Isotopic Composition Of Water Research Articles

A tipping point in stable isotope composition of Antarctic meteoric waters during Cenozoic glaciation.

Triple oxygen isotopes of Cenozoic intrusive rocks emplaced along the Ross Sea coastline in Antarctica, reveal that meteoric-hydrothermal waters imprinted their stable isotope composition on mineral phases, leaving a clear record of oxygen and hydrogen isotope variations during the establishment of the polar cap. Calculated O- and H-isotope compositions of meteoric waters vary from -9 ± 2‰ and -92 ± 5‰ at 40 ± 0.6 Ma, to -30 and -234 ± 5‰ at 34 ± 1.9 Ma, and intersect the modern Global Meteoric Water Line. These isotopic variations likely depict the combined variations in temperature, humidity, and moisture source regions, resulting from rearrangement of oceanic currents and atmospheric cooling during the onset of continental ice cap. Here, we report a paleo-climatic proxy based on triple oxygen geochemistry of crystalline rocks that reveals changes in the hydrological cycle. We discuss the magnitude of temperature changes at high latitudes during the Eocene-Oligocene climatic transition.

CHIRAL SWITCHING CONTROL OF PHARMACEUTICAL SUBSTANCES

Objective: The aim of this study was to demonstrate that chiral switching should be recognized as a widespread phenomenon that extends beyond the production of pure enantiomeric drugs. Methods: To investigate the optical activity of substances from various chemical classes, enantiomers of chiral compounds (Sigma-Aldrich, USA) were chosen: valine and its racemic form (D-valine, L-valine, and racemic valine with optical purity ≥ 99%), L-ascorbic acid (content ≥ 99%), carbohydrates (D-glucose, D-galactose, L-galactose, contents ≥ 99.5%). Solutions were prepared using deuterium-depleted water (DDW–"light" water, D/H=4 ppm), natural deionized high-ohmic water (BD, D/H=140 ppm), and heavy water (99.9% D2O; Sigma-Aldrich). Optical activity was measured using the Atago POL-1/2 polarimeter. Results: One of the components in the racemic medication mixture can act as an inert agent, exhibit toxicity, or undergo undesirable biotransformation mechanisms, resulting in the formation of products with unknown properties. It has been established that a change in the deuterium/protium (D/H) ratio in water leads to a change in the equilibrium and kinetic characteristics of optically active compounds across various chemical classes, such as amino acids, carboxylic acids, and carbohydrates. An inequality was observed in the absolute values of the optical rotation of the L-and D-isomers of valine and galactose, depending on the D/H isotope ratio. The impact of chiral water clusters on optical rotation accounts for the sudden shift in the specific rotation of dilute solutions (less than 0.5%) of L-ascorbic acid in water, based on the D/H ratio. The influence of the isotopic composition of water was confirmed by studying the temperature-dependent mutarotation kinetics of D-glucose and L-and D-galactose in Arrhenius coordinates. The mutarotation process in natural high-resistivity water is characterized by an activation energy (Ea) of 40.8±1.4 kJ mol-1, while in deuterium-depleted water, Ea = 63.6±3.5 kJ mol-1. This results in a kinetic isotope effect for deuterium (KIED) of 1.6. Conclusion: Methodological approaches have been developed to control chiral switching based on the isotopic composition of water in vivo and in vitro. The study of changes in the optical activity of hierarchical structures in the human body, the influence of solvent properties on the mechanisms of optical rotation, as well as the use of KIED values, can be utilized to monitor various chiral transitions in vitro and living organisms.

Authigenic quartz reveals the triple oxygen isotope composition and diagenetic temperature of saline brines

