ISOTOPE COMPOSITION OF NATURAL WATERS IN THE VERKH-TULA SETTLEMENT (THE NOVOSIBIRSK REGION)

The first data obtained in the isotope hydrogeochemical studies of natural waters in the Verkh-Tula settlement are presented in the work. The composition of these waters is mainly HCO Na-Mg-Ca with TDS varying from 542 to 731 mg/dm, and silicon content 0.46 to 7.04 mg/dm. The geochemical parameters of the medium vary from reductive to oxidative with Eh -157.4 - +231, weakly alkaline pH (7,4 - 8,1) and О 0.29 - 5.52 mg/dm3. It was established that δD and δ18O of surface and ground waters differ from each other substantially and vary from -105 to -126 ‰ and from -13.2 to -16.3 ‰ - for the former, and from -136 to -138 ‰, from -18.3 to -18.8 ‰ - for the latter. According to the data obtained, for the majority of groundwaters, the time of water residence in the aquifer is not less than 5 years, and their feeding is independent of local surface waters. The isotope composition of water-dissolved carbon (δС from -14.3 to -12.5 ‰) points to the biogenic origin of carbon dioxide participating in carbonate-silicate weathering.

The size and the age of the metabolically active carbon in tree roots

Little is known about the sources and age of C respired from tree roots. Previous research in tree stems has identified two functional pools of non-structural carbohydrates (NSC): an ‘active’ pool supplied directly from canopy photo-assimilates that supports metabolism and a ‘stored’ pool used when fresh C supplies are limited. We compared the C isotope composition of water soluble NSC and respired CO for aspen roots (Populus tremula hybrids) that were cut off fresh C supply via stem-girdling and prolonged incubation of excised roots. We used bomb radiocarbon to estimate the time elapsed since C fixation for respired CO, water-soluble C, and structural α-cellulose. While freshly excised roots respired CO with mean age <1 yr, within a week the age increased to 1.6-2.9 yr. Freshly excised roots from trees girdled ~3 months previously had similar respiration rates and NSC stocks as un-girdled trees, but respired older C (~1.2 yr). We estimate the NSC in girdled roots must be replaced 5-7 times by reserves remobilized from root-external sources. Using a mixing model and observed correlations between ΔC of water-soluble C and α-cellulose, we estimate ~30% of C is ‘active’ (~5 mg C g).

Seasonal deposition of authigenic calcite out of isotopic equilibrium with DIC and water, and implications for paleolimnological studies

We conducted year-round, monthly monitoring of the stable isotope composition of DIC and water in hypereutrophic Lake Kierskie, western Poland, along with isotope measures of calcite collected in sediment traps installed at 16 and 30 m water depth in the lake. Isotope data were supplemented by previously published data on physico-chemical variables in the lake water column. We sought to determine how carbon and oxygen isotopic disequilibria in calcite deposited in the lake’s laminated sediments vary seasonally, and what factors drive this variability. Deposition of calcite out of equilibrium with DIC and water was documented over the entire study period. For δ18O, the disequilibrium difference between successive months far exceeded the amplitude of the seasonal variability in the isotope composition of water. The biggest difference between the measured and calculated δ13Ccalcite and δ18Ocalcite values was observed during late autumn and winter sediment resuspension and redeposition (2.4‰ and 5.4‰, respectively). In the spring, δ13Ccalcite and δ18Ocalcite offsets from equilibria, 0.5‰ and 1.3‰, respectively, resulted from rapid precipitation of large calcite crystals. During summer, intense productivity and processes related to calcifying algae (“vital effects”) caused lower δ13C (0.5–1.8‰) and δ18O (2.8–2.9‰) in calcite. Differences between isotope values of calcite collected from the two water depths were small, and might have resulted from different settling velocities of small and large crystals, and/or preferential dissolution of smaller grains. We suggest that winter laminae should be excluded from isotope studies of varved sediments whenever possible, as they likely contain redeposited carbonate in which the isotope value is not indicative of conditions in the lake at the time of laminae formation. We also recommend supplementing isotope analysis of calcite in varved lake sediments with seasonally resolved analysis of carbonate content. It appears that major shifts in the proportion of carbonate deposited across seasons can cause notable changes in mean annual values of δ18Ocalcite and δ13Ccalcite, even if DIC and water isotopic compositions remain stable.

