutonic xenoliths from volcanic arcs provide unique insights into transcrustal magmatic systems in subduction zone settings. At Santorini volcano in the Central Aegean Volcanic Arc (Greece), plutonic xenoliths occur throughout a sequence of lavas and pyroclastic rocks erupted within the last ~360 ka. They are mineralogically variable, ranging from troctolites to olivine gabbros, gabbros, gabbronorites, and diorites. Thermobarometric calculations based on mineral and melt inclusion compositions indicate equilibration over a range of temperatures (1100 to 750 °C) at shallow to mid-crustal depths (P &lt;400 MPa), but there is no evidence for crystallisation at lower crustal depths. Oxygen isotope data of mineral separates and calculated δ18O melt values are in line with extensive closed-system fractional crystallisation at magmatic temperatures, without a requirement for extensive assimilation of the subvolcanic continental basement. The xenolith minerals compositionally overlap with phenocrysts from the volcanic rocks, but they also contain evidence for the presence of highly evolved melt compositions in the form of melt inclusions with extremely silica-rich compositions (up to 82 wt.% SiO2) and high enrichments of incompatible trace elements coupled with increasing negative Eu anomalies in clinopyroxenes. Since these characteristics correlate systematically with differentiation indices and rock type, they are interpreted to reflect melt evolution via fractional crystallisation as the dominant differentiation process with no significant role of reactive porous flow. These observations highlight that trapped melt fractions can influence mineral compositional variations in the plutonic xenoliths, and in turn the mineral compositions demonstrate a melt compositional variability not preserved in the volcanic rock record.

Devonian plutons in the eastern Meguma terrane, Nova Scotia, Canada: zircon U–Pb, Lu–Hf, and O isotopic compositions, age, and petrogenetic implications

Abundant granitic plutons intruded the eastern Meguma terrane of Nova Scotia in the middle- to late Devonian. Less voluminous diorite–tonalite and gabbro intrusions are associated with the granitic plutons along the northern margin of the terrane adjacent to the Cobequid–Chedabucto fault zone. All plutons contain metasedimentary xenoliths, and the mafic plutons show magma mingling textures with their adjacent granitic plutons. New U–Pb zircon data from autocrystic zircon in 13 samples indicate coeval emplacement of mafic and granitic plutons between ca. 382 and 368 Ma. However, the zircon grains contain numerous inherited domains that range in age from Palaeoproterozoic to Devonian. These inherited ages correspond to detrital zircon U–Pb dates from the Cambrian to Ordovician metasedimentary host rocks. Zircon oxygen isotopic data (δ18O) are between +7.4 ± 0.2‰ and +9.3 ± 0.3‰ indicating significant involvement of the crust as the magma source or contaminant. If the high δ18Ozrn values are a result of contamination, the contaminant was likely the metasedimentary rocks of the Meguma terrane. Hafnium isotopic data from autocrystic zircon have εHf( t) between −6.0 ± 1.5 and +2.1 ± 2.5. The new zircon U–Pb, O, and Hf isotopic data from plutons in the eastern Meguma terrane are indistinguishable from published data from the South Mountain Batholith. The data suggest that Devonian magmatism in the Meguma terrane post-dated the main orogenic event that caused folding and regional metamorphism and involved the same magma source and/or contaminants throughout the terrane.

Petrology, Mineralogy, and Stable Isotopic Composition of NWA 13943 (CK5) Carbonaceous Chondrite

Karoonda-like (CK) carbonaceous chondrites are highly oxidized meteorites, with metal-to-magnetite ratio close to zero. Unlike other carbonaceous chondrites (petrologic type: 1–3), most CK chondrites have undergone thermal metamorphism (550–1270 K) on their parent body with a petrologic type 4 or above. Lines of evidence suggest a genetic relationship between CK chondrites and Vigarano-like (CV) carbonaceous chondrites, which are predominantly type 3. However, observable petrographic distinctions persist between the two groups. Thus, a thorough reevaluation of their geochemical discrepancies is critical to test the CK-CV single parent body hypothesis. Northwest Africa (NWA) 13943, a newly discovered meteorite subjected to intense modification, was classified using scanning electron microscopy and electron microprobe techniques. High-precision measurements of the mass-independent chromium isotope compositions (ε53Cr and ε54Cr) and the mass-dependent oxygen isotope compositions (δ17O and δ18O) of NWA 13943 were reported for the first time. Integrating petrological, mineralogical, oxygen, and chromium isotopic data, it is legitimated to infer that CK and CV chondrites may originate from two proximal but distinct isotopic reservoirs within the protoplanetary disk.

