Water Isotope Fractionation Research Articles

Variation and fractionation of δ2H, δ18O, and δ17O stable isotopes from irrigation water to soil, grapes, and wine for the traceability of geographical origins

To investigate the variation and fractionation of stable isotopes from irrigation water to soil, grapes, and wine, δ2H, δ18O, and δ17O in different samples from 10 regions in China were determined using a water isotope analyser. The values were significantly different among regions according to the chemometric analysis. All isotopes were significantly and positively correlated with irrigation water–soil and grape–wine. A significant water isotopic fractionation effect was observed from the irrigation water to the soil, grapes, and wine. Stable isotope distribution characteristics correlated with longitude, latitude, altitude, temperature, precipitation, station pressure and wind speed. The linear discriminant analysis (LDA), random forest (RF), support vector machine (SVM), and feed-forward neural network (FNN) models 58.33–100 %, 80–100 %, 53.33–100 %, and 73.33–100 % accurate for distinguishing the geographical origins of all samples from training and test data, respectively. These findings provide a theoretical basis for authenticating the geographic origin of Chinese wines using stable isotope analysis.

Drivers of δ18O Variability Preserved in Ice Cores From Earth's Highest Tropical Mountain

AbstractIn 2019, four ice cores were recovered from the world's highest tropical mountain, Nevado Huascarán (Cordillera Blanca, Peru; 9.11°S, 77.61°W). Composite hydroclimate records of the two Col cores (6,050 masl) and the two Summit cores (6,768 masl) are compared to gridded gauge‐analysis and reanalysis climate data for the most recent 60‐year. Spatiotemporal correlation analyses suggest that the ice core oxygen stable isotope (δ18O) record largely reflects tropical Pacific climate variability, particularly in the NINO3.4 region. By extension, the δ18O record is strongly related to rainfall over the Amazon Basin, as teleconnections between the El Niño Southern Oscillation and hydrological behavior are the main drivers of the fractionation of water isotopes. However, on a local scale, modulation of the stable water isotopes appears to be more closely governed by upper atmospheric temperatures than by rainfall amount. Over the last 60 years, the statistical significance of the climate/δ18O relationship has been increasing contemporaneously with the atmospheric and oceanic warming rates and shifts in the Walker circulation. Isotopic records from the Summit appear to be more sensitive to large‐scale temperature changes than the records from the Col. These results may have substantial implications for modeling studies of the behavior of water isotopes at high elevations in the tropical Andes.

Hydrogen and Oxygen Isotope Fractionation Effects in Different Organ Tissues of Grapes under Drought Conditions.

A study of different grapevine tissues and organs (root, stem, leaf, fruit) water isotope fractionation models from high-quality wine grapes produced in the Helan Mountains, a key wine-producing area in northwestern China, was undertaken. Results showed that δ2H values of local groundwater sources were more negative than rivers and precipitation. Soil water δ2H and δ18O values were significantly higher than those of other environmental water sources. Water from the soil surface layer (0-30 cm, δ2H and δ18O values) was more positive than the deeper layer (30-60 cm), indicating that soil water has undergone a positive fractionation effect. δ2H and δ18O values of tissues and organs from different grape varieties followed a similar pattern but were more negative than the local atmospheric precipitation line (slope between 4.1 to 5.2). The 2H and 18O fractionation relationship in grapevine organs was similar, and 18O has a higher fractionation effect than 2H. δ2H and δ18O values showed a strong fractionation effect during the transportation of water to different grape organs (trend of stem > fruit > leaf). This study showed that 18/16O fractionation in grapes is more likely to occur under drought conditions and provides a theoretical basis to improve traceability accuracy and origin protection of wine production areas.

