Stable Oxygen Isotope Research Articles

Stable Isotope Hydrology of Karst Groundwaters in Romania

In this article we present the first investigation of the stable isotope composition of groundwater in Romania, East-Central Europe, with a focus on the karst areas. Our aim is twofold: (1) to provide a countrywide map with the distribution of stable oxygen and hydrogen isotope ratios in groundwater, and (2) to assess the recharge patterns of karst water. We collected more than 600 water samples from springs and wells across Romania for stable isotope analyses and monitored in detail the stable isotope composition of the waters as they pass through five cave systems. Our data show a spatial distribution of the stable isotope composition of the groundwater with low values in the mountainous area and high values in the surrounding lowlands and the central Transylvanian Depression. However, waters in karst areas induce departures from this distribution, resulting from the fast (hours to days) transfer of waters from high (ponor) to low (spring) altitudes. Water emerging from the karst springs has generally lower δ values than before sinking through the ponors, thus indicating a substantial contribution of winter recharge through diffuse infiltration and seepage. This contribution results in overall dilution of the water entering through ponors, likely resulting in changes in the chemical composition of the water and diluting potential pollutants. Our data call for careful separation between karst and non-karst spring/well waters, as indiscriminate common treatment might lead to erroneous interpretations.

Limestone water mixing process and hydrogen and oxygen stable isotope fractionation response under mining action

North China type coalfield are gradually mining deep, and the mixing of groundwater is intensified. Hydrogen and oxygen isotopes are important elements for tracing groundwater movement. The fractionation response mechanism under mining conditions is not clear. In this paper, combined with numerical simulation, MixSIAR isotope mixing model and other methods, according to the δD, δ18O and hydrochemical information of various water bodies, the impact of coal mining on hydrogen and oxygen isotope fractionation is analyzed from multiple perspectives. The results show that summer soil water is the main source of recharge for limestone water, accounting for 30.7%–41.5%, and the Zhan River is the main source of recharge for limestone water. Before groundwater recharge, evaporation leads to the increase of δ18O in surface water by 0.31‰–5.58‰, water loss by 1.81%–28.00%, the increase of δ18O in soil water by 0.47‰–6.33‰, and water loss by 2.74%–35.80%. Compared with the coal mining layer, the degree of hydrogen and oxygen isotope drift and water-rock interaction in the coal mine stopping layer are significantly improved. The results of numerical simulation show that the pumping activity reduces the 18O concentration in the mining layer. The ion ratio is used as a new variable to eliminate the influence of water-rock interaction when calculating the mixing ratio. The results show that the limestone water is in a state of receiving external recharge, and mixing effect increases the δ18O in limestone water by 0.86‰ on average, and the δD increases by 0.72‰ on average. The research results explain the controlled process of hydrogen and oxygen isotope fractionation under mining conditions, which is of great significance to coal mine safety production.

Late Holocene changes in the water table at an alkaline fen in Central Latvia: Their impacts on CaCO3 deposition at the fen and relation to the hydroclimate patterns of the Eastern Baltic Region

Sediments of CaCO3-precipitating alkaline fens, comprising biotic and abiotic indicators of water table changes, are among the most reliable archives for obtaining palaeohydrological data. The study uses a semiquantitative method based on a combination of selected indicators (plant macrofossils, mollusc shells, degree of peat decomposition) to estimate the relative changes in the water table position at Lustūžkalns alkaline fen, Latvia, Eastern Baltic Region. The study also aims to determine the time frames of CaCO3 deposition at the fen using loss on ignition and carbon and oxygen stable isotope records. The chronology of the three sediment sequences studied is based on the AMS radiocarbon dating of terrestrial plant macrofossils. Although the reconstructed water table positions revealed differences between the cores, the major shift from the low water tables persisting since ca. 5000 cal yr BP to the prevailing high water stands at ca. 3000 cal yr BP was common to all the sequences. The major shift observed is consistent with a change from low to high water tables in peatlands in Latvia and at numerous fens and bogs across the Eastern Baltic Region, Fennoscandia and NW Europe. Concurrent with the increase in the water tables was the onset of CaCO3 precipitation on the Lustūžkalns fen surface, which began at ca. 3000 cal yr BP and accelerated from ca. 2500 cal yr BP. The Late Holocene CaCO3 precipitation at Lustūžkalns can be attributed to the change from warm and dry conditions during the Holocene Thermal Maximum (HTM) to cooler but humid during the Late Holocene. In contrast, in Central and Western Europe, the main period of freshwater carbonate precipitation occurred during the warm and humid HTM.

