Isotopic Composition Of Water Research Articles

Stable water isotopic composition and evaporation to inflow ratios for high-mountain tropical Ecuadorian lakes

ABSTRACT In this study, we explore the utility of stable isotopes of water (δ2H and δ18O) as integrative proxies for evaporative condition in high-mountain tropical lakes using a set of small Ecuadorian lakes in the Cajas National Park. Specifically, we (1) characterize the variability of stable water isotopic composition across several lakes of varying size and depth and (2) determine the evaporation as a fraction of inflow using stable isotopes of water for these lakes. We have used the Hydrocalculator tool for estimation of the evaporation to inflow (E/I) ratio. Results indicated that larger lakes have lower seasonal variability in isotopic composition across their depth compared with the smaller lakes. Further, there was clear seasonal variation across the monthly E/I ratios estimated in several lakes, indicating that evaporation likely plays some (albeit limited) role in the water level variability experienced within a year.

Variations in water use strategies of Tamarix ramosissima at coppice dunes along a precipitation gradient in desert regions of northwest China

IntroductionThe precipitation pattern has changed significantly in arid desert areas, yet it is not clear how the water use strategies of Tamarix ramosissima Ledeb. on coppice dunes along a natural precipitation gradient are affected.MethodsIn this study, the hydrogen and oxygen isotope compositions of xylem water, soil water, precipitation, and groundwater were measured by stable isotope techniques in Huocheng, Mosuowan, and Tazhong. Additionally, the water use strategies of natural precipitation gradient were investigated in conjunction with the MixSIAR model.ResultsThe results indicated that the water sources of T. ramosissima exhibited significant variation from semi-arid to hyper-arid areas. In semi-arid areas, T. ramosissima mainly absorbed shallow, shallow-middle, and middle soil water; however, T. ramosissima shifted its primary water sources to middle and deep soil water in arid areas. In hyper-arid areas, it mainly utilized deep soil water and groundwater. In contrast, the water source contribution rate of T. ramosissima exhibited relative uniformity across each layer in an arid area. Notably, in hyper-arid areas, the proportion of groundwater by T. ramosissima was significantly high, reaching 60.2%. This is due to the relatively shallow groundwater supplementing the deep soil water content in the area. In conclusion, the proportion of shallow soil water decreased by 14.7% for T. ramosissima from semi-arid to hyper-arid areas, illustrating the occurrence of a gradual shift in potential water sources utilized by T. ramosissima from shallow to deep soil water and groundwater.DiscussionTherefore, T. ramosissima on coppice dunes shows flexible water use strategies in relation to precipitation and groundwater, reflecting its strong environmental adaptability. The findings hold significant implications for the conservation of water resources and vegetation restoration in arid areas.

Water-use characteristics of Populus euphratica trees in response to flood and groundwater depth in desert oasis

Populus euphratica, as the dominant species in arid desert area, plays an important role in maintaining the stability of desert ecosystem. However, P. euphratica water-use characteristics at different sizes and the effects of flooding and groundwater depth on water use remain unclear. In this study, the hydrogen and oxygen isotope compositions of xylem water, soil water, and floods were measured and coupled with the MixSIAR model to investigate the water-use patterns of P. euphratica at different sizes, flood periods (before, during, and after floods), and groundwater depths in the Taklimakan Desert hinterland. The carbon isotope composition of P. euphratica leaves was determined to investigate the water-use efficiency (WUE) of P. euphratica. The water-use patterns of P. euphratica at different sizes were consistent because of its reproductive mode (aswxual root tiller reproduction). P. euphratica showed a greater degree of ecological plasticity during different flood periods. Before the flood, the main water sources for P. euphratica were deep-soil-layer (140–220 cm) and near-groundwater-layer (220–300 cm). During the flood, it could absorb the flood directly, reducing water absorption from deep-soil-layer and near-groundwater-layer. After the flood, it resumed water absorption from deep-soil-layer and near-groundwater-layer. P. euphratica water absorption patterns differed at different groundwater depths. In the shallow and middle groundwater depth sample plots, the water sources were the deep-soil and near-groundwater layers, and the population of P. euphratica grew well. In the deep sample plot, water absorption was mainly near the groundwater layer, and the P. euphratica population showed a decreasing trend, further explaining the degradation of P. euphratica in terms of water-use patterns. WUE is related to the growth stage of P. euphratica and the water conditions of the living environment; the more mature the P. euphratica, the more deficit the water conditions, and the higher the WUE. This study provides a basis for maintaining the stability of P. euphratica forests in arid deserts and for water allocation.