Construction and testing of a low-cost device for the collection of rainfall samples destined for stable isotope analysis

Oxygen- and hydrogen-isotope ratios in rainfall provide important hydroclimatic information, yet despite a global network of rainfall isotope measurements, significant geographical gaps exist in data coverage, with only three long-term stations spanning the southern African region. Project-based, ad hoc collections of rainfall for isotope analysis can improve this coverage. However, all rainfall samples that are destined for stable isotope analysis must be collected in such a way to avoid evaporation and resultant isotope fractionation. While such rainwater collectors are available commercially, both the product and shipping are prohibitively costly. We describe the construction of a simple rainfall collector using a design from the literature and materials that are readily available in South African hardware stores. Our rainwater collector can be constructed for the much lower cost of just under ZAR820 in comparison with the cost of ZAR9300 inclusive of shipping from commercial outlets (2022 prices). Our design modifications have the added advantage of portability, with the rainwater collector housed in a bucket with a handle. The device was tested by comparing its performance, in terms of evaporative water loss and isotopic fractionation, with that of an open bottle, using tap water in both cases. Testing confirmed that the collector prevented evaporation over a one-week period, indicating that it is suitable for weekly or more frequent sampling of rainfall. Although the design described was based on materials procured in South Africa, it could easily be adapted for construction elsewhere. Significance: Hydrogen and oxygen isotope composition of rainfall provides valuable climatic information. Rainwater collectors for stable isotope samples must prevent evaporation, as evaporation will alter the isotopic signature. We describe the construction and testing of a bespoke, low-cost and portable device that can be used to collect rainfall samples destined for oxygen- and hydrogen-isotope analysis without significant evaporation.

An Improved Craig–Gordon Isotopic Model: Accounting for Transpiration Effects on the Isotopic Composition of Residual Water during Evapotranspiration

Evapotranspiration (ET) is a crucial process in the terrestrial water cycle, and understanding its stable isotopic evolution is essential for comprehending hydrological processes. The Craig–Gordon (C-G) model is widely used to describe isotopic fractionation during pure evaporation. However, in natural environments, ET involves both transpiration (T) and evaporation (E), and the traditional C-G model does not account for the effect of transpiration on isotopic fractionation. To address this gap, we propose the evapotranspiration-unified C-G (ET-UCG) model, which extends the C-G model by incorporating transpiration’s effect on water isotopes. We verified the validity of the ET-UCG model by comparing its simulation results with the traditional C-G model’s discrete results for a special scenario that simulated the isotopic evolution of residual water after daily transpiration consumption. Further, we simulated two different ET process scenarios using the ET-UCG model to investigate transpiration’s effect on the residual water’s isotopic composition. Our numerical experiments show that transpiration indirectly affects the degree of water isotope fractionation by reducing the true evaporation ratio, even though it does not directly produce isotope fractionation. Therefore, the isotopic composition of residual water estimated by the ET-UCG model is consistently lighter than that estimated using the traditional C-G model in the simulation of ET. Despite different T/ET conditions, the isotopic evolution process follows the same evaporation line. These results highlight the importance of considering transpiration effects when using the C-G model and provide valuable insights into ET processes with potential applications in the field.

Below‐cloud evaporation effect on stable water isotopes in precipitation at the eastern margin of Qinghai‐Tibet Plateau

AbstractQuantitatively assessing the evaporation‐caused stable water isotope fractionation in precipitation below the cloud base is of great significance to understand the modern hydrological circulation especially in a plateau climate. Based on the hourly meteorological data at eight meteorological stations of the Gannan Plateau at the eastern margin of Qinghai‐Tibet Plateau in 2020, we examined the spatial and temporal variations of below‐cloud evaporation effect on precipitation isotopes, and then discussed the factors influencing the below‐cloud evaporation across the Gannan Plateau. The contemporary observation of precipitation isotopes at one site in the Gannan Plateau is also applied to understand the local meteoric water line associated with the below‐cloud evaporation. From 9:00 to 21:00 Beijing Time, the impact of below‐cloud evaporation is greater than that during the rest periods. Within the study region, the below‐cloud evaporation in the central area is usually stronger than that of the surrounding area. The diurnal and monthly variability of relative humidity is highly consistent with that of the remaining raindrop mass fraction after evaporation as well as the isotope variation in raindrop below the cloud base. When the relative humidity is greater than 95%, there is a linear relationship between the remaining raindrop mass fraction and the below‐cloud deuterium‐excess variation of approximate 1.1‰/%. Global warming will increase the below‐cloud evaporation effect across the Gannan Plateau. The findings are useful to understand the below‐cloud evaporation and isotope fractionation under a plateau climate.