Global Multiproxy ENSO Reconstruction Over the Past Millennium

AbstractEl Niño‐Southern Oscillation (ENSO) is the leading mode of interannual climate variability that affects climate and society across the world. However, our understanding of ENSO variability is currently lacking due to short instrumental observations, which limit our confidence in predicting its future occurrence and impact. In this study, we use the nested principal component regression method to reconstruct the ENSO index based on a global‐scale proxy network of stable oxygen isotopes (δ18O). We account for the teleconnection changes that influence proxy records corresponding to different ENSO phases by using the isotope‐enabled Community Earth System Model. According to the precipitation δ18O–ENSO relationship, we reconstruct the ENSO index over the last eight hundred years based on the first two leading modes of the selected proxy records. The skill of ENSO reconstruction improves with an increased number of δ18O series distributed over the ENSO‐affected regions. Our new reconstruction shows high consistency with existing ENSO reconstructions during periods of strong ENSO variability, indicating that the global proxy records capture enhanced teleconnection signals during the phase of strong ENSO amplitude. There is a weak El Niño response 1 year after the large volcanic eruptions in our reconstruction, and the amplitude of ENSO is significantly correlated with volcanic intensity. The strengthened energetic interactions between the ocean and atmosphere following large volcanic eruptions result in enhanced sea surface temperature variability.

Nitrogen isotope ratio (δ15N): a nearly unexplored indicator that provides useful information in viticulture

The study of the natural abundance of nitrogen-stable isotopes is an aspect of viticulture research that has received limited attention. While stable isotopes of carbon, oxygen and hydrogen have received significant attention, nitrogen isotope ratio (δ15N) remains a less studied yet potentially informative parameter. This paper explores the implications of δ15N measurements in grapevines, shedding light on its utility as an indicator for nitrogen sources, plant water status, and within-field variability. The study examines the influence of nitrogen sources, dose, and sampling organs on δ15N values, revealing distinct trends in petioles, berries, and seeds. Organic fertilisers led to higher δ15N values compared to inorganic sources, while increasing nitrogen doses exhibited a much weaker effect on δ15N. Moreover, δ15N values vary spatially within vineyards, associating with its topography and potential soil composition, soil management and water availability. Our results highlight the importance of considering δ15N in viticulture, suggesting its integration with δ13C for comprehensive insights into nitrogen cycling and soil management practices. The findings advocate for further research to harness the full potential of δ15N as a valuable tool in viticultural studies.

Acid mine drainage from coal mines in the eastern Himalayan sub-region: Hydrogeochemical processes, seasonal variations and insights from hydrogen and oxygen stable isotopes

Uncontrolled coal mining using non-scientific methods has presented a major threat to the quality of environment, particularly the water resources in eastern himalayan sub-region of India. Water bodies in the vicinity of mining areas are contaminated by acid mine drainage (AMD) that is released into streams and rivers. This study attempted to assess the impact of AMD, deciphering hydrogeochemical processes, seasonal fluctuations, and stable isotope features of water bodies flowing through and around coal mining areas. Self-organizing maps (SOMs) used to separate and categorize AMD, AMD-impacted and non-AMD impacted water from the different study locations for two sampling seasons revealed four clusters (C), with C1 and C2 impacted by AMD, C3 and C4 showing negligible to no impact of AMD. AMD impacted water was SO42− - Mg2+- Ca2+ hydrochemical type with sulphide oxidation and evaporation dominating water chemistry, followed by silicate weathering during both the sampling seasons. Water with negligible-to-no AMD-impact was Mg2+- Ca2+- SO42− to Ca2+ - HCO3− to mixed hydrochemical type with rock weathering and dissolution, followed by ion exchange as major factors controlling water chemistry during both the sampling seasons. Most of physicochemical parameters of C1 and C2 exceeded the prescribed limits, whereas in C3 and C4 water samples, parameters were found within the prescribed limits. Stable isotopes of hydrogen (δ2H) and oxygen (δ18O) during post-monsoon (PoM) varied between -41.04 ‰ and -29.98 ‰, and −6.60 ‰ to −3.94 ‰; and during pre-monsoon (PrM) varied between −58.18 ‰ and - 33.76 ‰ and −8.60 ‰ to −5.46 ‰. Deuterium excess (d-excess) ranged between 1.57 ‰ and 12.47 ‰ during PoM and 5.70 ‰ to 15.17 ‰ during PrM season. The stable isotopes analysis revealed that evaporation, mineral dissolution and mixing with rainwater are the key factors in study area.