Triple oxygen isotope compositions of authigenic minerals are an emerging tool for the reconstruction of fluid temperatures and the fluid isotopic composition. In this study, we analyzed euhedral authigenic quartz crystals from a halite deposit of the Upper Permian Zechstein evaporitic basin for their triple oxygen isotope composition using laser fluorination isotope ratio mass spectrometry. In the triple oxygen isotope space, additional information, such as the triple oxygen isotope composition of the ambient water, provides insights into equilibrium conditions during quartz formation that cannot be identified from δ18O alone. The triple oxygen isotope composition of authigenic quartz shows, that single oxygen isotope (δ18O) thermometry is not applicable for samples from evaporitic environments, where the fluids' δ18O deviates from dynamic oxygen isotope equilibrium. By combining the Craig and Gordon evaporation model with H2O – SiO2 triple oxygen isotope equilibrium fractionation, we reconstruct the formation temperature of authigenic quartz and the triple oxygen isotope composition of the marine-derived saline brine pore fluid in equilibrium with the quartz. We obtain temperatures of 90 to 130 °C that is interpreted as crystallization temperatures of microcrystalline quartz in pore fluid of halite during burial diagenesis. The triple oxygen isotope composition of authigenic quartz from evaporitic environments is suited as a geochemical tracer for fluid oxygen isotope compositions and ancient fluid or diagenetic temperatures.

Spatial and temporal stable water isotope data from the upper snowpack at the EastGRIP camp site, NE Greenland, sampled in summer 2018

Abstract. Stable water isotopes stored in snow, firn and ice are used to reconstruct climatic parameters. The imprint of these parameters at the snow surface and their preservation in the upper snowpack are determined by a number of processes influencing the recording of the environmental signal. Here, we present a dataset of approximately 3800 snow samples analysed for their stable water isotope composition, which were obtained during the summer season next to the deep drilling site of the East Greenland Ice Core Project in northeast Greenland (75.635411° N, 36.000250° W). Sampling was carried out every third day between 14 May and 3 August 2018 along a 39 m long transect. Three depth intervals in the top 10 cm were sampled at 30 positions with a higher resolution closer to the surface (0–1 and 1–4 cm depth vs. 4–10 cm). The sample analysis was carried out at two renowned stable water isotope laboratories that produced isotope data with the overall highest uncertainty of 0.09 ‰ for δ18O and 0.8 ‰ for δD. This unique dataset shows the strongest δ18O variability closest to the surface, damped and delayed variations in the lowest layer, and a trend towards increasing homogeneity towards the end of the season, especially in the deepest layer. Additional information on the snow height and its temporal changes suggests a non-uniform spatial imprint of the seasonal climatic information in this area, potentially following the stratigraphic noise of the surface. The data can be used to study the relation between snow height (changes) and the imprint and preservation of the isotopic composition at a site with 10–14 cm w.e. yr−1 accumulation. The high-temporal-resolution sampling allows additional analyses on (post-)depositional processes, such as vapour–snow exchange. The data can be accessed at https://doi.org/10.1594/PANGAEA.956626 (Zuhr et al., 2023a).

Different responses of oxygen and hydrogen isotopes in leaf and tree-ring organic matter to lethal soil drought.

The oxygen and hydrogen isotopic composition (δ18O, δ2H) of plant tissues are key tools for the reconstruction of hydrological and plant physiological processes and may therefore be used to disentangle the reasons for tree mortality. However, how both elements respond to soil drought conditions before death has rarely been investigated. To test this, we performed a greenhouse study and determined predisposing fertilization and lethal soil drought effects on δ18O and δ2H values of organic matter in leaves and tree rings of living and dead saplings of five European tree species. For mechanistic insights, we additionally measured isotopic (i.e. δ18O and δ2H values of leaf and twig water), physiological (i.e. leaf water potential and gas-exchange) and metabolic traits (i.e. leaf and stem non-structural carbohydrate concentration, carbon-to-nitrogen ratios). Across all species, lethal soil drought generally caused a homogenous 2H-enrichment in leaf and tree-ring organic matter, but a low and heterogenous δ18O response in the same tissues. Unlike δ18O values, δ2H values of tree-ring organic matter were correlated with those of leaf and twig water and with plant physiological traits across treatments and species. The 2H-enrichment in plant organic matter also went along with a decrease in stem starch concentrations under soil drought compared with well-watered conditions. In contrast, the predisposing fertilization had generally no significant effect on any tested isotopic, physiological and metabolic traits. We propose that the 2H-enrichment in the dead trees is related to (i) the plant water isotopic composition, (ii) metabolic processes shaping leaf non-structural carbohydrates, (iii) the use of carbon reserves for growth and (iv) species-specific physiological adjustments. The homogenous stress imprint on δ2H but not on δ18O suggests that the former could be used as a proxy to reconstruct soil droughts and underlying processes of tree mortality.