Modeling the dynamic behavior of a droplet evaporation device for the delivery of isotopically calibrated low-humidity water vapor

Abstract. A model is presented that gives a quantitative description of the dynamic behavior of a low-humidity water vapor generator in terms of water vapor concentration (humidity) and isotope ratios. The generator is based on the evaporation of a nanoliter-sized droplet produced at the end of a syringe needle by balancing the inlet water flow and the evaporation of water from the droplet surface into a dry-air stream. The humidity level is adjusted by changing the speed of the high-precision syringe pump and, if needed, the dry-air flow. The generator was developed specifically for use with laser-based water isotope analyzers in Antarctica, and it was recently described in Leroy-Dos Santos et al. (2021). Apart from operating parameters such as temperature, pressure, and water and dry-air flows, the model has as “free” input parameters: water isotope fractionation factors and the evaporation rate. We show that the experimental data constrain these parameters to physically realistic values that are in reasonable to good agreement with available literature values. With the advent of new ultraprecise isotope ratio spectrometers, the approach used here may permit the measurement of not only the evaporation rate but also the effective fractionation factors and isotopologue-dependent diffusivity ratios, in the evaporation of small droplets.

First-Principles Diffusivity Ratios for Atmospheric Isotope Fractionation on Mars and Titan.

Recent work used the kinetic theory of molecular gases, along with state-of-the-art intermolecular potentials, to calculate from first principles the diffusivity ratios necessary for modeling kinetic fractionation of water isotopes in air. Here, we extend that work to the Martian atmosphere, employing potential-energy surfaces for the interaction of water with carbon dioxide and with nitrogen. We also derive diffusivity ratios for methane isotopes in the atmosphere of Titan by using a high-quality potential for the methane-nitrogen pair. The Mars calculations cover 100 K to 400 K, while the Titan calculations cover 50 K to 200 K. Surprisingly, the simple hard-sphere theory that is inaccurate for Earth's atmosphere is in good agreement with the rigorous results for the diffusion of water isotopes in the Martian atmosphere. A modest disagreement with the hard-sphere results is observed for the diffusivity ratio of CH3D in the atmosphere of Titan. We present temperature-dependent correlations, as well as estimates of uncertainty, for the diffusivity ratios involving HDO, H2 17O, and H2 18O in the Martian atmosphere, and for CH3D and 13CH4 in the atmosphere of Titan, providing for the first time the necessary data to be able to model kinetic isotope fractionation in these environments.

Sources, controls, and probabilistic health risk assessment of fluoride contamination in groundwater from a semi-arid region in Gujarat, Western India: An isotope-hydrogeochemical perspective.

Fluoride contamination in groundwaters of a rural region in semi-arid Western India has been studied using combination of geochemical-and-isotopic techniques, in conjunction with Health Quotient assessment approach. The objective of this study is to determine the sources and controls on fluoride content and to evaluate probabilistic non-carcinogenic risk associated with its long-term consumption. F- ranges from 0.3 to 12mg L-1, shows high spatial variability, and ~ 35% of the samples have F- > 1.5mg L-1 (WHO maximum limit for drinking). Two sources are identified: high F- results from water-rock interaction of F-bearing minerals in granites and gneisses, while phosphate fertilizers can contribute up to ~ 0.46mg L-1 of groundwater F- that can be significant for low F- samples. High F- samples are characterized by high pH, Na and alkalinity, and low Ca. Calcite precipitation drives the solubility of F-bearing minerals. Kinetic fractionation of water isotopes (18O and 2H) demonstrates that evaporation plays role in enriching groundwater F-. Non-carcinogenic risk, estimated by Hazard Quotient ([Formula: see text]), ranges from 0.13-5.72 to 0.26-11.86 for adult and children, respectively. Conservative estimate shows that ~ 0.467 million of adults and~0.073 million of children in four sub-districts are under the risk of fluorosis-while the residents of other five sub-districts remain safe from it. Finally, we suggest stakeholders to install F- treatment plants to ensure the health safety of local residents in the high-risk zones, create awareness in farmers for optimum use of fertilizers, and promote rainwater harvesting, for better management of groundwater resources and quality in the region.