Developing isotopic proxies to reconstruct the metabolic rates and thermal histories of octopus

Understanding an animal's metabolic rate and thermal history is pivotal for ecological research. Recent studies have proposed the use of stable carbon and oxygen isotopes (δ13C and δ18O) in biogenic carbonates as proxies of metabolic rate and experienced temperature, respectively, to overcome the challenges of directly measuring these data in the field. Our study represents the first experimental investigation to develop δ13C and δ18O proxies in octopus. Octopus berrima hatchlings were raised in captivity, at varying water temperatures, for up to 110 days. O. berrima statoliths were then subsequently analysed for δ13C and δ18O values. The proportion of metabolically derived carbon, or respired carbon (Cresp), increased as the octopus grew (slope = 0.076, R2 = 0.72), suggesting an influence of somatic growth rate and body mass on δ13C values. Additionally, we identified an inverse correlation between δ18O values and environmental temperature (slope = −0.163, R2 = 0.91), which was subsequently used to develop a thermal reconstruction model. Our experiment aids in interpreting stable isotopic values in statoliths and their application as temperature and metabolic proxies in wild-caught octopus. Such proxies will increase our monitoring capabilities of these ecologically and commercially significant cephalopods and contribute to their conservation and effective management.

Comparison of carbon, nitrogen, and oxygen stable isotope ratios and mercury concentrations in muscle tissues of five beaked whale species and sperm whales stranded in Hokkaido, Japan

ABSTRACT We studied δ 13C, δ 15N and δ 18O values, and total mercury (THg) concentrations in muscle samples from deep-sea predators – five beaked whale species and sperm whales – stranded along the coast of Hokkaido, in the north of Japan in 2010 and 2019. The δ 13C, δ 15N and δ 18O values, THg concentrations, and body length (BL) of Stejneger’s beaked whales were similar to those of Hubbs’ beaked whales, which belong to the same genus. In contrast, δ 13C values, THg concentrations, and BL of Sato’s beaked whales were markedly different from those of Baird’s beaked whales, which belong to the same genus. Stejneger’s and Hubbs’ beaked whales living around Hokkaido may compete in their ecological niches, whereas Sato’s and Baird’s beaked whales may segregate their ecological niches. Although Cuvier’s beaked whales and sperm whales belong to different genera and their BLs were significantly different, their δ 13C and δ 15N values were similar, probably because they can dive and stay in deeper waters than other beaked whale species. The δ 13C values in combined samples from all whales increased with increasing BL, probably owing to the larger whale species’ dietary preference for squid. The δ 13C values in combined samples from all whales were positively correlated with THg concentrations, whereas the δ 15N values in the combined samples were negatively correlated. The δ 18O values in combined samples from most whales tended to be positively correlated with THg concentrations. These correlations may be explained by a higher THg load from deep-sea feeding than from pelagic feeding and by a feeding shift towards lower trophic levels.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Characterizing the stable oxygen isotopic composition of the southeast Indian Ocean

