A continuous stream flash evaporator for the calibration of an IR cavity ring-down spectrometer for the isotopic analysis of water

A new technique for high-resolution simultaneous isotopic analysis of δ¹⁸O and δD in liquid water is presented. A continuous stream flash evaporator has been designed that is able to vapourise a stream of liquid water in a continuous mode and deliver a stable and finely controlled water vapour sample to a commercially available infrared cavity ring-down spectrometer. Injection of sub-microlitre amounts of the liquid water is achieved by pumping liquid water sample through a fused silica capillary and instantaneously vapourising it with 100% efficiency in a home-made oven at a temperature of 170?°C. The system's simplicity, low power consumption and low dead volume together with the possibility for automated unattended operation provides a solution for the calibration of laser instruments performing isotopic analysis of water vapour. Our work is mainly driven by the possibility to perform high-resolution online water isotopic analysis on continuous-flow analysis (CFA) systems typically used to analyse the chemical composition of ice cores drilled in polar regions. In the following, we describe the system's precision and stability and sensitivity to varying levels of sample size and we assess the observed memory effects. A test run with standard waters of different isotopic compositions is presented, demonstrating the ability to calibrate the spectrometer's measurements on a VSMOW scale with a relatively simple and fast procedure.     

Continuous analysis of δ¹⁸O and δD values of water by diffusion sampling cavity ring-down spectrometry: a novel sampling device for unattended field monitoring of precipitation, ground and surface waters

A novel sampling device suitable for continuous, unattended field monitoring of rapid isotopic changes in environmental waters is described. The device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ1?O and δD values by Cavity Ring-Down Spectrometry (CRDS). Separation of the analysed water vapour from non-volatile dissolved and particulate contaminants in the liquid sample minimises spectral interferences associated with CRDS analyses of many aqueous samples. Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling-CRDS (DS-CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS-CRDS data. The internal precision for an integration period of 3 min (standard deviation (SD) = 0.1‰ and 0.3‰ for δ1?O and δD values, respectively) is similar to analysis of water by CRDS using an autosampler to inject and evaporate discrete water samples. The isotopic effects of variable air temperature, water vapour concentration, water pumping rate and dissolved organic content were found to be either negligible or correctable by analysis of water standards. The DS-CRDS system was used to analyse the O and H isotope composition in short-lived rain events. Other applications where finely time resolved water isotope data may be of benefit include recharge/discharge in groundwater/river systems and infiltration-related changes in cave drip water.     

Saisonale Variation von Deuterium und Sauerstoff-18 in Luftfeuchte und Niederschlag über Antarktika

Abstract D and (18)O distributions were investigated in Antarctic precipitation (falling snow) and in water vapour to study their dependance on season and sampling site. Long-term sampling at the former German Georg Forster Station during 1978-93 and at the Japanese Syowa Station during 1994-97 allow conclusions about the present seasonal isotopic variations in the water inflow to Antarctica. The δD and δ(18)O values of precipitation at these East Antarctic coastal stations were compared with corresponding data from the West Antarctic Georg von Neumayer and Halley stations. The monthly means of these long-term data sets show typical hysteresis-like seasonal patterns of isotopic composition. Significant time lags exist regarding station temperatures, while water vapour δD values do not show such hysteresis patterns. Here, half-yearly and even quarter-yearly time components were found by Fourier analysis. Attempts were made to describe the variation in δD and δ(18)O values of water vapour and precipitation as well as in the resulting deuterium excess by the mixed cloud isotopic model (MCIM) of Ciais and Jouzel.     

Saisonale Variation von Deuterium und Sauerstoff-18 in Luftfeuchte und Niederschlag über Antarktika

Abstract

D and ¹⁸O distributions were investigated in Antarctic precipitation (falling snow) and in water vapour to study their dependance on season and sampling site. Long-term sampling at the former German Georg Forster Station during 1978–93 and at the Japanese Syowa Station during 1994–97 allow conclusions about the present seasonal isotopic variations in the water inflow to Antarctica. The δD and δ¹⁸O values of precipitation at these East Antarctic coastal stations were compared with corresponding data from the West Antarctic Georg von Neumayer and Halley stations. The monthly means of these long-term data sets show typical hysteresis-like seasonal patterns of isotopic composition. Significant time lags exist regarding station temperatures, while water vapour δD values do not show such hysteresis patterns. Here, half-yearly and even quarter-yearly time components were found by Fourier analysis. Attempts were made to describe the variation in δD and δ¹⁸O values of water vapour and precipitation as well as in the resulting deuterium excess by the mixed cloud isotopic model (MCIM) of Ciais and Jouzel.     