Value of long-term isotope monitoring of an index lake for tracking changes in lake water balances across a northern freshwater landscape

Study regionThe Peace-Athabasca Delta, northeastern Alberta, a Ramsar Wetland of International Importance. Study focusTo explore the cause of change in water isotope composition at an ‘index lake’ (δSSL; ‘PAD 18’), a terminal basin where inflow equals evaporation, and the consequences for characterizing lake water balance across a region subject to the same atmospheric conditions. For two decades, water isotope composition at PAD 18 provided a relatively constant, reliable estimate of δSSL, but experienced a pronounced shift in 2020–2021 when average flux-weighted ice-free season relative humidity increased by 4.6% from 66.2% (2015–2019) to 70.8% (2020–2021). Using flux-weighted air temperature and relative humidity data from 2020–2021, an independent calculation of δSSL was determined to be equivalent to the average isotope composition of PAD 18 during 2020–2021. New hydrological insightsResults reveal re-equilibration of the lake water with the atmosphere following the rise of relative humidity readily provides an explanation for the change in isotope composition of PAD 18. We demonstrate the importance of accurate characterization of δSSL, via the index lake method, for isotope-mass balance calculations using evaporation-to-inflow ratios from measurement of water isotope compositions of 61 lakes across the PAD in July 2021. Findings highlight the value of an index lake and appropriate parameterization of isotope-mass balance models for assessment and ongoing monitoring of water balances of nearby lakes, especially amidst future climatic variability.

Extracting paleo-weathering signals from authigenic phases in lake sediments: A case-study of Lake Baikal

Authigenic phases in lake sediments hold the potential to record changes in the isotope compositions of past lake water, potentially yielding valuable information on secular changes in continental weathering patterns and rates, including over past glacial cycles.Here, different leaching approaches are investigated with the aim of extracting Sr, Nd, Pb, and Be hosted in authigenic Fe-Mn (oxy)hydroxide sediment phases for precise isotope measurements. Elemental Al/Mn, Ca/Mn, and P/Mn ratios obtained via a mild reductive leach agree well with the composition of marine authigenic Fe-Mn phases. For core top sediments, leached Sr isotope compositions obtained with this leach agree well with the composition of lake water. The Be and Nd isotope compositions of core top leachates are consistent with the spatial variability observed in the water column. Due to high concentrations in Fe-Mn phases, leachate compositions are dominated by authigenic Be, Sr, Nd, and Pb, even in cases when as much as 40% of leached phases (by mass) are non-authigenic. These lines of evidence suggest that the mild reductive leach successfully extracts the modern lake isotope composition from modern sediments in terms of the isotope systems investigated. We further show that the leaching method is also reliable for older sediments (<340 ka): leached paleo-Sr isotope compositions are consistent between the current and previous interglacial periods, as well as for glacial periods. This suggests that reconstructed water isotope compositions are not affected by early diagenetic processes, instead reflecting environmental factors around the lake that determine the composition of weathering fluxes. Although more difficult to assess for Be, Nd, and Pb due to the heterogeneity of modern lake water, the data we present indicate the overall robustness of the leaching approach.These promising results open up lakes as archives for paleo-weathering reconstructions. Given that marine reconstructions face some important limitations (e.g., integration of basin-wide changes in weathering processes, long residence times for Sr, etc.Fe), lake records provide an avenue to improve our understanding of changes in regional weathering processes over glacial-interglacial timescales. The mild reductive leach used here may also be useful for meteoric Be studies in marine shelf settings, to prevent leaching of terrestrial sedimentary Fe-Mn oxy(hydroxide) phases.

