Isotopic Composition Of Water Vapor Research Articles

Constraining the global composition of D/H and 18O/16O in Martian water using SOFIA/EXES

ABSTRACT Isotopic ratios in water vapour carry important information about the water reservoir on Mars. Localized variations in these ratios can inform us about the water cycle and surface–atmosphere exchanges. On the other hand, the global isotopic composition of the atmosphere carries the imprints of the long-term fractionation, providing crucial information about the early water reservoir and its evolution throughout history. Here, we report the analysis of measurements of the D/H and 18O/16O isotopic ratios in water vapour in different seasons (LS = 15○, 127○, 272○, and 305○) made with the Echelon-Cross-Echelle Spectrograph (EXES) aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). These measurements, free of telluric absorption, provide a unique tool for constraining the global isotopic composition of Martian water vapour. We find the maximum planetary D/H ratio in our observations during the northern summer (D/H = 5.2 ± 0.2 with respect to the Vienna Standard Mean Ocean Water, VSMOW) and to exhibit relatively small variations throughout the year (D/H = 5.0 ± 0.2 and 4.3 ± 0.4 VSMOW during the northern winter and spring, respectively), which are to first order consistent though noticeably larger than the expectations from condensation-induced fractionation. Our measurements reveal the annually averaged isotopic composition of water vapour to be consistent with D/H = 5.0 ± 0.2 and 18O/16O = 1.09 ± 0.08 VSMOW. In addition, based on a comparison between the SOFIA/EXES measurements and the predictions from a Global Climate Model, we estimate the D/H in the northern polar ice cap to be $\sim\!{5}~{{\ \rm per\ cent}}$ larger than that in the atmospheric reservoir (D/Hice = 5.3 ± 0.3 VSMOW).

Is the Isotopic Composition of Precipitation a Robust Indicator for Reconstructions of Past Tropical Cyclones Frequency? A Case Study on Réunion Island From Rain and Water Vapor Isotopic Observations

AbstractBased on a 6‐year long record (2014–2020) of the isotopic composition of rain (δ18Op) at Réunion Island (55°E, 22°S), in the South‐West Indian Ocean, this study shows that the annual isotopic composition of precipitation in this region is strongly controlled by the number of cyclones, the number of best‐track days, and the proportion of cyclonic rain during the year. Our results support the use of δ18Op in annual‐resolved tropical climate archives as a reliable proxy of past cyclone frequency. The influence of the proportion of cyclonic rain on the annual isotopic composition arises from the systematically more depleted precipitation and water vapor during cyclonic events than during less organized convective systems. The analysis of the daily to hourly isotopic composition of water vapor (δ18Ov) during low‐pressure systems and the reproduction of daily δ18Ov observations by AGCMs with a global medium to coarse resolution (LMDZ‐iso and ECHAM6‐wiso) suggest that during cyclonic periods the stronger depletion mainly arises from both enhanced large‐scale precipitation and water vapor‐rain interactions under humid conditions.

From atmospheric water isotopes measurement to firn core interpretation in Adélie Land: a case study for isotope-enabled atmospheric models in Antarctica

