Characterization of a customized calibration unit for continuous measurements of the isotopic composition of water vapor

The objective of this work is the development, standardization and creation of a method to carry out continuous measurement of oxygen and hydrogen isotopic composition of the atmospheric water vapor using a wavelengthscanned cavity ring down spectroscopy (WS-CRDS) instrument produced by Picarro, L1102-i model. Some technical improvements of the standard instrument configuration have been made to create three different inlet gas lines: a “standard” line, a calibration line and a line connected with the external sampler. The calibration line is composed of a syringe-pump that continuously injects standard water into a steel tee heated at the temperature of 170◦C and flushed with dry nitrogen gas. In this way, instantaneous and complete vaporization of the standard water takes place. The resulting steam is characterized by a well-defined composition in δD e δ18O values. To allow comparison with other international data, we have characterized the individual instrumental response to variation of the isotopic composition of the water vapor. Several humidity-isotope response functions (6000-26000 ppmv) have been estimated with three different internal standards (0.35h -8.75h -29.11h and -40.28h for δ18O; 2.31h -58.91h -222.19h and -317.78h for δD). Moreover, we have measured the instrumental drift at regular time intervals to apply the opportune corrections to instrument data. The setup has been tested using a 3.5 day continuous measurements carried out with the Picarro sampling the water vapor outside our campus in Venice and parallel sampling using the classical cryogenic trapping procedure, obtaining excellent results. Furthermore, our analysis technique has given good results for the standards with values which are similar to those obtained with the isotope ratio mass spectrometry (IRMS) technique

The isotopic composition of water vapor: from discrete to continuous measurements. A focus on calibration methods

The water residence time in the atmosphere is approximately nine days, the shortest residence time in any major reservoir of the whole water cycle on the planet. Nevertheless, water vapor is a key factor in climate and hydrology due to its dynamic behavior. The isotopic composition of water vapor can highlight several processes of the water cycle that link the water reservoirs to the atmosphere (Galewsky et al., 2016). In the past, the isotopic composition of water vapor was generally inferred from precipitation data, assuming isotopic equilibrium between rain and water vapor. This assumption works well when precipitation is abundant but gives misleading results when precipitation is scarce. A common method to determine the isotopic composition of water vapor is the cryotrapping technique, proposed by Craig et al., (1963). Cryotrapping consists in freezing all the moisture content of the air (to avoid fractionation) and analyze the liquid sample with the regular mass spectrometry technique. This process includes the designing of customized cold traps and usually requires several man-hours due to the long sampling time (2 - 8 hours per sample). With the advent of the laser absorption spectrometry (LAS) technique is now possible to determine the isotopic composition of water vapor with sampling time down to seconds. This novel technique increases our knowledge about the isotopic composition of water vapor and gives a substantial help in our understanding of the water cycle, both on global and local scales. However, the continuous measurement of isotopic composition of water vapor requires a specific method to calibrate the large amount of data resulting as the output of a Cavity Ring-Down Spectroscopy (CRDS) analyzer. This includes the production of vapor with known isotopic composition, determination of the response of the analyzer to different humidity levels and correction of the instrumental drift. In this work, we present a summary of potential calibration techniques for continuous measurements of the isotopic composition of water vapor. The study goes in-depth on the developing of a customized calibration unit for a commercial CRDS analyzer (Picarro L1102i). Continuous measurements will be compared to water vapor samples collected with cryotraps and several continuous measurements will be presented highlighting sub-daily processes in the atmospheric boundary layer

Stable isotopes in water vapor and precipitation for a coastal lagoon at mid latitudes