Microcombustion of ng Amounts of Carbon in Non-Volatile Materials for isotope Ratio Evaluation

Abstract A novel microcombustion technique for carbon isotopic analysis of nanogram amounts of carbon in non-volatile materials based on isotope ratio monitoring (irm) mass spectrometry is described. Liquid or solid samples placed in a quartz sleeve are combusted at 1000°C in a continuous stream of helium and oxygen. CO(2) removed from the carrier gas stream by cryogenic trapping is transferred onto a GC column. Following GC separation, the CO(2) is transferred via an open split to the ion source of a gas isotope ratio mass spectrometer. Reproducibility for samples >25 nmol carbon is <1‰. Problems associated with blanks from various sources and with reproducible deposition of small sample amounts led to variable accuracy, which was dependent on the compound class being analysed. Minimum sample size was in the range from 5 to 10 nmol carbon. Measurements of dissolved organic carbon (DOC) of groundwater from Germany yielded consistent values of δ(13)C = -28.8‰.     

Influence of the balance of the intertropical front on seasonal variations of the isotopic composition in rainfall at Kisiba Masoko (Rungwe Volcanic Province,SW, Tanzania)

Tropical rainfall isotopic composition results from complex processes. The climatological and environmental variability in East Africa increases this complexity. Long rainfall isotope datasets are needed to fill the lack of observations in this region. At Kisiba Masoko, Tanzania, rainfall and rain isotopic composition have been monitored during 6 years. Mean year profiles allow to analyse the seasonal variations. The mean annual rainfall is 2099?mm with a rain-weighted mean composition of ?3.2?‰ for δ¹⁸O and ?11.7?‰ for δ²H. The results are consistent with available data although they present their own specificity. Thus, if the local meteoric water line is δ²H?=?8.6 δ¹⁸O?+?14.8, two seasonal lines are observed. The seasonality of the isotopic composition in rain and deuterium excess has been compared with precipitating air masses backtracking trajectories to characterize a simple scheme of vapour histories. The three major oceanic sources have two moisture signatures with their own trajectory histories: one originated from the tropical Indian Ocean at the beginning of the rainy season and one from the Austral Ocean at its end. The presented isotopic seasonality depends on the balance of the intertropical front and provides a useful dataset to improve the knowledge about local processes.     

Microcombustion of ng Amounts of Carbon in Non-Volatile Materials for isotope Ratio Evaluation

Abstract

A novel microcombustion technique for carbon isotopic analysis of nanogram amounts of carbon in non-volatile materials based on isotope ratio monitoring (irm) mass spectrometry is described. Liquid or solid samples placed in a quartz sleeve are combusted at 1000°C in a continuous stream of helium and oxygen. CO₂ removed from the carrier gas stream by cryogenic trapping is transferred onto a GC column. Following GC separation, the CO₂ is transferred via an open split to the ion source of a gas isotope ratio mass spectrometer. Reproducibility for samples >25 nmol carbon is <1‰. Problems associated with blanks from various sources and with reproducible deposition of small sample amounts led to variable accuracy, which was dependent on the compound class being analysed. Minimum sample size was in the range from 5 to 10 nmol carbon. Measurements of dissolved organic carbon (DOC) of groundwater from Germany yielded consistent values of δ¹³C = -28.8‰.     

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO₂ and water vapour were observed. The isotope ratios of both CO₂ and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ¹³C–CO₂ and δ¹⁸O–CO₂ increased, while δ²H–H₂Ov and δ¹⁸O–H₂Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO₂ and water vapour and the meteorological phenomena. Therefore, isotopic information of CO₂ and H₂Ov could be used as a tracer of meteorological information.     

Isotope fractionation of sandy-soil water during evaporation – an experimental study

Soil samples containing water with known stable isotopic compositions were prepared. The soil water was recovered by using vacuum/heat distillation. The experiments were held under different conditions to control rates of water evaporation and water recovery. Recoveries, δ¹⁸O and δ²H values of the soil water were determined. Analyses of the data using a Rayleigh distillation model indicate that under the experimental conditions only loosely bound water is extractable in cases where the recovery is smaller than 100?%. Due to isotopic exchange between vapour and remaining water in the micro channels or capillaries of the soil matrix, isotopic fractionation may take place under near-equilibrium conditions. This causes the observed relationship between δ²H and δ¹⁸O of the extracted water samples to have a slope close to 8. The results of this study may indicate that, in arid zones when soil that initially contains water dries out, the slope of the relationship between δ²H and δ¹⁸O values should be close to 8. Thus, a smaller slope, as observed by some groundwater and soil water samples in arid zones, may be caused by evaporation of water before the water has entered the unsaturated zone.     