Abstract. In a context of global warming and sea level rise acceleration, it is key to estimate the evolution of the atmospheric hydrological cycle and temperature in polar regions, which directly influence the surface mass balance of the Arctic and Antarctic ice sheets. Direct observations are available from satellite data for the last 40 years and a few weather data since the 1950s in Antarctica. One of the best ways to access longer records is to use climate proxies in firn or ice cores. The water isotopic composition in these cores is widely used to reconstruct past temperature variations. We need to progress in our understanding of the influence of the atmospheric hydrological cycle on the water isotopic composition of ice cores. First, we present a 2-year-long time series of vapor and precipitation isotopic composition measurement at Dumont d’Urville Station, in Adélie Land. We characterize diurnal variations of meteorological parameters (temperature, atmospheric water mixing ratio (hereafter humidity) and δ18O) for the different seasons and determine the evolution of key relationships (δ18O versus temperature or humidity) throughout the year: we find that the temperature vs. δ18O relationship is dependent on synoptic events dynamics in winter contrary to summer. Then, this data set is used to evaluate the atmospheric general circulation model ECHAM6-wiso (model version with embedded water stable isotopes) in a coastal region of Adélie Land where local conditions are controlled by strong katabatic winds which directly impact the isotopic signal. We show that a combination of continental (79 %) and oceanic (21 %) grid cells leads model outputs (temperature, humidity and δ18O) to nicely fit the observations, at different timescales (i.e., seasonal to synoptic). Therefore we demonstrate the added value of long-term water vapor isotopic composition records for model evaluation. Then, as a clear link is found between the isotopic composition of water vapor and precipitation, we assess how isotopic models can help interpret short firn cores. In fact, a virtual firn core built from ECHAM-wiso outputs explains much more of the variability observed in S1C1 isotopic record than a virtual firn core built from temperature only. Yet, deposition and post-deposition effects strongly affect the firn isotopic signal and probably account for most of the remaining misfits between archived firn signal and virtual firn core based on atmospheric modeling.

The Influence of Convective Aggregation on the Stable Isotopic Composition of Water Vapor

AbstractRemote sensing datasets of water vapor isotopic composition are used along with objective measures of convective aggregation to better understand the impact of convective aggregation on the atmospheric hydrologic cycle in the global tropics (30°N to 30°S) for the period 2015–2020. When convection is unaggregated, vertical velocity profiles are top‐heavy, mixing ratios increase and water vapor δD decreases as the mean precipitation rate increases, consistent with partial hydrometeor evaporation below anvils into a relatively humid atmospheric column. Aggregated convection is associated with bottom‐heavy vertical velocity profiles and a positive correlation between mixing ratio and δD, a result that is consistent with isotopic enrichment from detrainment of shallow convection near the observation level. Intermediate degrees of aggregation do not display significant variation in δD with mixing ratio or precipitation rate. Convective aggregation provides a useful paradigm for understanding the relationships between mixing ratio and isotopic composition across a range of convective settings. The results presented here may have utility for a variety of applications including the interpretation of paleoclimate archives and the evaluation of numerical simulations of convection.

Meteorological Analysis on Extremely Depleted 18O Rainfall Events during the Summer in Adelaide, Australia

Abstract The transport of atmospheric water vapor plays a crucial role in the production of precipitation and the variation of precipitation isotopic composition (δ18Op). This study investigates three precipitation events with extremely depleted heavy isotopes in the summer of Adelaide, Australia. Using fundamental water vapor diagnosis and moisture calculation method, this research analyzes the impact of rainout degrees along moisture transport paths, atmospheric circulation patterns, water vapor sources, and moisture transport on the extreme depletion of precipitation isotopes in the study area. The purpose of this study is to reveal the direct cause of extremely depleted δ18Op at the hourly time scale. The results show the diversity and complexity of δ18Op variation in summer precipitation events in Adelaide. The rainout caused by local and upstream large precipitation may be the main reason for extremely low values of δ18Op. The phenomenon of subcloud secondary evaporation, which is driven by the interaction between relatively low humidity and high temperature at near-surface levels, plays a pivotal role in the entire precipitation process. This mechanism is particularly pronounced during the onset or cessation of precipitation events, thereby resulting in the observed enrichment of δ18Op values. The oxygen stable isotopic composition of water vapor (δ18Oa) would usually become higher, when the air mass mixes with new moisture with relatively high δ18Oa, suppressing the influence of the previous rainout.