The stable oxygen and hydrogen isotope composition in precipitation can be used in hydrology to describe the signature of local meteoric water. The isotopic composition of water vapor is usually obtained indirectly from measurements of δD and δ18O in precipitation, assuming the isotopic equilibrium between rain and water vapor. Only few studies report isotopic data in both phases for the same area, thus providing a complete Local Meteoric Water Line (LMWL). The goal of this study is to build a complete LMWL for the lagoon of Venice (northern Italy) with observations of both water vapor and precipitation. The sampling campaign has started in March 2015 and will be carried out until the end of 2016. Water vapor is collected once a week with cold traps at low temperatures (−77◦C). Precipitation is collected on event and monthly basis with a custom automatic rain sampler and a rain gauge, respectively. Liquid samples are analyzed with a Picarro L1102-i and results are reported vs VSMOW. The main meteorological parameters are continuously recorded in the same area by the campus automatic weather station. Preliminary data show an LMWL close to the Global Meteoric Water Line (GMWL) with lower slope and intercept. An evaporation line is clearly recognizable, considering samples that evaporated between the cloud base and the ground. The deviation from the GMWL parameters, especially intercept, can be attributed to evaporated rain or to the humidity conditions of the water vapor source. Water vapor collected during rainfall shows that rain and vapor are near the isotopic equilibrium, just considering air temperature measured at ground level. Temperature is one of the main factor that controls the isotopic composition of the atmospheric water vapor. Nevertheless, the circulation of air masses is a crucial parameter which has to be considered. Water vapor samples collected in different days but with the same meteorological conditions (air temperature and relative humidity) show differences in terms of δ18O up to 3h. Isotopic ratios in rain events and water vapor are in fact dominated by a seasonal component but outliers are clearly linked to air parcel origin. The monthly measurements of δD and δ18O in precipitation of August 2015, for instance, are lower than in colder months, considering monthly average temperatures. Single rain events show a small sequence of precipitation, that leads to 40% of total precipitation of August, which lowers δ−values considerably. The sampling on event basis during occasional and discontinuous rain also allows to identify the rainout effect, which leads to lightening water during a rainfall. Statistics based on back trajectories (48 hours) show that the major part of air parcels travels across central Europe and derives from sources located in the north Atlantic, whereas, a smaller fraction of the water vapor can be attributed to editerranean sources

Spatial variability in isotopic composition of surface snow along the East Antarctic International Ice Sheet Traverse (EAIIST)

The isotopic signal of oxygen and hydrogen, archived in the Antarctic ice sheet through snow precipitation, is an important proxy of climatic conditions. This signal depends on several parameters such as local temperature, climatic conditions in the moisture source areas and air mass pathways. Moreover, the isotopic composition may be affected by spatial variability induced by the interactions of the snow surface with the overlying atmosphere along the direction of the prevailing winds. In regions where the snow accumulation is very low, interactions between the atmosphere and the snow surface could modify the pristine signal through isotopic exchanges, sublimation processes and mechanical mixing originated from wind action. The EAIIST (East Antarctic International Ice Sheet Traverse) traverse, that took place during the 2019-2020 Antarctic field season, starting from Concordia Station towards the South Pole, provides a perfect path of study. Along the EAIIST traverse, areas with homogeneous accumulation rates can be compared to areas influenced by wind scouring and mega-dunes formation. Extremely low accumulation and wind-surface snow interaction observed in these areas could be representative of glacial period conditions in the Antarctic Plateau. Here we present the isotopic composition (dD and d18O) of surface (a few cm of depth), bulk (1 m depth) and snow pit (2 m depth) samples along the EAIIST traverse to evaluate the parameters explaining the spatial variability of this proxy. The dD, d18O and, the deuterium excess will be evaluated with respect to geographical features (elevation, latitude, distance from the coast, slope) and climatic conditions (temperature, accumulation, wind speed and direction). Wind action is expected to play a major role in explaining the isotopic spatial variability in these areas. Understanding the spatial variability in the deposition process, which strongly decreases the ratio between signal and noise, is essential to better interpret high-resolution isotopic profiles from firn and ice cores, collected along the EAIIST traverse, which will be analyzed soon

The spatial variability in isotopic composition of surface snow and snowpits on the East Antarctic Ice Sheet

The water isotope composition of snow precipitations, archived in the Antarctic ice sheet every year, is an important proxy of climatic conditions. This signal depends on several parameters such as local temperature, altitude, moisture source areas and air mass pathways. However, especially in areas where snow accumulation is very low (as on the East Antarctic Plateau), the isotopic composition is affected by additional spatial variability induced by the interactions between the atmosphere and snow surface, and the pristine signal may be modified through isotopic exchanges, sublimation processes and mechanical mixing originated from wind action. Here, we present the isotopic composition (D and 18O) and the second-order parameter d-excess of surface snow and snowpit samples collected during the Italian-French campaign in Antarctica (2019-2020). The sampling sites cover the area from Dumont D'Urville to Concordia Station and from Concordia Station towards the South Pole (EAIIST – East Antarctic International Ice Sheet Traverse). These data, compared with a previous dataset of Antarctic surface snow isotopic composition (Masson-Delmotte et al. 2008), are analyzed to determine the variability of the spatial relationship between precipitation isotopic composition and local temperature in relation to geographical parameters (latitude, distance from the coast and elevation). The interpretation of these factors determining the isotope signature is the base to better define the amount of the effects caused by subsequent interaction between atmosphere and surface snow, and by the wind action. Understanding the spatial variability of this proxy, which strongly decreases the signal-to-noise ratio, could permit to improve the use of the “isotopic thermometer” to quantify past changes in temperature based on the stable isotopic record of deep ice cores