δ18O characteristics of lichens and their effects on evaporative processes of the subjacent soil

The study presents first data on the δ¹⁸O performance of poikilohydrous lichen ground cover, and its potential impact on the isotopic composition of water fluxes arising from subjacent soil layers. As a model organism, the globally distributed lichen Cladina arbuscula was studied under laboratory conditions as well as in the field. During a desiccation experiment, δ¹⁸O of the lichen's thallus water and of its respired CO₂ became enriched by ～7‰ and followed a similar enrichment pattern to that expected from homoiohydrous, vascular plants. However, the observed degree of enrichment was lower in comparison to vascular plants due to (i) the lichen's inherent lower evaporative resistances; and (ii) a stronger effect of the more depleted surrounding water vapour. In lichens growing in their natural habitat, this specific pattern may show substantial variations depending on prevailing microclimatic conditions. Within a field study, thallus water δ¹⁸O of lichens principally proved to become more depleted when close to equilibration with the surroundings. It thereby strongly depended on the absorption of surrounding water vapour. Moreover, the results indicate that lichen mats substantially reduce evaporation rates arising from subjacent soil layers, and may alter the isotopic signal of vapour diffusing away from these layers into more depleted values.     

There is no Temperature Dependence of Net Biochemical Fractionation of Hydrogen and Oxygen Isotopes in Tree-Ring Cellulose

Abstract

The isotopic composition of tree-ring cellulose was obtained over a two-year period from small diameter, riparian zone trees along an elevational transect in Big Cottonwood Canyon, Utah, USA to test for a possible temperature dependence of net biological fractionation during cellulose synthesis. The isotope ratios of stream water varied by only 3.6‰ and 0.2‰ in δD and δ¹⁸O, respectively, over an elevation change of 810m. The similarity in stream water and macroenvironment over the short (13km) transect produced nearly constant stem and leaf water δD and δ¹⁸O values. In addition, what few seasonal variations observed in the isotopic composition of source water and atmospheric water vapor or in leaf water evaporative enrichment were experienced equally by all sites along the elevational transect. The temperature at each site along the transect spanned a range of ≥ 5°C as calculated using the adiabatic lapse rate. Since the δD and δ¹⁸O values of stem and leaf water varied little for these trees over this elevation/ temperature transect, any differences in tree-ring cellulose δD and δ¹⁸O values should have been associated with temperature effects on net biological fractionation. However, the slopes of the regressions of elevation versus the δD and δ¹⁸O values of tree-ring cellulose were not significantly different from zero indicating little or no temperature dependence of net biological fractionation. Therefore, cross-site climatic reconstruction studies using the isotope ratios of cellulose need not be concerned that temperatures during the growing season have influenced results.     

In situ measurement of CO2 and water vapour isotopic compositions at a forest site using mid-infrared laser absorption spectroscopy

We conducted continuous, high time-resolution measurements of CO₂ and water vapour isotopologues (¹⁶O¹²C¹⁶O, ¹⁶O¹³C¹⁶O and ¹⁸O¹²C¹⁶O for CO₂, and H₂¹⁸O for water vapour) in a red pine forest at the foot of Mt. Fuji for 9 days from the end of July 2010 using in situ absorption laser spectroscopy. The δ¹⁸O values in water vapour were estimated using the δ²H–δ¹⁸O relationship. At a scale of several days, the temporal variations in δ¹⁸O-CO₂ and δ¹⁸O-H₂O are similar. The orders of the daily Keeling plots are almost identical. A possible reason for the similar behaviour of δ¹⁸O-CO₂ and δ¹⁸O-H₂O is considered to be that the air masses with different water vapour isotopic ratios moved into the forest, and changed the atmosphere of the forest. A significant correlation was observed between δ¹⁸O-CO₂ and δ¹³C-CO₂ values at nighttime (r²≈0.9) due to mixing between soil (and/or leaf) respiration and tropospheric CO₂. The ratios of the discrimination coefficients (Δ_a/Δ) for oxygen (Δ_a) and carbon (Δ) isotopes during photosynthesis were estimated in the range of 0.7–1.2 from the daytime correlations between δ¹⁸O-CO₂ and δ¹³C-CO₂ values.     

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ¹⁸O and δ²H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.     

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ²H and δ¹⁸O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ2H and δ1?O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R2=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.     