Triple oxygen isotope systematics of CO2 hydroxylation

Kinetic isotope effects occurring during carbonate precipitation impact the accuracy of paleoclimate records. One rate-limiting process is CO2 absorption, which, at high pH, primarily proceeds through hydroxylation, where aqueous CO2 and OH− react to form HCO3−. In this study, we investigated the triple oxygen isotope fractionation (18O/16O and 17O/16O) associated with the hydroxylation reaction. We experimentally determined the extent of the kinetic isotope effects superimposed on the reacting CO2 and OH− during hydroxylation, using high-pH precipitation reactions. These results were compared to the equilibrium triple oxygen isotope fractionation between H2O and OH− modeled using quantum chemical computations.Our quantum chemical modeling confirms the previously suggested equilibrium θeq.H2O/OH- of 0.5296 at 25 °C. Our empirical data show a kinetic isotope effect superimposed on the OH− involved in the hydroxylation reaction of approximately −16.4‰ for the fractionation of 18O/16O and a corresponding slope of 0.514 in triple oxygen isotope space. The θeffectiveH2O/OH- for the fractionation between water and the reacting OH− is 0.523.In order to identify and potentially correct kinetic isotope effects in carbonates, it is important to understand the fractionations occurring during precipitation. Our results enable a more accurate modeling of kinetic isotope effects in triple oxygen isotope space, particularly the slope of hydroxylation. The θhydroxylation is dependent on the isotope composition of the ambient water, CO2, and the temperature. We estimate that θhydroxylation is approximately 0.532 for carbonates growing in 25 °C seawater.

Stable Isotopes Constrain Water Seepage From Gnammas Into Bare Granitic Bedrock

AbstractSubtle bedrock depressions called gnammas allow the water in ephemeral pools to maintain contact with bare rock, thus serving as natural rock‐weathering experiments. Following filling by precipitation, evaporation is often assumed to be the sole process of water loss from gnammas. We evaluated this assumption by monitoring evolving stable isotope compositions of gnamma waters hosted in granite of Colorado's Front Range. Surprisingly, we found that a significant fraction of the water was lost by seepage through the underlying bedrock. Seepage dominated, with only 10%–20% loss by evaporation. We propose a conceptual model of gnamma formation in which enhanced weathering of the bedrock beneath the gnamma increases the water holding capacity and permeability of the underlying rock that in turn promotes efficient water loss through seepage and further weathering of the surrounding rock. This model has implications for bare‐rock weathering and hence the evolution of landscapes over geologic timescales.

Neodymium isotope composition and rare earth element distribution of East Antarctic continental shelf and deep waters

Circumpolar Deep Water (CDW) and Antarctic Bottom Water (AABW) play key roles in the Earth's climate system. Both water masses form critical components of the Antarctic Circumpolar Current and Meridional Overturning Circulation and therefore directly influence the large-scale redistribution of heat, nutrients and carbon. Reconstruction of past CDW transport and AABW production and export has been a key target in palaeoceanography. One promising proxy to achieve this has been the neodymium (Nd) isotope composition of seawater. The biogeochemical processes controlling Nd in the ocean, however, remain underconstrained, and modern observations of Nd isotopes in the Southern Ocean are still geographically limited.To overcome this limitation, 61 seawater samples were collected for Nd isotope and rare earth element (REE) analysis at nine stations along the Wilkes Land continental margin and in the Australian-Antarctic Basin (65°S 125°E) near East Antarctica. The results show that the different water masses have the following Nd isotope characteristics: Antarctic Surface Water (AASW), εNd = −9.0 ± 1.0 (2SD; n = 22); Modified CDW (MCDW), εNd = −8.8 ± 0.8 (2SD; n = 22); AABW, εNd = −8.3 ± 0.5 (2SD; n = 17).There is no evidence of continental REE inputs to surface waters on the Wilkes Land margin. Observed zonal variability of Nd isotope composition in AASW can be attributed to seasonal competition between the poleward flow of warm AASW from the AAG and the westward export of cold surface shelf waters by the Antarctic Slope Current.In terms of deep and bottom waters, mixing of upwelled CDW with AASW and AABW exclusively controls the Nd isotope composition of MCDW, with no indication of boundary processes modifying the Nd isotope composition of MCDW as it encroaches the shelf or slope. The regional Nd isotope signature for AABW is intermediate between published data for the Atlantic sector AABW (εNd = −9.1 ± 0.7) and Pacific sector AABW (εNd = −7.4 ± 0.9). In the absence of active convection, this Nd isotope signature can be explained by a mixture of advected AABW from the Adélie Land coast with a more dominant component of local MCDW and CDW.The data presented in this study constitute the first Nd isotope data set in this part of the Southern Ocean and suggest conservative behaviour of Nd in proximity to the old East Antarctic continent.