Technical note: Lessons from and best practices for the deployment of the Soil Water Isotope Storage System

Abstract. Soil water isotope datasets are useful for understanding connections between the hydrosphere, atmosphere, biosphere, and geosphere. However, they have been underproduced because of the technical challenges associated with collecting those datasets. Here, we present the results of testing and automation of the Soil Water Isotope Storage System (SWISS). The unique innovation of the SWISS is that we are able to automatically collect water vapor from the critical zone at a regular time interval and then store that water vapor until it can be measured back in a laboratory setting. Through a series of quality assurance and quality control tests, we tested whether the SWISS is resistant to both atmospheric intrusion and leaking in both laboratory and field settings. We assessed the accuracy and precision of the SWISS through a series of experiments in which water vapor of known composition was introduced into the flasks, stored for 14 d, and then measured. From these experiments, after applying an offset correction to report our values relative to Vienna Standard Mean Ocean Water (VSMOW), we assess the precision of the SWISS to be ±0.9 ‰ and ±3.7 ‰ for δ18O and δ2H, respectively. We deployed three SWISS units at three different field sites to demonstrate that the SWISS stores water vapor reliably enough that we are able to differentiate dynamics both between the sites as well within a single soil column. Overall, we demonstrate that the SWISS retains the stable isotope composition of soil water vapor for long enough to allow researchers to address a wide range of ecohydrologic questions.

A Case Study on Drivers of the Isotopic Composition of Water Vapor at the Coast of East Antarctica

AbstractStable water isotopes (SWIs) contain valuable information on the past climate and phase changes in the hydrologic cycle. Recently, vapor measurements in the polar regions have provided new insights into the effects of snow‐related and atmospheric processes on SWIs. The purpose of this study is to elucidate the drivers of the particularly depleted vapor isotopic composition measured on a ship close to the East Antarctic coast during the Antarctic Circumnavigation Expedition in 2017. Reanalysis data and backward trajectories are used to model the isotopic composition of air parcels arriving in the atmospheric boundary layer (ABL) above the ship. A simple model is developed to account for moisture exchanges with the snow surface. The model generally reproduces the observed trend with strongly depleted vapor δ18O values in the middle of the 6‐day study period. This depletion is caused by direct air mass advection from the ice sheet where the vapor is more depleted in heavy SWIs due to distillation during cloud formation. The time spent by the air masses in the marine ABL shortly before arrival at the ship is crucial as ocean evaporation typically leads to an abrupt change in the isotopic signature. Snow sublimation is another important driver when the isotopic composition of the sublimation flux differs substantially from that of the advected air mass, for example, marine air arriving at the coast or free‐tropospheric air descending from high altitudes. Despite strong simplifications, our model is a useful and computationally efficient method for understanding SWI dynamics at polar sites.

The premise of temperature effect playing in regions with complex moisture sources – Evidence from high-resolution water vapor isotopes

Atmospheric precipitation has widely taken part in the formation and accumulation of many geological archives. In these processes, the isotope fractionations are tightly related to the meteorological factors, such as temperature and precipitation amount. Therefore, precipitation isotopes are usually regarded as an effective proxy to reconstruct the paleoclimate and paleoenvironmental changes. However, with the deepening of research, it is found that the temperature effect is not suitable for all regions and time scales, especially in regions with complex moisture sources. Moreover, the applicable mechanism of the temperature effect is still unclear. Here, we chose Xi’an as our study site, because it is located in the transition zone of the East Asian Summer Monsoon (EASM) and the westerlies with relatively complex water vapor sources. Through conducting a three-year, high-resolution, relatively continuous water vapor isotopic composition measurements in Xi’an, we defined the duration of the EASM here, which normally starts in June and is over in September. By separating the δ18Op into monsoon and non-monsoon seasons, we found a significant temperature effect in the non-monsoon seasons, with a correlation coefficient of 0.54, while no temperature effect is observed in the monsoon seasons and the whole year. Our water vapor isotopic results suggested that the establishment of temperature effect of precipitation isotopes should follow two prerequisites: 1. single water vapor source; 2. large temperature gradient. Our results specify the applicable conditions of temperature effect and potentially help us to better use precipitation isotopes to understand the paleo-temperature variations in different regions.