New seawater stable oxygen isotope (δ18O) samples were collected from the southeast Indian Ocean as part of the Coring to Reconstruct Ocean Circulation and Carbon dioxide Across 2 Seas (CROCCA-2S) expedition in November – December of 2018. These data fill a gap in the δ18O sampling coverage of the southern Indian basin, providing new insights into the hydrologic and oceanographic processes influencing the δ18O distribution of the region and its relationship to salinity in the upper ocean. Our surface ocean data (<100 m)—in combination with decades of observations from the broader south Indian Ocean—show distinct δ18O – salinity characteristics on either side of ∼85°E. The balance between evaporation and precipitation yields a strong, robust δ18O – salinity relationship west of 85°E (δ18O = 0.50(±0.01) * S – 17.2(±0.22)). However, within the mesoscale eddy field initiated by the Leeuwin Current further east (∼85–120°E), our observations fall along a mixing line between the southwest Indian Ocean and data collected from the Australian coastal margin, illustrating for the first time how the unique eastern boundary system of the south Indian Ocean drives regional-scale variability in the δ18O – salinity relationship of the surface ocean. A comparison between our observations in the shallow subsurface (100–1000 m) and those from neighboring surveys reinforces this upper ocean connection across the Indo-Australian basin. Antarctic Intermediate Water from the Indian Ocean can be isotopically distinguished from the more regional Tasman Intermediate Water occupying the South Australian Bight, suggesting exchange between the two regions is most prevalent at surface and mode water depths. In deeper waters (> ∼1500 m), we observe a notable 0.87‰ spread in δ18O. This variability may represent interactions between distinct deep water masses in the region, although additional data are needed to confirm. Overall, our data provide a new look at the hydrography and isotopic chemistry of the southeast Indian Ocean, emphasizing the impact of the region's mesoscale eddy field and its interconnectivity with neighboring basins.

Evapotranspiration variation of soil‐plant‐atmosphere continuum in subalpine scrubland of Qilian Mountains in China

AbstractThe water cycle in the soil‐plant‐atmosphere continuum is an important element of hydrological and ecological studies, and differences in the composition characteristics of hydrogen and oxygen stable isotopes in different water bodies can indicate water cycling processes. In this study, hydrogen and oxygen isotopes of precipitation, soil water and plant water samples had been collected in the subalpine scrubland of the Qilian Mountains from May to October 2019. The Craig‐Gordon model, the isotopic steady‐state (ISS) assumption, the Keeling Plot model and the two‐source mixing model were used to analyse the stable isotope compositions of different water bodies, the stable isotope characteristics of water vapour of soil evaporation and plant transpiration and the variation of evapotranspiration in the SPAC of the subalpine scrubland. The results showed that plant transpiration (FT) contributed 87.28% and 86.95% to evapotranspiration and soil evaporation (FE) contributed 12.72% and 13.05% to evapotranspiration in the growing season on semi‐sunny and semi‐shaded aspects, respectively, indicating that evapotranspiration in the subalpine scrubland mainly came from the transpiration of scrubland plants. In the early of the growing season (May–June), due to the rapid expansion of plant leaves, the contribution of transpiration to evapotranspiration was at a high level, which intensified transpiration and led to a gradual increase of the transpiration contribution. In the middle of the growing season (July–August), owing to better conditions of rain and heat that made plants grow vigorously, plant transpiration made the highest contribution to evapotranspiration more than 90%, which caused to an overwhelming contribution of plant transpiration to evapotranspiration. In the later of growing season (September to October), the contribution of plant transpiration to evapotranspiration decreased significantly while that of soil evaporation increased, which was because plant photosynthesis and respiration gradually declined for losing their leaves of scrub plants and the relative atmospheric humidity was lower.

Effect of Water‐Rock Ratio on the Stable Isotope Record of Fluid‐Rock‐Deformation Interactions in Detachment Shear Zone

AbstractOxygen and hydrogen stable isotope analyses of quartz and muscovite veins from the footwall of the Raft River detachment shear zone (Utah) provide insight into the hydrology and fluid‐rock interactions during ductile deformation. Samples were collected from veins containing 90%–100% quartz with orientations either at a high angle or sub‐parallel to the surrounding quartzite mylonite foliation. Stable isotope analysis was performed on 10 samples and compared with previous quartzite mylonite isotope data sets. The results indicate that the fluid present during deformation of the shear zone was meteoric in origin, with a δ2H value of approximately −100‰ and a δ18O value of approximately −13.7‰. Oxygen stable isotope O18O depletion correlates with the muscovite content of the analyzed rocks. Many of the analyzed samples in this and other studies show an apparent lack of equilibrium between the oxygen and hydrogen isotope systems, which can be explained by hydrogen and oxygen isotope exchange at varying fluid‐rock ratios. Our results suggest that the Raft River detachment shear zone had a low static fluid‐rock ratio (&lt;0.1), yet experienced episodic influxes of fluids through semi‐brittle structures. This fluid was then expelled out into the surrounding mylonite following progressive shearing, causing further 18O‐depletion and fluid‐related embrittlement.