Isotopic and mineralogic bias introduced by pulverization of aragonite

RationaleStable carbon and oxygen isotope data of biogenic and abiogenic aragonite are of fundamental relevance in paleoclimate research. Wet‐chemical analysis of such materials requires well‐homogenized, fine‐grained powder. In the present study, the effect of different grinding/milling methods on sample homogeneity and the potential risk of unintentional calcite formation and isotope shift were evaluated.MethodsShells of Arctica islandica and aragonite sputnik crystals were pulverized using a set of commonly used methods, including a hand‐held drill, a vibromill operated at various settings (with and without liquid nitrogen cooling, changes in ball diameters, frequencies, and processing durations), and an agate mortar and pestle. Stable isotope values were measured using an isotope ratio mass spectrometer operated in continuous flow mode. Identification of mineral phases was obtained by powder X‐ray diffraction (PXRD), Raman spectroscopy, and attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy. Calcite content was quantified by PXRD Rietveld refinement.ResultsSamples showed substantial homogeneity, in particular after vibromilling (duration 3–10 min). More vigorous grinding resulted in larger fractions of calcite (0.5–4.2 wt%) and a concomitant δ18O and δ13C decrease, specifically in bivalve shells. The only method for producing pure aragonite powder was by pounding the aragonite sputniks manually with an agate mortar and pestle.ConclusionsNone of the studied, commonly used machine‐based pulverization methods produced pure aragonite powder from samples consisting originally of aragonite. These findings have significant implications for light‐stable isotope‐based paleoclimate reconstructions. Except for abiogenic aragonite powder produced by pounding in an agate mortar, paleotemperatures would be overestimated.

Elemental and oxygen isotopic fractionation recorded in highly vaporized cosmic spherules from Widerøefjellet, Sør Rondane Mountains (East Antarctica)

AbstractUpon passage through Earth's atmosphere, micrometeorites undergo variable degrees of melting and evaporation. Among the various textural and chemical groups recognized among cosmic spherules, that is, melted micrometeorites, a subset of particles may indicate anomalously high degrees of vaporization based on their chemical and isotopic properties. Here, a selection of such refractory element‐enriched cosmic spherules from Widerøefjellet (Sør Rondane Mountains, East Antarctica) is characterized for their petrographic features, major and trace element concentrations (N = 35), and oxygen isotopic compositions (N = 23). Following chemical classification, the highly vaporized particles can be assigned to either the “CAT‐like” or the “High Ca‐Al” cosmic spherule groups. However, through the combination of major and trace element concentrations and oxygen isotopic data, a larger diversity of processes and precursor materials are identified that lead to the final compositions of refractory element‐enriched particles. These include fragmentation, disproportional sampling of specific mineral constituents, differential melting, metal bead extraction, redox shifts, and evaporation. Based on specific element concentrations (e.g., Sc, Zr, Eu, Tm) and ratios (e.g., Fe/Mg, CaO + Al2O3/Sc + Y + Zr + Hf), and variations of O isotope compositions, “CAT‐like” and “High Ca‐Al” cosmic spherules likely represent a continuum between mineral endmembers from both primitive and differentiated parent bodies that experienced variable degrees of evaporation.

Hydroclimate of the Messinian Salinity Crisis constrained from paleo-water triple oxygen, hydrogen, and strontium isotopes

Giant evaporite deposits formed during the Messinian Salinity Crisis (MSC) in the Mediterranean Sea during the upper Miocene. The primary cause is a restricted Atlantic-Mediterranean connection, but the detailed hydroclimate evolution of this event is still a matter of debate. Here we reconstruct the triple oxygen and hydrogen isotopic composition of paleo brines from structurally bonded water in Messinian gypsum from Cyprus. A two-stage evaporation model is constructed to best approximate the hydrological conditions at which Messinian gypsum formed in marginal basins of the Mediterranean Sea. Subsequently, hydroclimatic parameters like paleo relative humidity (RH) are modelled using an iterative curve fitting isotope model approach. The results of our limited dataset reveal a slightly lower RH during the third compared to the second stage of the MSC. This apparent drop in RH is consistent with previous observations from the literature.Besides absolute values of RH, our model allows reconstructing the triple oxygen and hydrogen isotopic composition of the open Mediterranean Sea. This provides an estimate for the proportions of continental water vs. Atlantic seawater flowing into the basin, serving as a proxy for the size of the strait of Gibraltar. The model implies a continental water fraction of around 75–81 % both for the second and third stage of the MSC. In addition, we determined the 87Sr/86Sr of our samples to: i) confirm their stratigraphy; and ii) estimate the relative proportion of continental water vs. Atlantic seawater entering the Mediterranean using Sr mass balance calculations. The combined oxygen and Sr isotope records indicate a persistent connection to the Atlantic supporting the hypothesis that the striking drop in 87Sr/86Sr at the beginning of MSC stage 3 is mainly related to an increased contribution of continental water with low 87Sr/86Sr and high Sr concentrations from the Paratethys. Our results show that the combination of triple oxygen, hydrogen, and Sr isotope data provides a powerful tool to disentangle paleo-hydroclimate even in such complicated hydrological settings as the Mediterranean Sea during the MSC.

