Investigating oxygen and carbon isotopic relationships in speleothem records over the last millennium using multiple isotope-enabled climate models

The incorporation of water isotopologues into the hydrology of general circulation models (GCMs) facilitates the comparison between modelled and measured proxy data in paleoclimate archives. However, the variability and drivers of measured and modelled water isotopologues, and indeed the diversity of their representation in different models are not well constrained. Improving our understanding of this variability in past and present climates will help to better constrain future climate change projections and decrease their range of uncertainty. Speleothems are a precisely datable paleoclimate archive and provide well preserved (semi-)continuous multivariate isotope time series in the lower and mid-latitudes, and are, therefore, well suited to assess climate and isotope variability on decadal and longer timescales. However, the relationship between speleothem oxygen and carbon isotopes to climate variables also depends on site-specific parameters, and their comparison to GCMs is not always straightforward. Here we compare speleothem oxygen and carbon isotopic signatures from the Speleothem Isotopes Synthesis and AnaLysis database version 2 (SISALv2) to the output of five different water-isotope-enabled GCMs (ECHAM5-wiso, GISS-E2-R, iCESM, iHadCM3, and isoGSM) over the last millennium (850–1850 common era, CE). We systematically evaluate differences and commonalities between the standardized model simulation outputs. The goal is to distinguish climatic drivers of variability for both modelled and measured isotopes. We find strong regional differences in the oxygen isotope signatures between models that can partly be attributed to differences in modelled temperatures. At low latitudes, precipitation amount is the dominant driver for water isotope variability, however, at cave locations the agreement between modelled temperature variability is higher than for precipitation variability. While modelled isotopic signatures at cave locations exhibited extreme events coinciding with changes in volcanic and solar forcing, such fingerprints are not apparent in the speleothem isotopes, and may be attributed to the lower temporal resolution of speleothem records compared to the events that are to be detected. Using spectral analysis, we can show that all models underestimate decadal and longer variability compared to speleothems, although to varying extent. We found that no model excels in all analyzed comparisons, although some perform better than the others in either mean or variability. Therefore, we advise a multi-model approach, whenever comparing proxy data to modelled data. Considering karst and cave internal processes through e.g. isotope-enabled karst models may alter the variability in speleothem isotopes and play an important role in determining the most appropriate model. By exploring new ways of analyzing the relationship between the oxygen and carbon isotopes, their variability, and co-variability across timescales, we provide methods that may serve as a baseline for future studies with different models using e.g. different isotopes, different climate archives, or time periods.

Quantifying the glacial meltwater contribution to streams in mountainous regions using highly resolved stable water isotope measurements

This study aims to determine the contribution of glacial meltwater to streams in mountainous regions based on stable water isotope measurements (δ18O and δ2H). For this purpose, three partially glaciated catchments were selected as the study area in the central Swiss Alps being representative of catchments that are used for hydropower energy production in Alpine regions. The glacial meltwater contribution to the catchments’ stream discharges was evaluated based on high-resolution δ18O and δ2H measurements of the end-members that contribute to the stream discharge (ice, rain, snow) and of the discharging streams. The glacial meltwater contribution to the stream discharges could be unequivocally quantified after the snowmelt in August and September when most of the annual glacial meltwater discharge occurs. In August and September, the glacial meltwater contribution to the stream discharges corresponds to up to 95 ± 2 % and to 28.7 % ± 5 % of the total annual discharge in the evaluated catchments. The high glacial meltwater contribution demonstrates that the mountainous stream discharges in August and September will probably strongly decrease in the future due to global warming-induced deglaciation, which will be, however, likely compensated by higher discharge rates in winter and spring. Nevertheless, the changing mountainous streamflow regimes in the future will pose a challenge for hydropower energy production in the mountainous areas. Overall, this study provides a successful example of an Alpine catchment monitoring strategy to quantify the glacial meltwater contribution to stream discharges based on stable isotope water data, which leads to a better validation of existing modelling studies and which can be adapted to other mountainous regions.

Determining Water Isotope Compositions for the IAEA WICO and North West Villages, South Africa

Deuterium (2H) and oxygen 18 (18O) stable isotopes in water are the key indicators of hydrological and ecological patterns and processes. The water isotopes δ2H and δ18O have been employed widely as tracers in hydrological and ecological research, as they are integrated into geological and biological systems in a predictable manner. The aim of this study was to determine the water isotope composition of the International Atomic Energy Agency’s (IAEA) Water Isotope Inter-laboratory Comparison (WICO) samples and to determine the Local Meteoric Water Line for North West Province (NWP) villages in South Africa. The IAEA WICO 2020 samples were obtained from the IAEA, Vienna, and borehole water samples from selected villages in the North West province of South Africa were randomly collected to investigate the relationship between the stable isotopes (18O and 2H) and the climate in underground water aquifers. A cavity ring-down spectroscopy analyzer with laser-current-tuned cavity resonance, Picarro L2140-i, was used to measure triple water–isotope ratios with high precision. The IAEA WICO results obtained for the d-excess were in a satisfactory range and the margins of error were close to those required by the IAEA. The δ2H values ranged between −33.00‰ and −8.00‰, while the δ18O values ranged between −5.50‰ and −2.00‰. The results of this work have shown that our water science and management lab is capable of undertaking inter-laboratory comparisons for the IAEA.