The Use of the Characteristics of Water Isotopic Composition for Assessing the Contribution of Winter and Summer Precipitation to the Upper Ob Runoff during the Open-Water Period

The Use of the Characteristics of Water Isotopic Composition for Assessing the Contribution of Winter and Summer Precipitation to the Upper Ob Runoff during the Open-Water Period

Late Quaternary hydroclimate variability in Madagascar and its connection to atmospheric circulation patterns

Large uncertainties still exist about the long-term mechanisms influencing the hydroclimate variability of southeast Africa where proxy data and model simulations indicate rainfall dipoles between subtropical and tropical areas. The topography of Madagascar, located off the southeastern coast of Africa, modulates these dipoles while its climate is influenced by the position of the Intertropical Convergence Zone (ITCZ) and the Subtropical High as well as the sea surface temperature (SST) of SW Indian Ocean. The island can thus be considered a key location for the understanding of the tropical SE African climatic variability and the interplay between atmospheric patterns. However, the scarcity of continuous records from Madagascar has made the evolution of regional late Quaternary climate and its driving mechanisms difficult to assess. Here, we present a 26-kyr record of the deuterium/hydrogen isotope ratio (δD) of biomarkers (n-alkanes) from the central eastern part of the island at Antananarivo at around 1250 m a.s.l. Preliminary summary pollen data are also presented as a comparison. The δD profiles of aquatic plant and terrestrial plant-derived n-alkanes generally exhibit similar trends implying that they all record changes in the isotope composition of source water, namely meteoric water that recharges soil and lake waters. In this tropical region, the δD variability of precipitation is mainly influenced by the amount effect reflecting the intensity of precipitation associated with the monsoon. We observe: (i) stable and wet conditions during the Last Glacial Maximum, (ii) drier conditions from 18.5 to 15 ka (ka before present) during the Heinrich Stadial 1 (iii) high humidity after 15 ka culminating at the Younger Dryas (YD), (iv) drier conditions from 11.7 ka to 8.2 ka, (v) a return to humid climate until 2.8 ka, and (vi) an arid phase followed by increased wetness after 0.9 ka, although the record is likely influenced by human-induced vegetation changes the last 1.2 ka. This climate signal is similar to other records from the Mozambique Channel but opposite to records from the East African mainland and the subtropical southern Africa, especially between 20 and 25°S. Although there is a good correspondence of our record with insolation- driven migrations of ITCZ during the LGM and the early Holocene, the dipoles are largely consistent with the modern rainfall anomaly and are best explained by the interlinked effects of the SST changes and the variability of the Mozambique Channel Trough.

Identification of a primordial high D/H component in the matrix of unequilibrated ordinary chondrites

Deuterium to hydrogen isotope ratios in unequilibrated ordinary chondrites (UOCs) which have undergone little-to-no thermal metamorphism pose an interesting problem when looking at water in the early Solar System. Bulk chondrite studies have shown that UOCs of the lowest subtypes have D/H ratios as high as comets from the outer Solar System, which, along with bulk UOC water abundances, decrease with thermal metamorphism. Since bulk UOC analyses represent a complex mixture of organic and hydrated phases, it is not clear what phase(s) is responsible for the high bulk D/H values. In this study, we report in situ secondary ion mass spectrometry (SIMS) measurements of the H isotope composition of the fine-grained matrix of UOCs with petrological subtypes ranging from 3.00 to 3.9. We find that for matrix areas in UOCs of petrologic subtype ≥3.2, correlations between D-rich organic material and D-poor phyllosilicates give relatively D-poor intrinsic water isotopic compositions, with δD values between −320 ± 91 ‰ and −71 ± 71 ‰, which are inherited from parent body accretion. Therefore, we conclude that OC parent bodies accreted D-poor water ice that had an H isotopic composition similar to that of CM and CV chondrite parent bodies. We find that matrix in UOCs of the lowest subtypes (Semarkona, Bishunpur, and Ngawi) show similar water and organic H isotope compositions to higher type UOCs. Our in situ analyses also show that matrix areas in these pristine UOCs contain a third, thus far unidentified, component that carries the high D/H signature, with δD values up to ∼6000 ‰. We propose that this component is pristine amorphous silicates preserved from the molecular cloud or early protoplanetary disc that is extremely sensitive to thermal and aqueous alteration on asteroidal parent bodies.