Advances in Limnogeology: The lake‐basin‐type model revisited 25 years after…anomalies, conundrums and upgrades

AbstractThe lake‐basin‐type model classified the stratigraphic record of ancient lake systems according to rates of potential accommodation relative to sediment + water supply. The model convolved all modes and paths of water supply (direct fall, surficial, subsurface) with amounts and types of sediment supply (clastic, biogenic, chemical) into a single basin‐filling volume term (sediment + water); its major strength was its widespread applicability. This was supported by subsequent investigations confirming the utility of this approach, but it also revealed some important limitations due to simplifications in the original model. The model has been expanded here to address all inland waters (lakes, ponds, wetlands, playas) as well as adding two major subdivisions of the sediment + water term: (1) water supply paths and (2) the volume of water supply relative to sediment supply. Water supply flow paths in the subsurface are subdivided into ‘throughflow’, ‘recharge’ and ‘discharge’. Each of these groundwater hydrology states can be defined quite precisely by the ratio of net outflow to inflow, from persistently open to consistently closed. These paths can be deciphered using stable carbonate and oxygen isotope composition of primary lacustrine limestones, detailed sedimentology, stratigraphy, palaeontology and mineralogy. Distinguishing water supply paths provides additional insights into playa systems and the occurrence and character of evaporites and carbonates. The volume ratio of water to sediment supply most directly influences the water depths of lakes, ponds and wetlands, which affect water body hydrodynamics and ecosystem behaviour as well as the details of stratal stacking and depositional sequences. It helps fine‐tune estimates of the distribution of sediment texture, bedding, composition and organic matter content. The aim of this contribution is to address questions about the fundamental types of inland water bodies and to explain the new lake‐basin subtypes and provide examples that illustrate their potential to enable higher‐resolution, robust analysis of inland water systems and their stratigraphic records.

Stable isotope evidence for long-term stability of large-scale hydroclimate in the Neogene North American Great Plains

Abstract. The Great Plains of North America host a stark climatic gradient, separating the humid and well-watered eastern US from the semi-arid and arid western US, and this gradient shapes the region's water availability, its ecosystems, and its economies. This climatic boundary is largely set by the influence of two competing atmospheric circulation systems that meet over the Great Plains – the wintertime westerlies bring dominantly dry air that gives way to moist, southerly air transported by the Great Plains low-level jet in the warmer months. Climate model simulations suggest that, as CO2 rises, this low-level jet will strengthen, leading to greater precipitation in the spring but less in the summer and, thus, no change in mean annual precipitation. Combined with rising temperatures that will increase potential evapotranspiration, semi-arid conditions will shift eastward, with potentially large consequences for the ecosystems and inhabitants of the Great Plains. We examine how hydroclimate in the Great Plains varied in the past in response to warmer global climate by studying the paleoclimate record within the Ogallala Formation, which underlies nearly the entire Great Plains and provides a spatially resolved record of hydroclimate during the globally warmer late Miocene. We use the stable isotopes of oxygen (δ18O) as preserved in authigenic carbonates hosted within the abundant paleosol and fluvial successions that comprise the Ogallala Formation as a record of past hydroclimate. Today, and coincident with the modern aridity gradient, there is a sharp meteoric water δ18O gradient with high (−6 ‰ to 0 ‰) δ18O in the southern Great Plains and low (−12 ‰ to −18 ‰) δ18O in the northern plains. We find that the spatial pattern of reconstructed late Miocene precipitation δ18O is indistinguishable from the spatial pattern of modern meteoric water δ18O. We use a recently developed vapor transport model to demonstrate that this δ18O spatial pattern requires air mass mixing over the Great Plains between dry westerly and moist southerly air masses in the late Miocene – consistent with today. Our results suggest that the spatial extents of these two atmospheric circulation systems have been largely unchanged since the late Miocene and any strengthening of the Great Plains low-level jet in response to warming has been isotopically masked by proportional increases in westerly moisture delivery. Our results hold implications for the sensitivity of Great Plains climate to changes in global temperature and CO2 and also for our understanding of the processes that drove Ogallala Formation deposition in the late Miocene.

