17 O-excess and d-excess of atmospheric water vapor measured by cavity ring-down spectrometry: Evidence of a matrix effect and implication for the calibration procedure.

RATIONALE: Producing robust high-frequency time series of raw atmospheric water vapor isotope data using laser spectrometry requires accurate calibration. In particular, the chemical composition of the analyzed sample gas can cause isotope bias. This study assesses the matrix effect on calibrated δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess values of atmospheric water vapor. METHODS: A Picarro L2140-i cavity ring-down spectrometer with an autosampler and a vaporizer is used to analyze δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess of two water standards. Isotope data obtained using synthetic air and dry ambient air as carrier gas at water mixing ratios ranging from 2000 to 30 000 ppmv are compared. Based on the results, atmospheric water vapor measurements are calibrated. The expected precision is estimated by Monte Carlo simulation. RESULTS: The dry air source strongly impacts raw isotope values of the two water standards but has no effect on the mixing ratio dependency functions. When synthetic air is used, δ17 O, δ18 O, and 17 O-excess of calibrated atmospheric water vapor are overestimated by 0.6‰, 0.7‰, and 217 per meg, respectively, whereas δ2 H and d-excess are underestimated by 1.5‰ and 7.3‰. Optimum precisions for the calibrated δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess values and 12 min integration time are 0.02‰, 0.03‰, 0.4‰, 14 per meg, and 0.4‰, respectively. CONCLUSIONS: Regarding the obtained results, recommendations for the calibration of atmospheric water vapor isotope measurements are presented. The necessity to use dry ambient air as dry air source when running the standards for calibration is pointed out as a prerequisite for accurate atmospheric water vapor 17 O-excess and d-excess measurements.

Improving memory effect correction to achieve high-precision analysis of δ17 O, δ18 O, δ2 H, 17 O-excess and d-excess in water using cavity ring-down laser spectroscopy.

RATIONALE: The precision obtained in routine isotope analysis of water (δ17 O, δ18 O, δ2 H, 17 O-excess and d-excess values) using cavity ring-down spectroscopy is usually below the instrument specifications provided by the manufacturer. This study aimed at reducing this discrepancy, with particular attention paid to mitigating the memory effect (ME). METHODS: We used a Picarro L2140i analyzer coupled with a high-precision A0211 vaporizer and an A0325 autosampler. The magnitude and duration of the ME were estimated using 24 series of 50 successive injections of samples with contrasting compositions. Four memory correction methods were compared, and the instrument performance was evaluated over a 17-month period of routine analysis, using two different run architectures. RESULTS: The ME remains detectable after the 30th injection, implying that common correction procedures only based on the last preceding sample need to be revised. We developed a new ME correction based on the composition of several successive samples, and designed a run architecture to minimize the magnitude of the ME. The standard deviation obtained from routine measurement of a quality assurance water sample over a seven-month period was 0.015‰ for δ17 O, 0.023‰ for δ18 O, 0.078‰ for δ2 H, 0.006‰ for 17 O-excess and 0.173‰ for d-excess. In addition, we provided the first δ17 O and 17 O-excess values for the GRESP certified reference material. CONCLUSIONS: This study demonstrates the long-term persistence of the ME, which is often overlooked in routine analysis of natural samples. As already evidenced when measuring labelled water, it calls for consideration of the compositions of several previous samples to obtain an appropriate correction, a prerequisite to achieve high-precision data.

Water transit time and active recharge in the Sahel inferred by bomb-produced 36Cl.

The lack of data and suitable methods to quantify regional hydrological processes often hinders sustainable water management and adaptation to climate change in semiarid regions, particularly in the Sahel, which is known for its climatic variability. Here we show that 36Cl from nuclear tests is a promising method to estimate water transit times and groundwater recharge rates on the catchment scale, and to distinguish water and chloride cycles. 36Cl was measured in 131 surface and groundwater samples in the Chari-Logone sub-catchment of the emblematic Lake Chad Basin, located in central Sahel. It was found that only 12 ± 8% of the catchment is connected to the main rivers. Groundwater supporting rivers in the upper humid part of the catchment has a mean transit time of 9.5 ± 1 years and a recharge rate of 240 ± 170 mm yr-1. In the lower Sahelian part of the catchment, stream-focused recharge yields recharge rates up to 78 ± 7 mm yr-1 in riparian groundwater against 16 ± 27 mm yr-1 elsewhere. Our estimates suggest that aquifers in the Sahel host a significant amount of renewable water, which could therefore be used as a strategic freshwater resource.

A global database of water vapor isotopes measured with high temporal resolution infrared laser spectroscopy.

The isotopic composition of water vapour provides integrated perspectives on the hydrological histories of air masses and has been widely used for tracing physical processes in hydrological and climatic studies. Over the last two decades, the infrared laser spectroscopy technique has been used to measure the isotopic composition of water vapour near the Earth's surface. Here, we have assembled a global database of high temporal resolution stable water vapour isotope ratios (δ18O and δD) observed using this measurement technique. As of March 2018, the database includes data collected at 35 sites in 15 Köppen climate zones from the years 2004 to 2017. The key variables in each dataset are hourly values of δ18O and δD in atmospheric water vapour. To support interpretation of the isotopologue data, synchronized time series of standard meteorological variables from in situ observations and ERA5 reanalyses are also provided. This database is intended to serve as a centralized platform allowing researchers to share their vapour isotope datasets, thus facilitating investigations that transcend disciplinary and geographic boundaries.

Pan-derived isotopic composition of atmospheric vapour in a Mediterranean wetland (Rhône River Delta, France).

A continuous record of atmospheric vapour isotopic composition (delta(A)) can be derived from the isotope mass balance of a water body submitted to natural evaporation. In this paper, we present preliminary results of the application of this method to a drying evaporation pan, located in a Mediterranean wetland, during a two-month summer period. Results seem consistent with few atmospheric vapour data based on the assumption of isotopic equilibrium with precipitation, but we observed a shift between pan-derived delta(A) and the composition of vapour samples collected by cold trapping. These results suggest that further investigations are necessary to evaluate the effect of diurnal variations of atmospheric conditions on the applicability of the pan-evaporation method, and on the representative of grab atmospheric samples. We also propose a sensitivity analysis for evaluating the impact of the different measured components on delta(A) calculation, and show an improvement in the method efficiency as the pan is drying.