Modelling water isotopologues (1H2H16O, 1H217O) in the coupled numerical climate model iLOVECLIM (version 1.1.5)

Abstract. Stable water isotopes are used to infer changes in the hydrological cycle for different climate periods and various climatic archives. Following previous developments of δ18O in the coupled climate model of intermediate complexity, iLOVECLIM, we present here the implementation of the 1H2H16O and 1H217O water isotopes in the different components of this model and calculate the associated secondary markers deuterium excess (d-excess) and oxygen-17 excess (17O-excess) in the atmosphere and ocean. So far, the latter has only been modelled by the atmospheric model LMDZ4. Results of a 5000-year equilibrium simulation under preindustrial conditions are analysed and compared to observations and several isotope-enabled models for the atmosphere and ocean components. In the atmospheric component, the model correctly reproduces the first-order global distribution of the δ2H and d-excess as observed in the data (R=0.56 for δ2H and 0.36 for d-excess), even if local differences are observed. The model–data correlation is within the range of other water-isotope-enabled general circulation models. The main isotopic effects and the latitudinal gradient are properly modelled, similarly to previous water-isotope-enabled general circulation model simulations, despite a simplified atmospheric component in iLOVECLIM. One exception is observed in Antarctica where the model does not correctly estimate the water isotope composition, a consequence of the non-conservative behaviour of the advection scheme at a very low moisture content. The modelled 17O-excess presents a too-important dispersion of the values in comparison to the observations and is not correctly reproduced in the model, mainly because of the complex processes involved in the 17O-excess isotopic value. For the ocean, the model simulates an adequate isotopic ratio in comparison to the observations, except for local areas such as the surface of the Arabian Sea, a part of the Arctic and the western equatorial Indian Ocean. Data–model evaluation also presents a good match for the δ2H over the entire water column in the Atlantic Ocean, reflecting the influence of the different water masses.

Distribution of stable Н, О and С isotopes in natural waters in the area of the Taz oil and gas condensate field (Yamalo-Nenets autonomous region)

Relevance. The study of isotopic composition of water and dissolved substances makes it possible to determine not only their genesis, but also the fractionation processes occurring in the “water–rock–gas–organic matter” system over time, i. e. as different stages of the evolution of water composition pass through. Interest in the groundwater of the Arctic regions of Western Siberia is additionally associated with the widespread occurrence of oil deposits at the depths of formation waters and the possible influence of cryogenic metamorphization processes on composition of near-surface waters. Aim. To study and compare the isotopic composition of oxygen, hydrogen and carbon in natural waters of the Yamalo-Nenets autonomous region to identify conditional isotopic markers, as well as to be able to trace the evolution of the isotopic composition of waters along a vertical section in the area of the Taz oil and gas condensate field. Objects. Surface (river, soil and lake), underground waters of the active water exchange zone of the Yamalo-Nenets autonomous region and formation waters of oil and gas deposits of the Taz field. Methods. The study of the isotopic composition of oxygen, hydrogen, and carbon of water-dissolved carbon dioxide was carried out in the Research Equipment Sharing Center at the Institute of Geology and Mineralogy SB RAS using Isotope Ratio Mass Spectrometer FinniganTM MAT 253 equipped with H/Device and GasBench II for sample preparation. Results and conclusions. The paper introduces the data on isotopic composition of O, H and C for natural waters of the Yamalo-Nenets autonomous region. The authors have determined the characteristic trends in changes in the isotopic composition of water and dissolved carbon dioxide for various water bodies. Surface and underground waters with active water exchange in terms of isotopic composition (δD and δ18О) are infiltration. As water moves down the section, with an increase in the time of interaction of the “water–rock” system and increase in temperatures, the isotopic composition becomes significantly heavier with a slope from the GMWL to the right. The authors compiled the diagram of the evolution of water-dissolved carbon isotopic composition in the region according to the obtained and some literature data. Despite the wide range of δ13C values from –30.4 to 23.6 ‰, there are, obviously, only two sources of carbon dioxide in the region: biogenic and atmospheric, with biogenic being predominant for groundwater.