Reflection of Daily, Seasonal and Interannual Variations in Run-Off of a Small River in the Water Isotopic Composition (δ2H, δ18O): A Case of the Ala-Archa Mountain River Basin with Glaciation (Kyrgyzstan, Central Asia)

Small intermountain river basins are most suitable for developing new methods to estimate water balance due to their well-defined catchment boundaries, relatively rapid runoff processes, and accessible landscapes for study. In general terms, dissecting the hydrograph of a small mountain river requires calibration of the flow model against multi-year data sets, including (a) glacier mass balance and snow water content, (b) radiation balance calculation, (c) estimation of the groundwater contribution, and (d) water discharge measurements. The minimum primary data set is limited to the precipitation and temperature distributions at the catchment. This approach postulates that the conditions for the formation of all components of river flow are known in advance. It is reduced to calculating the dynamic balance between precipitation (input part) and runoff, ablation, and evaporation (output part). In practice, accurately accounting for the inflow and outflow components of the balance, as well as the impact of regulating reservoirs, can be a challenging task that requires significant effort and expense, even for the extensively researched catchments. Our studies indicate the potential benefits of an approach based on one-time, but detailed, observations of stable isotope composition, temperature, and water chemistry, in addition to standard datasets. This paper presents the results of the 2022–2023 work conducted in the basin of the small mountain river Ala-Archa, located on the northern slope of the Kyrgyz Range in Tien-Shan, which was chosen as an example due to its well-studied nature. Our approach could identify previously unknown factors of flow formation and assess the time and effectiveness of work in similar conditions.

Fluid Chemical and Isotopic Signatures Insighting the Hydrothermal Control of the Wahongshan-Wenquan Fracture Zone (WWFZ), NE Tibetan Plateau

Compared to the southern Tibetan Plateau, the northern part has been regarded as relatively lacking geothermal resources. However, there is no lack of natural hot springs exposed in beads along large-scale fracture systems, and research on them is currently limited to individual hot springs or geothermal systems. This paper focuses on the Wahongshan-Wenquan Fracture Zone (WWFZ), analyzes the formation of five hydrothermal activity zones along the fracture zone in terms of differences in hot water hydrochemical and isotopic composition, and then explores the hot springs’ hydrothermal control in the fracture zone. The results show that the main fractures of the WWFZ are the regional heat control structures, and its near-north–south- and near-east–west-oriented fractures form a fracture system that provides favorable channels for deep hydrothermal convection. Ice and snow meltwater from the Elashan Mountains, with an average elevation of more than 4,500 m above sea level, infiltrates along the fractures, and is heated by deep circulation to form deep geothermal reservoirs. There is no detectable mantle contribution source heat to the hot spring gases, and the heat source is mainly natural heat conduction warming, but the “low-velocity body (LVB)” in the middle and lower crust may be the primary heat source of the high geothermal background in the area. The hot springs’ hydrochemical components show a certain regularity, and the main ionic components, TDS, and water temperature tend to increase away from the main rupture, reflecting the WWFZ controlling effect on hydrothermal transport. In the future, the geothermal research in this area should focus on the hydrothermal control properties of different levels, the nature of fractures, and the thermal contribution of the LVB in the middle and lower crust.