Validation of a coupled <i>δ</i>²H_{<i>n</i>-alkane}–<i>δ</i>¹⁸O_sugar paleohygrometer approach based on a climate chamber experiment

The hydrogen isotope composition of leaf-wax-derived biomarkers, e.g., long-chain n-alkanes (δ2Hn-alkane), is widely applied in paleoclimate. However, a direct reconstruction of the isotope composition of source water based on δ2Hn-alkane alone is challenging due to the enrichment of heavy isotopes during evaporation. The coupling of δ2Hn-alkane with δ18O of hemicellulose-derived sugars (δ18Osugar) has the potential to disentangle this limitation and additionally to allow relative humidity reconstructions. Here, we present δ2Hn-alkane as well as δ18Osugar results obtained from leaves of Eucalyptus globulus, Vicia faba, and Brassica oleracea, which grew under controlled conditions. We addressed the questions of (i) whether δ2Hn-alkane and δ18Osugar values allow reconstructions of leaf water isotope composition, (ii) how accurately the reconstructed leaf water isotope composition enables relative humidity (RH) reconstruction, and (iii) whether the coupling of δ2Hn-alkane and δ18Osugar enables a robust source water calculation. For all investigated species, the n-alkane n-C29 was most abundant and therefore used for compound-specific δ2H measurements. For Vicia faba, additionally the δ2H values of n-C31 could be evaluated robustly. Regarding hemicellulose-derived monosaccharides, arabinose and xylose were most abundant, and their δ18O values were therefore used to calculate weighted mean leaf δ18Osugar values. Both δ2Hn-alkane and δ18Osugar yielded significant correlations with δ2Hleaf water and δ18Oleaf water, respectively (r2=0.45 and 0.85, respectively; p<0.001, n=24). Mean fractionation factors between biomarkers and leaf water were found to be −156 ‰ (ranging from −133 ‰ to −192 ‰) for εn-alkane/leaf water and +27.3 ‰ (ranging from +23.0 ‰ to 32.3 ‰) for εsugar/leaf water, respectively. Modeled RHair values from a Craig–Gordon model using measured Tair, δ2Hleaf water and δ18Oleaf water as input correlate highly significantly with modeled RHair values (R2=0.84, p<0.001, RMSE = 6 %). When coupling δ2Hn-alkane and δ18Osugar values, the correlation of modeled RHair values with measured RHair values is weaker but still highly significant, with R2=0.54 (p<0.001, RMSE = 10 %). Finally, the reconstructed source water isotope composition (δ2Hs and δ18Os) as calculated from our coupled approach matches the source water in the climate chamber experiment (δ2Htank water and δ18Otank water). This highlights the great potential of the coupled δ2Hn-alkane–δ18Osugar paleohygrometer approach for paleoclimate and relative humidity reconstructions.

The triple oxygen isotope composition of phytoliths, a new proxy of atmospheric relative humidity: controls of soil water isotope composition, temperature, CO₂ concentration and relative humidity

Continental atmospheric relative humidity is a major climate parameter whose variability is poorly understood by global climate models. Models' improvement relies on model–data comparisons for past periods. However, there are no truly quantitative indicators of relative humidity for the pre-instrumental period. Previous studies highlighted a quantitative relationship between the triple oxygen isotope composition of phytoliths, particularly the 17O excess of phytoliths, and atmospheric relative humidity. Here, as part of a series of calibrations, we examine the respective controls of soil water isotope composition, temperature, CO2 concentration and relative humidity on phytolith 17O excess. For that purpose, the grass species Festuca arundinacea was grown in growth chambers where these parameters were varying. The setup was designed to control the evolution of the triple oxygen isotope composition of phytoliths and all the water compartments of the soil–plant–atmosphere continuum. Different analytical techniques (cavity ring-down spectroscopy and isotope ratio mass spectrometry) were used to analyze water and silica. An inter-laboratory comparison allowed to strengthen the isotope data matching. Water and phytolith isotope compositions were compared to previous datasets obtained from growth chamber and natural tropical sites. The results show that the δ′18O value of the source water governs the starting point from which the triple oxygen isotope composition of leaf water, phytolith-forming water and phytoliths evolves. However, since the 17O excess varies little in the growth chamber and natural source waters, this has no impact on the strong relative humidity dependency of the 17O excess of phytoliths, demonstrated for the 40 %–80% relative humidity range. This relative humidity dependency is not impacted by changes in air temperature or CO2 concentration either. A relative humidity proxy equation is proposed. Each per meg of change in phytolith 17O excess reflects a change in atmospheric relative humidity of ca. 0.2 %. The ±15 per meg reproducibility on the measurement of phytolith 17O excess corresponds to a ±3.6 % precision on the reconstructed relative humidity. The low sensitivity of phytolith 17O excess to climate parameters other than relative humidity makes it particularly suitable for quantitative reconstructions of continental relative humidity changes in the past.