Examination of the parameters controlling the triple oxygen isotope composition of grass leaf water and phytoliths at a Mediterranean site: a model–data approach

Abstract. Triple oxygen isotopes (17O-excess) of water are useful to trace evaporation at the soil–plant–atmosphere interface. The 17O-excess of plant silica, i.e., phytoliths, inherited from leaf water, was previously calibrated in growth chambers as a proxy of atmospheric relative humidity (RH). Here, using a model–data approach, we examine the parameters that control the triple oxygen isotope composition of bulk grass leaf water and phytoliths in natura, at the O3HP experimental platform located in the French Mediterranean area. A grass plot was equipped to measure for 1 year, all environmental and plant physiological parameters relevant for modeling the isotope composition of the grass leaf water. In particular, the triple oxygen and hydrogen isotope composition of atmospheric water vapor above the grass was measured continuously using a cavity ring-down spectrometer, and the grass leaf temperature was monitored at plot scale using an infrared (IR) radiometer. Grass leaves were collected in different seasons of the year and over a 24 h period in June. Grass leaf water was extracted by cryogenic vacuum distillation and analyzed by isotope ratio mass spectrometry (IRMS). Phytoliths were analyzed by IR–laser fluorination–IRMS after chemical extraction. We showed that the traditional Craig–Gordon steady-state model modified for grass leaves reliably predicts the triple oxygen isotope composition of leaf water during daytime but is sensitive to uncertainties on the leaf-to-air temperature difference. Deviations from isotope steady state at night are well represented in the triple oxygen isotope system and predictable by a non-steady-state model. The 17O-excess of phytoliths confirms the applicability of the 17O-excessphyto vs. RH equation established in previous growth chamber experiments. Further, it recorded average daytime RH over the growth period rather than daily RH, related to low transpiration and silicification during the night. This model–data approach highlights the utility of the triple oxygen isotope system to improve the understanding of water exchange at the soil–plant–atmosphere interface. The in natura experiment underlines the applicability of 17O-excess of phytoliths as a RH proxy.

Measurement of δ18O in water vapor using a tunable diode laser-based spectrometer

A gas detection system based on tunable diode laser absorption spectroscopy (TDLAS) was reported, which can be used for real-time, continuity, high-precision, and rapid time response measurement of the isotope ratio of 18O/16O in water vapor from 3729.8 cm−1 to 3730.8 cm−1. A detailed description of the system's implementation was provided and preliminary measurement precision was analyzed with a short path length sample cell (20.4 cm) after verification in the laboratory environment. Allan variance analytical method was used to evaluate the reliability of the developed laser spectroscopic isotope analysis system and the results showed that a precision of 5.274‰ was obtained for 18O/16O ratio at 1 s signal averaging time, which can be improved to 0.088‰ at the integration time of approximate 191 s. By combining with a long optical path absorption cell, the developed TDLAS isotope detection system provides great potential for determining the oxygen isotope composition of water vapor for various applications in environmental, geological, ecological, and energy fields.

Leaf water δ18O, δ2H and d‐excess isoscapes for Australia using region‐specific plant parameters and non‐equilibrium vapour

AbstractOxygen (δ18O) and hydrogen (δ2H) isotope ratios, and their relationship to one another (d‐excess) are altered as water travels from the atmosphere to the land surface, into soils and plants and back to the atmosphere. Plants return water to the atmosphere through transpiration (evaporation through the stomata), which causes isotopic fractionation concentrating the heavier isotopes (18O and 2H) in the water that remains behind in the leaves. The degree of isotopic fractionation during transpiration is controlled largely by climate, and as a result can be predicted using process‐based models and climate data. The modelled transpirational isotopic fractionation can be applied to plant source water isotopic values to predict leaf water isotope ratios and generate maps of isotopic composition, or isoscapes. This approach of mechanistic modelling has been well demonstrated in the first generation of global leaf water isoscapes (PLoS One, 3(6), e2447, 2008). However, use of leaf water isoscapes in fields such as hydrology, ecology, and forensics requires a new generation of updated region‐specific isoscapes. Here, we generate leaf water isoscapes of δ18O, δ2H and d‐excess for Australia, the driest vegetated continent on Earth, where leaf water represents a critical water resource for ecosystems. These isoscapes represent an improvement over previous global isoscapes due to their higher resolution, region‐specific, empirically derived plant parameters, and non‐equilibrium corrections for water vapour isotopic composition. The new isoscapes for leaf water are evaluated relative to observed isotope ratios of leaf cellulose and cherry juice. The model predictions for annual average leaf water isotope ratios showed strong correlations with these plant tissues that integrate over time. Moreover, inclusion of region‐specific leaf temperature estimates and non‐equilibirum vapour corrections improved prediction accuracy. Regionally based isoscapes provide improved characterisations of average leaf water isotope ratios needed to support research in hydrology, plant ecophysiology, atmospheric science, ecology, and geographic provenancing of biological materials.