Rapid decrease of the Labrador Sea’s influence on black spruce ecosystems with distance inland

In eastern Canada, Black spruce (Picea mariana Mill. B.S.P.) grows in a wide variety of climates, from maritime-oceanic conditions near the Labrador Sea, to more continental climates, inland. Along this gradient, timing and provenance of heat and moisture that support growth are uncertain, weakening our capacity to predict the response of boreal ecosystems to climate variability. Here, we measured the stable oxygen isotopic composition of black spruce tree-ring cellulose at three sites in eastern Canada and provide evidence of a rapid decrease of Labrador Sea’s influence on adjacent ecosystems. Our results report a landwards decrease in the oxygen isotope composition of both tree-ring cellulose (δ18OTRC) and precipitation water (δ18Op). We also reveal a rapid landwards decoupling between δ18OTRC variability (1950-2013), maximum temperature and Sea Surface Temperature variations over the Northwest Atlantic. Thus, despite their apparent ecological homogeneity, eastern Canada’s black spruce ecosystems rely on heterogeneous sources of heat and moisture.

Water Uptake Characteristics of Stipa bungeana Trin: Affected by Subsidence in the Coal Mining Areas of Northwest China

Revealing the water use pattern of plants influenced by coal-mining-caused land subsidence is crucial to understand plant–water interactions and guide ecological restoration. However, available information on herbaceous plants, the dominant species in most arid and semi-arid regions with abundant coal resources, remains inadequate. We investigated the water use patterns of Stipa bungeana Trin. by measuring soil water content, root distribution, and stable isotopes of hydrogen (δ2H) and oxygen (δ18O) of soil water and plant stem water both before and after a rainfall event. The results revealed that prior to rainfall, both areas exhibited a low soil water content with no discernible difference in soil drought. However, the soil waters δ2H and δ18O were found to be more enriched at varying depths within the subsidence area, indicating a heightened level of soil evaporation. Both soil water content and soil water isotopic composition responded sensitively to rainfall, with rainfall primarily replenishing the shallow layer (0–20 cm), thereby reflecting an infiltration mode dominated by piston flow. More water seeped into deeper soil layers in the subsidence area compared to the non-subsidence area, with more preferential flow. Before rainfall, the sources of plant water uptake were consistent both at shallow and deep soil layers, implying that the proportion of water uptake gradually decreased with increasing depth. After rainfall, the sources of plant water uptake differed slightly between the two soil layers. The plants in non-subsidence and subsidence areas dominantly extracted soil water at depths greater than 10 cm and 20 cm, respectively. The root system in the subsidence area was more developed than that in the non-subsidence area. Plant water uptake was primarily influenced by the spatial distribution of roots, as well as the post-rainfall water distribution, regardless of whether they were in the subsidence area or not. Although land subsidence affected soil water transport, the water uptake pattern of Stipa bungeana Trin. was similar before and after rainfall, indicating the adaptive growth of plants through their roots in the subsidence area. The high adaptability of herbs such as Stipa bungeana Trin. makes them a viable option for vegetation restoration in subsidence areas. This study has significant implications for evaluating plant–water relationships in subsidence areas due to coal mining, thereby providing a fundamental basis and valuable reference for ecological restoration and management strategies within such affected regions.

Comparative Analysis of Water Isotopic Compositions: Evaluating Isotope Analyzer for Soil and Extraction Method for Stem Water

Stable isotopes of water (δ2H and δ18O) are reliable tracers for the investigation of plant–soil–water interactions in forest ecosystems. However, variations in isotopic compositions may arise due to differences in analytical instruments and water extraction methods. In this study, we conducted three different experiments to identify isotopic differences caused by analytical and methodological variations. First, we analyzed soil water by using the two most commonly applied methods: isotope ratio mass spectrometry (IRMS) and cavity ring-down spectroscopy (CRDS). Second, we compared the isotopes in xylem water extracted from the stems of nine tree species using cryogenic vacuum distillation (CVD) with different heating times. Third, we compared the compositions in xylem water extracted with three different methods: mechanical squeezing using a pressure chamber (PC), an induction module (IM), and CVD. The differences in isotopic composition between IRMS and CRDS were significant but minimal. Soil properties were not significant factors contributing to differences between the two instruments. For the xylem water extraction with CVD, each of the nine tree species required heating for more than three hours. Significant differences were observed in δ2H among the three extraction methods for xylem water. Xylem water extracted by CVD showed more depleted values compared to those obtained by PC and IM. Our results highlight the importance of considering analytical and methodological variations in stable isotope analysis.