Rayleigh Fractionation of Stable Water Isotopes during Equilibrium Freezing

Rayleigh Fractionation of Stable Water Isotopes during Equilibrium Freezing

The impact of temperature on the water isotope (2H/1H, 17O/16O, 18O/16O) fractionation upon transport through a low-density polyethylene membrane

ABSTRACT In the present study we investigated the isotope effects associated with water loss from closed low-density polyethylene (LDPE) bottles via diffusion at temperatures between 4 and 60 °C. While at low temperatures (4 and 10 °C) no substantial diffusional loss of water was observed within storage time, a pronounced loss was found for the experiments at room temperature and 60 °C. The latter was associated with a substantial increase in δ 18O, δ 17O, and δ 2Η values, and a decrease in the deuterium excess. The magnitude of the isotope effects essentially depended on the extent of water evaporation from the closed bottles through the LDPE membrane.

The Soil Water Evaporation Process from Mountains Based on the Stable Isotope Composition in a Headwater Basin and Northwest China

Soil water is a link between different water bodies. The study of soil water evaporation is of great significance to understand the regional hydrological process, promote environmental remediation in arid areas, and rationalize ecological water use. On the basis of soil water δ2H and δ18O data from April to October 2017 in the Xiying River basin in the upper reaches of the Qilian mountains, the lc-excess and Craig-Gordon model were applied to reflect the evaporating fractionation of soil water. The results show that the change in evaporation loss drives the enrichment of soil water isotopes. The signal of evaporative fractionation of soil water isotopes at different elevations has spatiotemporal heterogeneity. From the perspective of time dynamics, the evaporation loss of the whole region during the observation period was affected by temperature before July, while after July, it was controlled jointly by temperature and humidity, evaporation was weakened. Soil salt content and vegetation played an important role in evaporation loss. In terms of spatial dynamics, the soil moisture evaporation at the Xiying (2097 m) and Huajian (2390 m) stations in the foothills area is larger than that at the Nichan station (2721 m) on the hillside and Lenglong station (3637 m) on the mountain top. The surface soil water evaporation is strong, and the evaporation becomes weak with the increase of depth. The research has guiding significance for the restoration and protection of vegetation in arid areas and the formulation of reasonable animal husbandry policies.

First-Principles Diffusivity Ratios for Kinetic Isotope Fractionation of Water in Air.

Kinetic isotope fractionation between water vapor and liquid water or ice depends on the ratio of the diffusivities of the isotopic species in air, but there is disagreement as to the values of these ratios and limited information about their temperature dependence. We use state-of-the-art intermolecular potential-energy surfaces for the water-nitrogen and water-oxygen pairs, along with the kinetic theory of molecular gases, to calculate from first principles the diffusivities of water isotopologues in air. The method has sufficient precision to produce accurate diffusivity ratios. For the HDO/H2O ratio, we find that the often used hard-sphere kinetic theory is significantly in error, and confirm the 1978 experimental result of Merlivat. For the ratios involving 17O and 18O, the simple kinetic theory is relatively close to our more rigorous results. We provide diffusivity ratios from 190 K to 500 K, greatly expanding the range of temperatures for which these ratios are available.

Magnesium isotopes reveal bedrock impacts on stream organisms

Magnesium is an essential element to aquatic organisms and understanding the origin of Mg is important for understanding their growth. Ultimately, Mg in streams is derived from the chemical weathering of bedrock in the catchment. In this study, we used Mg stable isotope ratios (δ26Mg) to test whether stream organisms reflect lithological sources in stream catchments. In November 2017 and May 2018, we sampled aquatic insects and small gobies from six temperate streams in the Lake Biwa area (central Japan). Three of these streams had up to 38% limestone in their catchment (limestone streams), and three streams lacked limestone (non-limestone streams). We hypothesised that stream organisms from limestone streams had significantly lower δ26Mg values compared to those of the same organisms from non-limestone streams. Aquatic insects from limestone streams had an average of 0.78‰ lower δ26Mg values than those of the same organisms from non-limestone streams, thereby indicating a lithological control on the δ26Mg of aquatic insects. Aquatic insects often showed an offset to higher δ26Mg values compared to those of stream water, thereby pointing to a 26Mg-enriched diet as an additional Mg source to water and/or Mg isotope fractionation during Mg accumulation. Instead, stream water was the main Mg source for small gobies, as their bones reflected the δ26Mg of water. We concluded that δ26Mg could trace Mg sources of aquatic organisms, and the same methodology can be applied to other metals.