What Controls the Mesoscale Variations in Water Isotopic Composition Within Tropical Cyclones and Squall Lines? Cloud Resolving Model Simulations in Radiative‐Convective Equilibrium

AbstractWater isotopes are tracers of convective processes and are often used as proxies for past precipitation. These applications require a better understanding of the impact of convective processes on the isotopic composition of water vapor and precipitation. One way to advance this understanding is to analyze the isotopic mesoscale variations during organized convective systems such as tropical cyclones or squall lines. The goal of this study is to understand these isotopic mesoscale variations with particular attention to isotopic signals in near‐surface vapor and precipitation that may be present in observations and in paleoclimate proxies. With this aim, we run cloud resolving model simulations in radiative‐convective equilibrium in which rotation or wind shear is added, allowing us to simulate tropical cyclones or squall lines. The simulations capture the robust aspects of mesoscale isotopic variations in observed tropical cyclones and squall lines. We interpret these variations using a simple water budget model for the sub‐cloud layer of different parts of the domain. We find that rain evaporation and rain‐vapor diffusive exchanges are the main drivers of isotopic depletion within tropical cyclones and squall lines. Horizontal advection spreads isotopic anomalies, thus reshaping the mesoscale isotopic pattern. This study contributes to our understanding of mesoscale isotopic variability and provides physical arguments supporting the interpretation of paleoclimate isotopic archives in tropical regions in terms of past cyclonic activity.

Vehicle-based in situ observations of the water vapor isotopic composition across China: spatial and seasonal distributions and controls

Abstract. Stable water isotopes are natural tracers in the hydrological cycle and have been applied in hydrology, atmospheric science, ecology, and paleoclimatology. However, the factors controlling the isotopic distribution, both at spatial and temporal scales, are debated in low and middle latitude regions, due to the significant influence of large-scale atmospheric circulation and complex sources of water vapor. For the first time, we made in situ observations of near-surface vapor isotopes over a large region (over 10 000 km) across China in both pre-monsoon and monsoon seasons, using a newly designed vehicle-based vapor isotope monitoring system. Combined with daily and multiyear monthly mean outputs from the isotope-incorporated global spectral model (Iso-GSM) and infrared atmospheric sounding interferometer (IASI) satellite to calculate the relative contribution, we found that the observed spatial variations in both periods represent mainly seasonal mean spatial variations, but are influenced by more significant synoptic-scale variations during the monsoon period. The spatial variations of vapor δ18O are mainly controlled by Rayleigh distillation along air mass trajectories during the pre-monsoon period, but are significantly influenced by different moisture sources, continental recycling processes, and convection during moisture transport in the monsoon period. Thus, the North–South gradient observed during the pre-monsoon period is counteracted during the monsoon period. The seasonal variation of vapor δ18O reflects the influence of the summer monsoon convective precipitation in southern China and a dependence on temperature in the North. The spatial and seasonal variations in d-excess reflect the different moisture sources and the influence of continental recycling. Iso-GSM successfully captures the spatial distribution of vapor δ18O during the pre-monsoon period, but the performance is weaker during the monsoon period, maybe due to the underestimation of local or short-term high-frequency synoptic variations. These results provide an overview of the spatial distribution and seasonal variability of water isotopic composition in East Asia and their controlling factors, and they emphasize the need to interpret proxy records in the context of the regional system.