Oven Design for In‐Situ Thermal Extraction of Volatiles From Lunar Regolith

AbstractExtracting volatiles from lunar regolith for analysis or utilization is one of the most important aspects of future lunar exploration. However, the low thermal conductivity of lunar regolith poses a challenge. Here, we conduct simulations to analyze the heat and mass transfer processes within the sample inside the oven. We identify three main factors affecting oven heat‐up rate: water ice content (WIC) in the regolith, oven diameter, and power supply. Taking these factors into account, we devise an oven design and apply it to three case studies: (a) assessing water ice and isotopic composition in Permanently Shadowed Regions, akin to Chang'e‐7 mini‐fly probe missions; (b) measuring noble gases, as Chang'e‐7 and Luna‐27 landers; and (c) large‐scale in‐situ resources utilization (ISRU). The simulation results indicate that water ice can be extracted using sufficiently high heating power without issues. However, the complete extraction of noble gases is challenging and may require alternative heating methods. For ISRU purposes, large ovens can be subdivided into smaller ones by adding internal structures, for example, honeycomb, to improve the heat‐up rate by at least 1.5 times. Additionally, we find that the oven can serve as a scientific payload for WIC measurement using the heating curve. A flowchart of this new WIC measurement method is provided, offering an alternative method to mass spectrometry or spectroscopy measurements.

Nitrogen Assimilation and Nitrification in Surface Waters of the Amazon and Pará Estuaries

AbstractUnder increasing anthropogenic impacts, the hydrology, weathering, turbidity, and biogeochemistry of the Amazon and Pará river catchments are changing, potentially affecting the concentration and speciation of nitrogen (N) entering the estuary, as well as the subsequent primary productivity. Primary production and several N‐cycling rates have been studied in the northern river plume, and new studies focusing on specific processes in the river mouth emerged. Yet, a general overview is still lacking. For the first time, we provide an overview of primary production along with nitrification, ammonium (NH4+), nitrate (NO3−), and amino acid uptake rates in the Amazon and Pará river mouths which exhibit different degrees of catchment land use. Our results indicate that the Amazon supplies tenfold more NH4+ and NO3−, and its nitrification rates are four times higher than in the Pará River. The stable isotope composition of ambient water and NO3− confirmed that nitrification is a dominant pathway, with fluxes reaching 8.5 × 108 mol N d−1 in the Amazon. Nutrients are transported to regions with reduced turbidity and little nitrification, facilitating NH4+ (0.2–2.4 × 108 mol N d−1) and carbon uptake (4.6 and 14.0 × 108 mol C d−1 in the Pará and the Amazon, respectively) by phytoplankton. The lower N‐cycling rates measured in the Pará relative to the Amazon River mouth likely originate from differences in river discharge and watershed characteristics.

Isotope Hydrograph Separation Reveals Rainfall on the Glaciers Will Enhance Ice Meltwater Discharge to the Himalayan Rivers

AbstractThe Indian Summer Monsoon (ISM) and meltwater from the Himalayan are the two most important sources of water in the Indian subcontinent. However, the impact of ISM on Himalayan glaciers and subsequent stream hydrology remains largely unknown. To provide new insight into the impact of rainfall on glacial hydrology, here we present hydro‐meteorological and time‐series observations of meltwater stable water isotope compositions from the snout of the Chorabari glacier in the Upper Ganga Basin, Central Himalayas across the ablation season corresponding to 2019. We observe that rainfall events (>2 mm d−1) on the glacier enhance discharge driven by ice meltwater in River Mandakini. Energy balance calculations reveal that one of the drivers behind enhanced ice meltwater contribution could be rain‐induced melting of the glacier where rainfall on the ice surface melts the glacier producing up to 13% of the total discharge at the glacier snout. Further, rainfall on glacier surface have other control on glacial processes—for example, snow metamorphism, ice flow dynamics such as short‐term acceleration in ice speed flow, and reorganization of the englacial and subglacial drainage network—that are poorly studied and needs further investigation. We conclude rainfall events on the glacier have a complex control on mountain hydrology. This study, therefore, provides an interpretative framework that calls for additional assessments of the direct and indirect impact of rainfall in glacial hydrology.

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.

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.

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.