Possible soil tension controls on the isotopic equilibrium fractionation factor for evaporation from soil

AbstractThe stable isotopes of hydrogen and oxygen (δ2H and δ18O) are useful conservative tracers for tracking the movement of water in soil. But although the tracking of water infiltrating through the soil profile and its movement as run‐off and groundwater recharge are well developed, water movement through the soil can also include evaporative fractionation. Soil water fractionation factors have, until now, been largely empirical. Unlike open water evaporation where temperature, humidity, and vapour pressure gradient define fractionation, soil water evaporation includes fractionation by soil matrix effects. These effects are still poorly characterized. Here, we present preliminary results from a simple laboratory experiment with four soil admixtures with grain sizes that range from sand to silt and clay. Our results show that soil tension seems to control the isotope fractionation of resident soil water. The relationship between soil tension and equilibrium fractionation appears to be independent of soil texture and appears well supported by thermodynamic theory. Although these results are preliminary, they suggest that future work should go after soil tension effects as a possible explanatory factor of soil water and water vapour fractionation.

Kinetic mass-transfer calculation of water isotope fractionation due to cloud microphysics in a regional meteorological model

Abstract. In conventional atmospheric models, isotope exchange between liquid, gas, and solid phases is usually assumed to be in equilibrium, and the highly kinetic phase transformation processes inferred in clouds are yet to be fully investigated. In this study, a two-moment microphysical scheme in the National Center for Atmospheric Research (NCAR) Weather Research and Forecasting (WRF) model was modified to allow kinetic calculation of isotope fractionation due to various cloud microphysical phase-change processes. A case of a moving cold front is selected for quantifying the effect of different factors controlling isotopic composition, including water vapor sources, atmospheric transport, phase transition pathways of water in clouds, and kinetic-versus-equilibrium mass transfer. A base-run simulation was able to reproduce the ∼ 50 ‰ decrease in δD that was observed during the frontal passage. Sensitivity tests suggest that all the above factors contributed significantly to the variations in isotope composition. The thermal equilibrium assumption commonly used in earlier studies may cause an overestimate of mean vapor-phase δD by 11 ‰, and the maximum difference can be more than 20 ‰. Using initial vertical distribution and lower boundary conditions of water stable isotopes from satellite data is critical to obtain successful isotope simulations, without which the δD in water vapor can be off by about 34 ‰ and 28 ‰, respectively. Without microphysical fractionation, the δD in water vapor can be off by about 25 ‰.

ISOLESC: A Coupled Isotope‐LSM‐LES‐Cloud Modeling System to Investigate the Water Budget in the Atmospheric Boundary Layer

AbstractStable isotopes of water (H2O, HDO, and H218O) are tracers that provide powerful constraints on water transport processes in the atmosphere. This paper presents a description of an atmospheric boundary layer (ABL) simulation system called ISOLESC that couples water isotope fractionation processes with a land surface model, a large eddy simulation model, and a two‐moment cloud microphysics parameterization. Results from two model configurations—one with shallow precipitating cumulus and the other for a cloud‐free ABL—are presented to evaluate the model performance and determine its sensitivity to isotopic parameterizations. The coupled model successfully reproduces important ABL statistics (ABL height, cloud fraction, and cloud liquid water content), the expected effects of mixing and fractionation on the time evolution of ABL vapor isotopic composition, and observed diurnal variations of near‐surface water vapor isotopic composition. For the current configuration, nondiscriminating entrainment contributes 17% to the subdaily time variation of near‐surface vapor deuterium excess, while surface evapotranspiration contributes 83%. The isotopic compositions of water vapor and cloud water are insensitive to mesh resolution, but the profiles of cloud water specific humidity, rainwater specific humidity, and its isotopic ratios show moderate response to changes in grid size. Since ISOLESC resolves the energy containing scales of turbulent motions in the ABL and incorporates microphysical processes, it can be used for constraining ABL parameterizations. We find that a further improvement of raindrop reevaporation in the current cloud microphysical scheme is required in order to produce realistic near‐surface raindrop deuterium excess for the case simulated here. We suggest that ISOLESC provides a quantitative framework for utilizing vapor‐phase isotopic measurements to study local hydrological processes.