SISALv3: a global speleothem stable isotope and trace element database

Abstract. Palaeoclimate information on multiple climate variables at different spatiotemporal scales is becoming increasingly important to understand environmental and societal responses to climate change. A lack of high-quality reconstructions of past hydroclimate has recently been identified as a critical research gap. Speleothems, with their precise chronologies, widespread distribution, and ability to record changes in local to regional hydroclimate variability, are an ideal source of such information. Here, we present a new version of the Speleothem Isotopes Synthesis and AnaLysis database (SISALv3), which has been expanded to include trace element ratios and Sr isotopes as additional, hydroclimate-sensitive geochemical proxies. The oxygen and carbon isotope data included in previous versions of the database have been substantially expanded. SISALv3 contains speleothem data from 365 sites from across the globe, including 95 Mg/Ca, 85 Sr/Ca, 52 Ba/Ca, 25 U/Ca, 29 P/Ca, and 14 Sr-isotope records. The database also has increased spatiotemporal coverage for stable oxygen (892) and carbon (620) isotope records compared with SISALv2 (which consists of 673 and 430 stable oxygen and carbon records, respectively). Additional meta information has been added to improve the machine-readability and filtering of data. Standardized chronologies are included for all new entities along with the originally published chronologies. Thus, the SISALv3 database constitutes a unique resource of speleothem palaeoclimate information that allows regional to global palaeoclimate analyses based on multiple geochemical proxies, permitting more robust interpretations of past hydroclimate and comparisons with isotope-enabled climate models and other Earth system and hydrological models. The database can be accessed at https://doi.org/10.5287/ora-2nanwp4rk (Kaushal et al., 2024).

Robust sulfur and oxygen isotope evidence for a highly anoxic paleoenvironment in Late Devonian seawater: Insights from marine anhydrites in the Zaige Formation, South China

A global-scale mass extinction event occurred in the Late Devonian, and its triggering mechanisms have remained a subject of controversy. The key to resolving this controversy lies in elucidating paleoenvironmental characteristics and their coupling relationship with the mass extinction. Marine evaporites serve as sensitive indicators that can be used for reconstructing the geochemical history of ancient oceans. In this study, we present a dual sulfur and oxygen isotopic dataset of marine anhydrites in the Lunatian gypsum deposit (Yunnan, China), and investigate its paleoenvironmental significance within the framework of the Late Devonian mass extinction. These anhydrites originate in arid and hot continental margin seas near convergent plate boundaries, forming as a result of the dehydration of marine gypsums during burial processes. Anhydrites exhibit a conspicuous positive anomaly in δ34S values (23.6–25.1‰, averaging 24.3‰), primarily attributed to bacteria-mediated sulfate reduction. The δ18O values of the Lunatian anhydrites (12.2–15.2‰, averaging 14.0‰) indicate a slightly higher oxygen isotope composition for Late Devonian seawater (8.7–11.7‰, averaging 10.5‰) compared to those of contemporary seawater (9.5–10.1‰). Such an oxygen isotopic characteristic for the Lunatian anhydrites is intricately associated with the chemical processes that occur during the diffusion of sulfides into the upper seawater. The anhydrite-forming evaporating system has a noticeable brine layering where the surface seawater is less dense than the deeper brine, and bacterial processes gradually increase δ34S in the deep brine. When the deep brine and surface seawater rapidly mix, it leads to a significant positive shift in the sulfur isotope composition of the resulting evaporites. Our sulfur and oxygen isotope data from Lunatian anhydrites validate the existence of an exceedingly anoxic marine environment during the Late Devonian, potentially serving as a pivotal factor in the mass extinction event.