The early Cretaceous was cold but punctuated by warm snaps resulting from episodic volcanism

The Cretaceous is characterized as a greenhouse climate from elevated atmospheric carbon dioxide concentrations, transgressive seas, and temperate ecosystems at polar paleolatitudes. Here we test the hypothesis that the early Cretaceous was a cold climate state with a new Aptian atmospheric carbon dioxide record from the C3 plant proxy and early Cretaceous sea level curve from stable oxygen isotopes of belemnites and benthic foraminifera. Results show that carbon dioxide concentrations were persistently below 840 ppm during the Aptian, validating recent General Circulation Model simulations of ice sheets on Antarctica at those concentrations. In addition, sea level was estimated to be within the ice sheet window for much of the early Cretaceous prior to the Albian. This background state appears to have been episodically interrupted by Large Igneous Province volcanism followed by long-term carbon burial from weathering. We hypothesize that the early Cretaceous was largely an icehouse punctuated by warm snaps.

Tracing the sources and evaporation fate of surface water and groundwater using stable isotopes of hydrogen and oxygen

Recognizing the origins and movement processes of surface water and groundwater is crucial for understanding hydrochemical genesis, conserving water supplies, and managing water resources. Estimating the source water typically involves identifying the intersection of evaporation line (EL) and meteoric water line. However, there is currently confusion in determining the regional EL and selecting strategies for estimating the source water. This study aimed to explore the source of surface water and groundwater, as well as evaporation effect utilizing stable isotope tracing (δ2H and δ18O). The line-conditioned excess was adopted to differentiate evaporated water and non-evaporated water, then Craig-Gordon model and an analytical framework with Bayesian theory were used to investigate the source of surface water and groundwater and the evaporation influence. The findings revealed that surface water and groundwater in the northern region of the Weihe River suffered more sever evaporation impacts that the south, and the evaporated surface water (7.54 % to 27.34 %) with a wider range of mean evaporation ratio than evaporated groundwater (5.38 % to 8.52 %). Monsoon precipitation is the main contributor to both surface water (contribution ratio: 0.46) and groundwater (0.49) sources. This research provides specific information on evaporation and detailed insights into the source water of surface water and groundwater, aiding in understanding the evaporation effect during the hydrological cycle and facilitating the management of regional water resources.

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).

A guide to precise measurements of isotope abundance by ESI-Orbitrap MS.

Stable isotopes of carbon, hydrogen, nitrogen, oxygen and sulfur are widespread in nature. Nevertheless, their relative abundance is not the same everywhere. This is due to kinetic isotope effects in enzymes and other physical principles such as equilibrium thermodynamics. Variations in isotope ratios offer unique insights into environmental pollution, trophic relationships in ecology, metabolic disorders and Earth history including climate history. Although classical isotope ratio mass spectrometry (IRMS) techniques still struggle to access intramolecular information like site-specific isotope abundance, electrospray ionization-Orbitrap mass spectrometry can be used to achieve precise and accurate intramolecular quantification of isotopically substituted molecules ('isotopocules'). This protocol describes two procedures. In the first one, we provide a step-by-step beginner's guide for performing multi-elemental, intramolecular and site-specific stable isotope analysis in unlabeled polar solutes by direct infusion. Using a widely available calibration solution, isotopocules of trifluoroacetic acid and immonium ions from the model peptide MRFA are quantified. In the second approach, nitrate is used as a simple model for a flow injection routine that enables access to a diverse range of naturally occurring isotopic signatures in inorganic oxyanions. Each procedure takes 2-3 h to complete and requires expertise only in general mass spectrometry. The workflows use optimized Orbitrap IRMS data-extraction and -processing software and are transferable to various analytes amenable to soft ionization, including metabolites, peptides, drugs and environmental pollutants. Optimized mass spectrometry systems will enable intramolecular isotope research in many areas of biology.