Concomitant variability in high-latitude aerosols, water isotopes and the hydrologic cycle

The interpretation of ice-core records rests on understanding the processes affecting trace constituents of the atmosphere that are preserved in ice. Stable-isotope ratios of ice are widely used as a palaeothermometer, an interpretation backed by well-established theory. In contrast, the interpretation of aerosols such as mineral dust and sea salts has remained a topic of debate. Here, we demonstrate that both the fractionation of water isotopes and the scavenging of aerosols are fundamentally driven by the same process, the condensation of water from the atmosphere. Water isotope ratios and aerosol concentrations in ice cores are remarkably coherent on all timescales longer than a few centuries. This shared low-frequency variability is dominated by the essential physics of the hydrologic cycle, which also accounts for the difference in variability between marine- and terrestrial-sourced aerosols in ice cores, as well as the global spatial pattern of aerosol changes recorded in both marine sediments and ice. These results have implications for past changes in radiative forcing and other fundamental aspects of climate, such as polar amplification, which are imprinted on the relationships between these proxy records. On timescales of centuries and longer, aerosol concentrations in Antarctic ice are controlled by changes in the nature of mid- and high-latitude precipitation, according to analyses of palaeoclimate data.

Isotopic (δ18O and δ2H) Integrity of Water Samples Collected and Stored by Automatic Samplers

Core Ideas Isotopic integrity (δ18O/δ2H) of water samples stored in autosamplers was assessed. Uncertainty in isotope values increased with increasing storage time and temperature. Addition of mineral oil to samples decreased evaporation and isotope fractionation. Stable water isotopes are increasingly becoming part of routine monitoring programs that use automatic samplers. The objectives of this study were to quantify the uncertainty in isotope signatures due to the length of sample storage (1–24 d) inside autosamplers over a range of air temperatures (5–35°C) and to evaluate the effectiveness of two evaporation reduction measures (mineral oil and high density polyethylene balls). Results of the laboratory study showed that up to 11.8% of the sample volume evaporated when samples were stored in an autosampler at 35°C for 24 d. To prevent significant water isotope fractionation, samples should be retrieved from autosamplers <7 d following sample collection when air temperatures are <22°C and <3 d following sample collection when the air temperature is 35°C. If samples need to be stored in an autosampler for longer periods of time, we found that mineral oil added to sample bottles effectively decreases evaporation and the potential for isotope fractionation.

Evaluation of modeled land‐atmosphere exchanges with a comprehensive water isotope fractionation scheme in version 4 of the Community Land Model

AbstractAll physical process models and field observations are inherently imperfect, so there is a need to both (1) obtain measurements capable of constraining quantities of interest and (2) develop frameworks for assessment in which the desired processes and their uncertainties may be characterized. Incorporation of stable water isotopes into land surface schemes offers a complimentary approach to constrain hydrological processes such as evapotranspiration, and yields acute insight into the hydrological and biogeochemical behaviors of the domain. Here a stable water isotopic scheme in the National Center for Atmospheric Research's version 4 of the Community Land Model (CLM4) is presented. An overview of the isotopic methods is given. Isotopic model results are compared to available data sets on site‐level and global scales for validation. Comparisons of site‐level soil moisture and isotope ratios reveal that surface water does not percolate as deeply into the soil as observed in field measurements. The broad success of the new model provides confidence in its use for a range of climate and hydrological studies, while the sensitivity of simulation results to kinetic processes stands as a reminder that new theoretical development and refinement of kinetic effect parameterizations is needed to achieve further improvements.