A modular field system for near-surface, vertical profiling of the atmospheric composition in harsh environments using cavity ring-down spectroscopy

Abstract. Cavity ring-down spectroscopy (CRDS) has allowed for increasingly widespread, in situ observations of trace gases, including the stable isotopic composition of water vapor. However, gathering observations in harsh environments still poses challenges, particularly in regard to observing the small-scale exchanges taking place between the surface and atmosphere. It is especially important to resolve the vertical structure of these processes. We have designed the ISE-CUBE system as a modular CRDS deployment system for profiling stable water isotopes in the surface layer, specifically the lowermost 2 m above the surface. We tested the system during a 2-week field campaign during February–March 2020 in Ny-Ålesund, Svalbard, Norway, with ambient temperatures down to −30 ∘C. The system functioned suitably throughout the campaign, with field periods exhibiting only a marginal increase in isotopic measurement uncertainty (30 %) as compared to optimal laboratory operation. Over the 2 m profiling range, we have been able to measure and resolve gradients on the temporal and spatial scales needed in an Arctic environment.

The role of radiative cooling and leaf wetting in air–leaf water exchange during dew and radiation fog events in a temperate grassland

During prolonged dry periods, non-rainfall water (NRW) plays a vital role as water input into temperate grasslands, affecting the leaf surface water balance and plant water status. Previous chamber and laboratory experiments investigated air–leaf water exchange during dew deposition, but overlooked the importance of radiative cooling on air–leaf water exchange because the chamber is a heat trap, preventing radiative cooling. To complement these previous studies, we conducted a field study, in which we investigated the effect of radiatively-induced NRW inputs on leaf water isotope signals and air–leaf water exchange in a temperate grassland during the dry-hot summers of 2018 and 2019. We carried out field measurements of the isotope composition of atmospheric water vapor, NRW droplets on foliage, leaf water, xylem water of root crown, and soil water, combined with meteorological and plant physiological measurements. We combined radiation measurements with thermal imaging to estimate leaf temperatures using different methods, and computed the corresponding leaf conductance and air–leaf water exchange. Our results indicate that radiative cooling and leaf wetting induced a switch of direction in the net water vapor exchange from leaf-to-air to air-to-leaf. The leaf conductance and air–leaf water exchange varied by species due to the species-specific biophysical controls. Our results highlight the ecological relevance of radiative cooling and leaf wetting in natural temperate grasslands, a process which is expected to influence land surface water budgets and may impact plant survival in many regions in a drier climate.

Conditions of groundwater recharge in the hyperarid southern Atacama Desert

Weather systems that produced recharge to the aquifers in the Atacama Desert between 24.5 and 25.5°S were investigated using δ 18 O and δ 2 H data in groundwater and precipitation combined with remote sensing methods. Atmospheric systems that produced rain and snow from 1984 to 2017 were analysed using isotopic data for precipitation from the literature and this investigation. δ 18 O-lapse rates on a west to east transect for a series of precipitation events ranged from −5.0 to −1.1 ‰/km, which is similar to the global average. Groundwater stable isotopes plotted against the average elevation of the catchment basin for each spring or well sampled produce a lapse rate identical to precipitation isotopes but are enriched in δ 18 O relative to δ 2 H due to the effects of evaporation before water enters the groundwater system. Data show a seasonal cycle in the isotopic composition of precipitation, as does δ 2 H data obtained from Tropospheric Emission Spectrometer (TES) on-board the Aura satellite. These analyses demonstrate that an important source of moisture is the Pacific Ocean. Although usually discounted in climate and paleoclimate analyses of northern Chile, this source of moisture is consistent with two features of the regional land-atmosphere system. First, the hyper-arid core of the Atacama Desert at these latitudes lies in a secondary rain shadow created by the Cordillera de Domeyko which exceeds 4000 m a.s.l., which blocks further westward passage of moisture that might have crossed from the east over the Andes. Second, the weather events responsible for precipitation between 2000 and 2018 are distributed between winter systems which initiate from the south, and exceptional events at other times of the year in which moisture originates from the tropics. Particle tracking indicates that air masses resided between 10 and 30°S over the Pacific at least 4 days prior to weather events which produced rain, or snow that persisted on the ground for more than one month between 2000 and 2018, even though the triggers for these events originated in higher latitudes. Pacific moisture sources need to be better accounted for in paleoclimate studies and groundwater resources evaluation. • Precipitation collected in the southern part of the Atacama Desert is isotopically characterized. • Seasonal patterns are found in the isotope composition of precipitation and atmospheric water vapor. • Isotope data indicate moisture is derived from the Pacific Ocean, and is confirmed from particle tracking. • Groundwater isotope data indicates moisture has been derived from the Pacific Ocean on millennial timescales.