Supported Nickel-Cobalt Oxide Catalysts for the Isotopic Exchange of Deuterium between Hydrogen and Water Vapour

The specific catalytic activity of supported nickel-cobalt (II) oxide catalysts for the isotopic exchange of deuterium between hydrogen and water in the vapour phase was tested. The specific surface area of the catalysts was evaluated by nitrogen adsorption at ?195.8 °C and application of the BET-equation. The specific metallic surface area for these catalysts was carried out at liquid nitrogen temperature by hydrogen adsorption. Comparison between the specific activity of the catalysts and the specific surface area and specific metallic surface area teas made. The results of this study indicated that nickel catalysis supported with 15 – 20 mole% CoO exhibit a relatively high catalytic activity for the isotopic exchange reaction between hydrogen and water vapour, high specific surface area and high specific metallic surface area.     

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ2H and δ18O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ²H and δ¹⁸O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R ²=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.     

A high-resolution Fourier transform spectrometer for far infrared magneto-optic spectroscopy of magnetic materials

We describe a high-resolution (0.015 cm⁻¹) Fourier transform spectrometer which has been developed to investigate bulk and surface magnetic polaritons in magnetic media by far infrared magneto-optic spectroscopy. The spectrometer uses a novel combination of laser-controlled sampling of the interferogram and phase modulation of the infrared beam to combine very accurate sampling and low signal-to-noise ratio. The spectrometer is coupled to a liquid helium cryostat with a 7 T superconducting magnet, and a liquid helium-cooled silicon bolometer is used as the detector. Samples can be mounted in the cryostat for polarised oblique incidence reflection measurements in the Voigt geometry with the applied magnetic field vertical. Measurements on surface polaritons are made by using attenuated total reflection (ATR) spectroscopy with silicon prisms to obtain the necessary wave vector enhancement. The resolution of the instrument is demonstrated with measurements on the rotational lines of water vapour, and a selection of measurements on a bulk single crystal of FeF₂, a uniaxial antiferromagnet, is presented to illustrate the performance of the instrument as a probe of magnetic excitations.     

δ2H and δ18O of human body water: a GIS model to distinguish residents from non-residents in the contiguous USA

An understanding of the factors influencing the isotopic composition of body water is important to determine the isotopic composition of tissues that are used to reconstruct movement patterns of humans. The δ(2)H and δ(18)O values of body water (δ(2)H(bw) and δ(18)O(bw)) are related to the δ(2)H and δ(18)O values of drinking water (δ(2)H(dw) and δ(18)O(dw)), but clearly distinct because of other factors including the composition of food. Here, we develop a mechanistic geographical information system (GIS) model to produce spatial projections of δ(2)H(bw) and δ(18)O(bw) values for the USA. We investigate the influence of gender, food, and drinking water on the predicted values by comparing them with the published values. The strongest influence on the predicted values was related to the source of δ(2)H(dw) and δ(18)O(dw) values. We combine the model with equations that describe the rate of turnover to produce estimates for the time required for a non-resident to reach an isotopic equilibrium with a resident population.     

Isotopic composition of sulfates: similarities - differences - misleadings

Abstract In the hydrosphere sulfates of the following origin may exist: (1) evaporitic; they come from the leaching of sulfate rocks, (2) biological, formed by sulfur-oxidizing bacteria and (3) anthropogenic, which get into water with wastes, fertilizers or acid rains. Chemical analyses may reveal sulfates in water, but their origin cannot be assessed by means of chemical analysis. The sulfates of various origin may differ in their isotopic compositions. However, sometimes we can observe the similarity of δ(34)S of sulfates whose origin was entirely different. This similarity may be so suggestive that it could be misleading. This paper presents patterns of completely different sulfates whose δ(34)S are similar, though they have nothing in common. Other tables present patterns of sulfates whose origin is similar or even the same but their δ(34)S are characterized by great variety. All of the isotopic data presented in the tables were specially chosen from some of the results of the studies of the sulfates in waters in Poland. Isotopes techniques are becoming more popular and are useful for studies in many fields. These patterns may be a warning against drawing hasty conclusions from the results of δ-measuring.     

Deuterium and Oxygen-18 in Surface Waters of GDR draining to the Baltic Sea

A general view is presented of deuterium and ¹⁸O measurements of water samples collected at running and standing surface waters in German Democratic Republic. The values confirm earlier observations that the surface waters are influenced by evaporation with respect to the isotopic composition of groundwater. Nevertheless, stronger evaporation effects are restricted to larger lakes. The amount of surface water discharge from GDR to the Baltic Sea and the δD and δ¹⁸O values are discussed. The river Oder provides about 90% of the whole surface run-off. The other watercourses to the coast are unimportand. The mean heavy isotope content of surface run-off was calculated to be ?8.3‰ for δ¹⁸O and ?61‰ for δD (vs. SMOW), respectively.