Shallow and deep groundwater moderate methane dynamics in a high Arctic glacial catchment

Glacial groundwater can mobilize deep-seated methane from beneath glaciers and permafrost in the Arctic, leading to atmospheric emissions of this greenhouse gas. We present a temporal, hydro-chemical dataset of methane-rich groundwater collected during two melt seasons from a high Arctic glacial forefield to explore the seasonal dynamics of methane emissions. We use methane and ion concentrations and the isotopic composition of water and methane to investigate the sources of groundwater and the origin of the methane that the groundwater transports to the surface. Our results suggest two sources of groundwater, one shallow and one deep, which mix, and moderate methane dynamics. During summer, deep methane-rich groundwater is diluted by shallow oxygenated groundwater, leading to some microbial methane oxidation prior to its emergence at the surface. Characterization of the microbial compositions in the groundwater shows that microbial activity is an important seasonal methane sink along this flow-path. In the groundwater pool studied, we found that potential methane emissions were reduced by an average of 29% (±14%) throughout the summer due to microbial oxidation. During winter, deep groundwater remains active while many shallow systems shut down due to freezing, reducing subsurface methane oxidation, and potentially permitting larger methane emissions. Our results suggest that ratios of the different groundwater sources will change in the future as aquifer capacities and recharge volumes increase in a warming climate.

Complexity of Arctic Ocean water isotope (δ18O, δ2H) spatial and temporal patterns revealed with machine learning

The stable isotope compositions of water (δ18O, δ2H, deuterium-excess) are important tracers that help illuminate the changing Arctic water cycle and how Arctic-sourced water can influence lower latitudes. We present simultaneous boundary layer water vapor and ocean water isotope data that were measured continuously in the western Arctic Ocean. Sea surface water isotopes varied between the shallower continental Chukchi Shelf and the deeper Chukchi Borderlands to the north. The Chukchi Borderlands surface waters were less saline than the offshore Chukchi Shelf, as the Borderlands are influenced by greater sea ice cover and contribution of sea ice melt to surface freshwater. This greater contribution of sea ice melt resulted in lower deuterium-excess (δ2H − 8*δ18O) in surface water values in the deeper Chukchi Borderlands than on the shallower Chukchi Shelf. Additionally, the sea ice melt contributions to freshwater were less prominent than river runoff, but freshwater from both sources decreased substantially below 70 m depth in the Chukchi Borderlands. Our observed water isotope values provided the foundation for producing water isotope maps (isoscapes) based on remote sensing and machine learning which incorporate parameters that can influence ocean circulation and thus water isotopes (e.g., salinity, sea surface temperature, water depth). These isoscapes suggest spatial complexity in the distribution of stable water isotopes in the Arctic, including sharp gradients in the distribution of the isotopes in seawater that were studied. These isoscapes can be improved in future iterations, for example, with the availability of more spatially continuous, remotely sensed oceanic variables or continuous ship-based measurements to use as additional predictors. As a result, the generation of these isoscapes could become a useful tool for understanding the past, present, and future Arctic water cycle in the context of the global hydrologic cycle.

Pushing the limits of C3 intrinsic water use efficiency in Mediterranean semiarid steppes: Responses of a drought‐avoider perennial grass to climate aridification