Inverse relationships between salinity and hydrogen isotope fractionation of n-alkanes in the Aegiceras corniculatum leaves and surface sediments from Zhanjiang mangrove estuary of China

Hydrogen isotope ratios of mangrove lipids have recently gained increasing interest because of their potential for reconstructing past water salinity and paleohydrology conditions. Although it has been suggested that the deuterium fractionation in mangrove leaf lipids appears to be primarily affected by water salinity, it remains an important research topic if this inverse relationship between salinity and hydrogen fractionation in leaf wax can be universally applied. In this regard, we have investigated the hydrogen isotopic composition of n-alkanes in leaves of Aegiceras corniculatum and surface sediments and the environmental water (surface water; αn-alkane-Water), collected along a 30 ppt salinity gradient in the Zhanjiang mangrove estuary of China, aiming to evaluate the impact of water salinity on the hydrogen isotopic fractionation of leaf wax derived n-alkanes. δ2H values of A. corniculatum leaf wax n-alkanes were between −183‰ and − 127‰ for C27, C29, and C31n-alkanes, and their αn-alkane-Water values range from 0.823 to 0.887. Sedimentary δ2H values range from −171‰ to −132‰ for C27, C29, and C31n-alkanes, and their αn-alkane-Water values were between 0.832 and 0.887. Inverse relationships between αn-alkane-Water and salinity were observed in mangrove A. corniculatum and surface sediment. This relationship for mangrove A. corniculatum may result from the selective utilization of freshwater during the rain event, changes in biosynthetic fractionation, and the relatively high humidity and/or larger changes in water vapour isotopic composition. For surface sediment, the inverse relationship could be mainly attributed to the mangrove-derived organic matter input, as the principal component analysis (PCA) results demonstrated a strong connection between the studied mangrove tree and the surface sediment. The consistent negative correlations between αn-alkane-Water and salinity for mangrove leaf waxes and surface sediments provide encouraging evidence for applying the hydrogen isotopic composition of mangrove leaf wax for paleohydrological reconstruction.

Stable water isotope signals in tropical ice clouds in the West African monsoon simulated with a regional convection-permitting model