Preservation of chemical and isotopic signatures within the Weißseespitze millennial old ice cap (Eastern Alps), despite the ongoing ice loss

Alpine ice core research has long focused on a few suitable drilling sites at high elevation in the Western European Alps, assuming that the counterparts at lower elevation in the eastern sector are unsuitable for paleoenvironmental studies, due to the presence of melting and temperate basal conditions. However, it has been demonstrated that even in the Eastern Alpine range, below 4,000 m a.s.l., cold ice frozen to bedrock can exist. In fact, millennial-old ice has been found at some locations, such as at the Weißseespitze (WSS) summit ice cap (Ӧtztal Alps, 3,499 m a.s.l.), where about 6 kyrs appear locked into 10 m of ice. In this work, we present a full profile of the stable water isotopes (δ18O, δ2H), major ions (Na+, K+, Mg2+, Ca2+, NH4+, Cl−, NO3−, SO42−), levoglucosan, and microcharcoal for two parallel ice cores drilled at the Weißseespitze cap. We find that, despite the ongoing ice loss, the chemical and isotopic signatures appear preserved, and may potentially offer an untapped climatic record. This is especially noteworthy considering that chemical signals of other archives at similar locations have been partially or full corrupted by meltwater (i.e., Silvretta glacier, Grand Combin glacier, Ortles glacier). In addition, the impurity concentration near the surface shows no signs of anthropogenic contamination at WSS, which constrains the age at the surface to fall within the pre-industrial age

Investigating two possible schemes of Laser Ablation – Cavity Ring Down Spectrometry for water isotope measurements on ice cores

Thinning of the deep ice core layers must be considered when the water isotopic composition of the Oldest Ice Core is to be analyzed. From an experimental point of view, a novel instrument combining a micro-destructive cold femtosecond - Laser Ablation (LA) sampling system, that provides high spatial resolution together with minimal usage of ice sample, and a Cavity Ring Down Spectrometer is being built for high-quality water isotope measurements. Laser ablation results in crater formation and its morphology depends on the laser parameters used. Optical images that show crater morphology under different experimental conditions allow crater characterization towards an efficient cold LA sampling. An ablation chamber and a transfer line are both the connecting parts between the LA system and the CRDS instrument. They are to be designed and constructed in the optimal size and shape to collect the ablated mass and guarantee its smooth delivery to the CRDS analyzer with minimum disturbance. Coupling a Laser Ablation system with a CRDS analyzer has already been achieved using a laser operating at the nanosecond regime and a cryo-cell as the ablation chamber. Comparison of the two Laser Ablation systems, by the means of ice sampling and collection of the ablated material, will be of great importance to understand the ablation mechanism and post-ablation processes on ice and further develop a system dedicated to water isotope measurements

An upgraded CFA - FLC - MS/MS system for the semi-continuous detection of levoglucosan in ice cores

A new Continuous Flow Analysis (CFA) system coupled with Fast Liquid Chromatography – tandem Mass Spectrometry (FLC-MS/MS) has been recently developed for determining organic markers in ice cores. In this work we present an upgrade of this innovative technique, optimized for the detection of levoglucosan in ice cores, a crucial tracer for reconstructing past fires. The upgrade involved a specific optimization of the chromatographic and mass spectrometric parameters, allowing for a higher sampling resolution (down to 1 cm) and the simultaneous collection of discrete samples, for off-line analysis of water stable isotopes and additional chemical markers. The robustness and repeatability of the method has been tested by the analysis of multiple sticks of ice cut from the same shallow alpine ice core, and running the system for several hours on different days. The results show similar and comparable trends between the ice sticks. With this upgraded system, a higher sensitivity and a lower limit of detection (LOD) was achieved compared to discrete analysis of alpine samples for levoglucosan measurements. The new LOD was as low as 66 ng L−1, a net improvement over the previous LOD of 600 ng L−1