Using Stable Isotopes to Determine the Water Balance of Utah Lake (Utah, USA)

To investigate the hydrology of Utah Lake, we analyzed the hydrogen (δ2H) and oxygen (δ18O) stable isotope composition of water samples collected from the various components of its system. The average δ2H and δ18O values of the inlets are similar to the average values of groundwater, which in turn has a composition that is similar to winter precipitation. This suggests that snowmelt-fed groundwater is the main source of Utah Valley river waters. In addition, samples from the inlets plot close to the local meteoric water line, suggesting that no significant evaporation is occurring in these rivers. In contrast, the lake and its outlet have higher average δ-values than the inlets and plot along evaporation lines, suggesting the occurrence of significant evaporation. Isotope data also indicate that the lake is poorly mixed horizontally, but well mixed vertically. Calculations based on mass balance equations provide estimates for the percentage of input water lost by evaporation (~47%), for the residence time of water in the lake (~0.5 years), and for the volume of groundwater inflow (~700 million m3) during the period April to November. The short water residence time and the high percentage of total inflow coming from groundwater might suggest that the lake is more susceptible to groundwater pollution than to surface water pollution.

Correcting the impact of the isotope composition on the mixing ratio dependency of water vapour isotope measurements with cavity ring-down spectrometers

Recent advances in laser spectroscopy enable high-frequency in situ measurements of the isotope composition of water vapour. At low water vapour mixing ratios, however, the measured stable water isotope composition can be substantially affected by a measurement artefact known as the mixing ratio dependency, which is commonly considered independent of the isotope composition. Here we systematically investigate how the mixing ratio dependency, in a range from 500 to 23 000 ppmv of three commercial cavity ring-down spectrometers, is affected by the isotope composition of water vapour. We find that the isotope composition of water vapour has a substantial and systematic impact on the mixing ratio dependency for all three analysers, particularly at mixing ratios below 4000 ppmv. This isotope composition dependency can create a deviation of ±0.5 ‰ and ±6.0 ‰ for δ18O and δD, respectively, at ∼2000 ppmv, resulting in about 2 ‰–3 ‰ deviation for the d-excess. An assessment of the robustness of our findings shows that the overall behaviour is reproducible over up to 2 years for different dry gas supplies, while being independent of the method for generating the water vapour and being the first order of the evaluation sequence. We propose replacing the univariate mixing ratio dependency corrections with a new, combined isotope composition–mixing ratio dependency correction. Using aircraft- and ship-based measurements in an Arctic environment, we illustrate a relevant application of the correction. Based on our findings, we suggest that the dependency on the isotope composition may be primarily related to spectroscopy. Repeatedly characterising the combined isotope composition–mixing ratio dependency of laser spectrometers when performing water vapour measurements at high elevations, on aircraft, or in polar regions appears critical to enable reliable data interpretation in dry environments.

²H and ¹⁸O depletion of water close to organic surfaces

Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average −0.91 ± 0.22 ‰ for 18∕16O and −20.6 ± 2.4 ‰ for 2∕1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded −4 ‰ for 18∕16O and −44 ‰ for 2∕1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid–water interface.

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotope observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ18Ov ranged from −40.2 to −15.9 ‰ and δ2Hv ranged from −278.7 to −113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess (dv) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in dv, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol−1) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. Based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.

Isotopic offset between unconfined water and water adsorbed to organic matter in equilibrium

Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid:water ratio and the enrichment of heavy isotopes in adsorbed water compared with unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, enrichment of the adsorbed water was significant and negative (on average −0.91 ‰ for 18O and −20.6 ‰ for 2H at an average solid:water ratio of 0.9). The observed enrichment was not caused by solutes, volatiles or old water because the enrichment did not disappear for washed or oven dried silage, the enrichment was also found in filter paper and cotton, and the enrichment was independent of the isotopic composition of the unconfined water. Enrichment became linearly more negative with increasing volumetric solid:water ratio and even exceeded −4 ‰ for 18O and −44 ‰ for 2H. This enrichment behavior could be modeled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapor. When we applied the model to soil water under grassland, the soil water extracted from 7 cm and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid:water ratio is larger than 0.5 or for processes occurring at the solid-water interface.