Abstract. Tropical ice clouds have an important influence on the Earth's radiative balance. They often form as a result of tropical deep convection, which strongly affects the water budget of the tropical tropopause layer. Ice cloud formation involves complex interactions on various scales. These processes are not yet fully understood and lead to large uncertainties in climate projections. In this study, we investigate the formation of tropical ice clouds related to deep convection in the West African monsoon, using stable water isotopes as tracers of moist atmospheric processes. We perform convection-permitting simulations with the regional Consortium for Small-Scale Modelling isotope-enabled (COSMOiso) model for the period from June to July 2016. First, we evaluate our model simulations using space-borne observations of mid-tropospheric water vapour isotopes, monthly station data of precipitation isotopes, and satellite-based precipitation estimates. Next, we explore the isotope signatures of tropical deep convection in atmospheric water vapour and ice based on a case study of a mesoscale convective system (MCS) and a statistical analysis of a 1-month period. The following five key processes related to tropical ice clouds can be distinguished based on isotope information: (1) convective lofting of enriched ice into the upper troposphere, (2) cirrus clouds that form in situ from ambient vapour under equilibrium fractionation, (3) sedimentation and sublimation of ice in the mixed-phase cloud layer in the vicinity of convective systems and underneath cirrus shields, (4) sublimation of ice in convective downdraughts that enriches the environmental vapour, and (5) the freezing of liquid water just above the 0 ∘C isotherm in convective updraughts. Importantly, we note large variations in the isotopic composition of water vapour in the upper troposphere and lower tropical tropopause layer, ranging from below −800 ‰ to over −400 ‰, which are strongly related to vertical motion and the moist processes that take place in convective updraughts and downdraughts. In convective updraughts, the vapour is depleted by the preferential condensation and deposition of heavy isotopes, whereas the non-fractionating sublimation of ice in convective downdraughts enriches the environmental vapour. An opposite vapour isotope signature emerges in thin-cirrus cloud regions where the direct transport of enriched (depleted) vapour prevails in large-scale ascent (descent). Overall, this study demonstrates that isotopes can serve as useful tracers to disentangle the role of different processes in the West African monsoon water cycle, including convective transport, the formation of ice clouds, and their impact on the tropical tropopause layer.

Diagnoses of Antarctic Inland Water Cycle Regime: Perspectives From Atmospheric Water Vapor Isotope Observations Along the Transect From Zhongshan Station to Dome A

Water stable isotopes are crucial for paleoclimate reconstruction and water cycle tracing in Antarctica. Accurate measurement of atmospheric water vapor isotopic composition of hydrogen and oxygen is required urgently for understanding the processes controlling the atmosphere–snow interaction and associated isotope fractionation. This study presents in situ real-time measurements of water vapor isotopes along the transect from Zhongshan Station to Dome Argus (hereafter Dome A) in East Antarctica for the first time. The results reveal that the surface vapor stable isotopes of δ18O and δ D showed a gradual decreasing trend in the interior plateau region with the distance away from the coast, with significant δ18O-temperature correlation gradient of 1.61‰°/C and δ18O-altitude gradient of –2.13‰/100 m. Meanwhile, d-excess gradually arises with elevation rise. Moreover, the spatial variation of vapor isotopic composition displays three different characters implying different atmosphere circulation backgrounds controlling the inland water cycle; it can be divided as the coastal steep area below 2,000 m, a vast inland area with an elevation varied between 2,000 and 3,000 m, and high central plateau. Thirdly, observed high inland Antarctica water vapor d-excess quantitatively confirms stratosphere air intrusion and vapor derived from low latitudes by Brewer–Dobson circulation. Finally, the diurnal cycle signals of interior area water vapor isotopes δ18O, δ D, and air temperature highlighted the substantial domination of the supersaturation sublimation/condensation effect in inland, and this suggests that fractionation occurs during sublimation and vapor–snow exchanges should no longer be considered insignificant for the isotopic composition of near-surface snow in Antarctica.

Marine Boundary Layer Decoupling and the Stable Isotopic Composition of Water Vapor

AbstractDecoupling of the subcloud layer in stratocumulus‐topped marine boundary layers (STMBL) influences low‐cloud cover by limiting the supply of water vapor from the surface. However, the relative importance of mixing between surface fluxes and other reservoirs of water vapor as a function of the degree of decoupling is poorly understood. Water vapor transport within the STMBL and its response to decoupling is explored using surface measurements of water vapor isotopic composition that were obtained from Graciosa Island, Azores, during the summer and fall of 2018. The data show an inverse relationship between the decoupling metric, Δq, and the degree of drying from an isotopically depleted water vapor source. The isotopic data require some degree of drying with an isotopically depleted source for coupled conditions, and likely require a small amount of mixing even for strongly decoupled conditions. The data are consistent with mixing between purely local reservoirs of water vapor, subjected to a small amount of condensation and fractionation, and do not require the invocation of large‐scale transport of water vapor aloft or additional cloud‐formation effects aloft.