Clumped and in situ carbon and oxygen isotopes of calcite as tracers for oxidation of hydrocarbons in deep siliciclastic strata

The oxidation of hydrocarbons, including methane, is part of interrelated hydrogeochemical reactions affecting the carbon budget in Earth’s crust. To investigate these processes in deep siliciclastic strata, we analyzed core samples from Lower Triassic red beds in the Mahu Sag (Junggar Basin, northwest China) by coupling petrological observations with high-resolution in situ secondary ion mass spectroscopy stable carbon and oxygen isotope analyses and clumped isotopes (Δ47) of authigenic calcite. The strata contain variable oil and gas content as well as abundant high-valence Fe and/or Mn oxides. Three sequential generations of cement occur, which are characterized as (1) non-luminescent, early diagenetic calcite (MnO &amp;lt;0.3%, δ13CVPDB [Vienna Peedee belemnite] = −5.6‰ to −4.1‰); (2) bright-orange luminescent late-stage I calcite (0.75%−5.23% MnO, δ13C = −51.4‰ to −25.8‰); and (3) dull-orange late-stage II calcite (4.10%−12.93% MnO, δ13C = −91.4‰ to −30.9‰). Clumped isotopic thermometry reveals that the calcite precipitation temperature increases successively from &amp;lt;40 °C, to 81−107 °C, to finally 107−132 °C, corresponding to three precipitation time periods: before the Late Triassic, from the Early Jurassic to the Early Cretaceous, and from the Early Cretaceous to the present, respectively. δ13C values of −55.7‰ to −25.8‰ indicate that late-stage I calcite is the final product of oxidation of both methane and C2+ hydrocarbons, whereas δ13C values as low as −91‰ indicate that late-stage II calcite is mainly derived from the thermochemical oxidation of methane (δ13C = −46.8‰ to −39.3‰) induced by high-valence Mn and/or Fe oxides. For late-stage I calcite, hydrocarbon oxidation was most likely promoted by high temperatures, although microbial oxidation cannot be completely ruled out. The higher precipitation temperature of late-stage II calcite demonstrates that the oxidation of methane requires higher activation energies than oxidation of C2+ hydrocarbons. We provide reliable geochemical evidence for thermally induced sequential oxidation of hydrocarbons within deep siliciclastic strata.

Modeling the Oxygen Isotope Anomaly (Δ17O) of Reactive Nitrogen in the Community Multiscale Air Quality Model: Insights into Nitrogen Oxide Chemistry in the Northeastern United States.

Atmospheric nitrate, including nitric acid (HNO3), particulate nitrate (pNO3), and organic nitrate (RONO2), is a key atmosphere component with implications for air quality, nutrient deposition, and climate. However, accurately representing atmospheric nitrate concentrations within atmospheric chemistry models is a persistent challenge. A contributing factor to this challenge is the intricate chemical transformations involving HNO3 formation, which can be difficult for models to replicate. Here, we present a novel model framework that utilizes the oxygen stable isotope anomaly (Δ17O) to quantitatively depict ozone (O3) involvement in precursor nitrogen oxides photochemical cycling and HNO3 formation. This framework has been integrated into the US EPA Community Multiscale Air Quality (CMAQ) modeling system to facilitate a comprehensive assessment of NO x oxidation and HNO3 formation. In application across the northeastern US, the model Δ17O compares well with recently conducted diurnal Δ17O(NO2) and spatiotemporal Δ17O(HNO3) observations, with a root mean square error between model and observations of 2.6 ‰ for Δ17O(HNO3). The model indicates the major formation pathways of annual HNO3 production within the northeastern US are NO+OH (46 %), N2O5 hydrolysis (34 %), and organic nitrate hydrolysis (12 %). This model can evaluate NO x chemistry in CMAQ in future air quality and deposition studies involving reactive nitrogen.