Abstract Intrinsic water use efficiency (WUEi) reflects the trade‐off between photosynthetic carbon gain and water loss through stomatal conductance and is key for understanding dryland plant responses to climate change. Stipa tenacissima is a perennial tussock C3 grass with an opportunistic, drought‐avoiding water use strategy that dominates arid and semiarid steppes across the western Mediterranean region. However, its ecophysiological responses to aridification and woody shrub encroachment, a major land‐use change in drylands worldwide, are not well‐understood. We investigated the variations in leaf stable isotopes (δ18O, δ13C, δ15N), nutrient concentrations (N, P, K), and culm water content and isotopic composition (δ18O, δ2H) of paired pure‐grass and shrub‐encroached S. tenacissima steppes along a 350 km aridity gradient in Spain (10 sites, 160 individuals). Culm water isotopes revealed that S. tenacissima is a shallow‐rooted grass that depends heavily on recent rainwater for water uptake, which may render it vulnerable to increasingly irregular rainfall combined with faster topsoil drying under climate warming and aridification. With increasing aridity, S. tenacissima enhanced leaf‐level WUEi through more stringent stomatal regulation of plant water flux and carbon assimilation (higher δ13C and δ18O), reaching exceptionally high δ13C values (−23‰ to −21‰) at the most arid steppes. Foliar N concentration was remarkably low across sites regardless of woody shrub encroachment, evidencing severe water and N co‐limitation of photosynthesis and productivity. Shrub encroachment decreased leaf P and K but did not affect S. tenacissima water status. Perennial grass cover decreased markedly with both declining winter rainfall and shrub encroachment suggesting population‐level rather than individual‐level responses of S. tenacissima to these changes. The fundamental physiological constraints of photosynthetic C3 metabolism combined with low foliar N content may hamper the ability of S. tenacissima and other drought‐avoider species with shallow roots to achieve further adaptive improvements in WUEi under increasing climatic stress. A drought‐avoiding water use strategy based on early stomatal closure and photosynthesis suppression during prolonged rainless periods may thus compromise the capacity of semiarid S. tenacissima steppes to maintain perennial grass cover, sustain productivity and cope with ongoing climate aridification at the drier parts of their current distribution. Read the free Plain Language Summary for this article on the Journal blog.

Water isotopic composition traces source and dynamics of water supply in a semi‐arid agricultural landscape

AbstractChanges in seasonality and form of precipitation alter the structure and function of grassland and steppe ecosystems and pose challenges for land management and crop production in regions like the Northern Great Plains, North America. This research uses isotopic composition of water (δ18O and δ2H) to explore the sources and fate of soil water in lower‐elevation agricultural areas of the Judith River watershed, in the headwaters of the Missouri River, USA. Extensive non‐irrigated cereal crop production in this area occurs on well‐drained soils and depends on careful water management. Our observations indicate that colder precipitation contributes isotopically distinct water to cultivated terrace soils relative to downgradient groundwaters and streams. Riparian waters also exhibit a higher fraction of contributions from colder precipitation relative to terrace groundwaters and streams. Apparent contributions from colder precipitation in terrace and riparian soil waters suggest that snowmelt is a key component of the water supply to these systems. Riparian waters also show evidence of evaporation suggesting that water spends sufficient time in some ponds and open channels in the riparian corridor to reflect fractionation by evaporation. The evolution of water isotopic composition from soils to shallow aquifers to stream corridors indicates source water partitioning as precipitation moves through this semi‐arid agricultural landscape. The apparent mixing processes evident in this evolution reveal source water dynamics that are necessary to understand plant transpiration, solute processing, and contaminant leaching processes.

Subaqueous carbonate speleothems as paleotemperature archives – clumped isotope thermometry and stable isotope compositions of inclusion-hosted water

Clumped isotope measurements of carbonates and stable isotope analyses of water trapped in fluid inclusions are both promising techniques to determine carbonate formation temperatures. Cave-hosted carbonate deposits (speleothems) are excellent targets for such studies, but kinetic fractionations and diagenetic influences frequently deteriorate the temperature data obtained from these methods. However, subaqueous carbonate deposits may provide reliable data, as kinetic fractionations are less significant in underwater environments. In this study, subaqueous speleothems, whose formation temperatures were directly measured in the water, were investigated. Additionally, temperatures calculated from the oxygen isotope fractionations between calcite and fluid inclusion-hosted water were compared with clumped isotope temperatures obtained for subaqueous carbonate formations in cave-hosted lakes. The clumped isotope temperatures fit the measured and calculated fluid inclusion temperatures within the analytical precisions. Carbonate deposits formed at elevated temperatures (~50°C or above) may undergo post-formational calcite-water oxygen isotope exchange, altering the composition of the inclusion-hosted water. In contrast, subaqueous speleothems formed at about 20-25°C appear to preserve the primary isotopic compositions. Our study shows that subaqueous carbonate speleothems are useful targets for clumped isotope and inclusion water analyses, making them valuable paleotemperature archives.