A passive method for sampling water in the soil-plant-atmosphere continuum for stable hydrogen and oxygen isotope analyses.

RATIONALE: Hydrogen and oxygen isotopes in water molecules are powerful tools to constrain the dynamics of water cycling within the soil-plant-atmosphere continuum (SPAC). However, the recovery of water from the SPAC requires logistical arrangements and implementation of different time- and cost-consuming techniques in either the field or the laboratory. METHODS: We developed a passive method to sample water from the three compartments of the SPAC by using a hygroscopic salt of a high water absorbance capacity (CaCl2 ). This method allows either H2 O(V) -H2 O(L) isotope equilibration in the case of infinite water reservoir (atmospheric water vapor (WV)) or quantitative absorption of water from a finite water reservoir (e.g. soil and plants). The water absorbed by CaCl2 was distilled first and subsequently processed for hydrogen and triple oxygen isotope mass spectrometry analyses. The distillation step can be bypassed when employing isotope analytical techniques that are based on equilibration. RESULTS: Our experiments show that anhydrous CaCl2 absorbs WV of 210 ± 6% and 130 ± 6% of its dry weight from an infinite WV reservoir at relative humidity of 60% and 30%, respectively. Chemical and isotope equilibrations between WV and absorbed water were attained within 3 days at room temperature, enabling the back-calculation of the isotope composition of atmospheric WV. Preliminary experiments to extract water from plant and sand (i.e. finite WV reservoir) demonstrate a quasi-complete recovery of water in these matrices without significant isotope fractionation. The reproducibility of our method is better than 1.6‰, 0.32‰, 0.17‰ and 6‰ per meg for δ2 H, δ18 O, δ17 O and 17 O-excess. CONCLUSIONS: The CaCl2 -H2 O absorption (passive) method requires very limited logistics in the field facilitating spatial and temporal water vapor/water sampling from atmosphere and soil at low resolution (i.e. average of 3-5 days). Moreover, it allows high sample throughput for the extraction of plant water in the laboratory. The reproducibility of this method is similar to the analytical uncertainty in mass spectrometry analyses.

Optimizing sulfate pyrolysis triple oxygen isotope analysis for samples from desert environments.

RATIONALE: The triple oxygen isotope composition of sulfate may reveal the formation pathway and depositional sources and may indicate slow biologic cycling in the environment. Pyrolysis mass spectrometry is better suited for large sample workloads during environmental profiling but sufficient precision and a thorough verification of accuracy are required for comparison with higher precision laser fluorination data. METHODS: Quantitative sulfate extraction from soil samples at neutral pH, purification, conversation into Ag-sulfate, and pyrolysis mass spectrometry were modified for high sample throughput. Samples were analyzed after pyrolysis in quartz cups and gold capsules in a modified EuroVector model 3000 elemental analyzer. Sample O2 was measured in continuous He-flow after purification by cryo-trapping and chromatography on a Thermo Finnigan MAT253 isotope ratio mass spectrometer. A protocol for routine quality control and data normalization ensures long-term accuracy of the pyrolysis method. RESULTS: The 1σ SD external reproducibility is 0.12‰ for Δ17 OSO4 values on 30 µmol samples. Careful normalization for a daily analytical session accounts for changing pyrolysis conditions over the course of multiple sessions. The precision and accuracy obtained with quartz cups are comparable with those obtained with gold capsules. Pyrolysis and fluorination data for in-house standards from four laboratories and from an Atacama Desert gypsum-soil profile are identical and demonstrate the accuracy of our simplified method. CONCLUSIONS: Pyrolysis of sulfate in quartz cups and a modified simple elemental analyzer setup allows for accurate, precise, fast, cost-efficient, and non-hazardous mass spectrometric analysis. Exchangeability of data from pyrolysis and laser fluorination methods was demonstrated by repeat analysis of standards and natural samples despite high contents of interfering, easily soluble nitrates and chlorides.

Impact of climate change on the transition of Neanderthals to modern humans in Europe.

Two speleothem stable isotope records from East-Central Europe demonstrate that Greenland Stadial 12 (GS12) and GS10-at 44.3-43.3 and 40.8-40.2 ka-were prominent intervals of cold and arid conditions. GS12, GS11, and GS10 are coeval with a regional pattern of culturally (near-)sterile layers within Europe's diachronous archeologic transition from Neanderthals to modern human Aurignacian. Sterile layers coeval with GS12 precede the Aurignacian throughout the middle and upper Danube region. In some records from the northern Iberian Peninsula, such layers are coeval with GS11 and separate the Châtelperronian from the Aurignacian. Sterile layers preceding the Aurignacian in the remaining Châtelperronian domain are coeval with GS10 and the previously reported 40.0- to 40.8-ka cal BP [calendar years before present (1950)] time range of Neanderthals' disappearance from most of Europe. This suggests that ecologic stress during stadial expansion of steppe landscape caused a diachronous pattern of depopulation of Neanderthals, which facilitated repopulation by modern humans who appear to have been better adapted to this environment. Consecutive depopulation-repopulation cycles during severe stadials of the middle pleniglacial may principally explain the repeated replacement of Europe's population and its genetic composition.

Simultaneous analysis of (17) O/(16) O, (18) O/(16) O and (2) H/(1) H of gypsum hydration water by cavity ring-down laser spectroscopy.

RATIONALE: The recent development of cavity ring-down laser spectroscopy (CRDS) instruments capable of measuring (17) O-excess in water has created new opportunities for studying the hydrologic cycle. Here we apply this new method to studying the triple oxygen ((17) O/(16) O, (18) O/(16) O) and hydrogen ((2) H/(1) H) isotope ratios of gypsum hydration water (GHW), which can provide information about the conditions under which the mineral formed and subsequent post-depositional interaction with other fluids. METHODS: We developed a semi-automated procedure for extracting GHW by slowly heating the sample to 400°C in vacuo and cryogenically trapping the evolved water. The isotopic composition (δ(17) O, δ(18) O and δ(2) H values) of the GHW is subsequently measured by CRDS. The extraction apparatus allows the dehydration of five samples and one standard simultaneously, thereby increasing the long-term precision and sample throughput compared with previous methods. The apparatus is also useful for distilling brines prior to isotopic analysis. A direct comparison is made between results of (17) O-excess in GHW obtained by CRDS and fluorination followed by isotope ratio mass spectrometry (IRMS) of O2 . RESULTS: The long-term analytical precision of our method of extraction and isotopic analysis of GHW by CRDS is ±0.07‰ for δ(17) O values, ±0.13‰ for δ(18) O values and ±0.49‰ for δ(2) H values (all ±1SD), and ±1.1‰ and ±8 per meg for the deuterium-excess and (17) O-excess, respectively. Accurate measurement of the (17) O-excess values of GHW, of both synthetic and natural samples, requires the use of a micro-combustion module (MCM). This accessory removes contaminants (VOCs, H2 S, etc.) from the water vapour stream that interfere with the wavelengths used for spectroscopic measurement of water isotopologues. CRDS/MCM and IRMS methods yield similar isotopic results for the analysis of both synthetic and natural gypsum samples within analytical error of the two methods. CONCLUSIONS: We demonstrate that precise and simultaneous isotopic measurements of δ(17) O, δ(18) O and δ(2) H values, and the derived deuterium-excess and (17) O-excess, can be obtained from GHW and brines using a new extraction apparatus and subsequent measurement by CRDS. This method provides new opportunities for the application of water isotope tracers in hydrologic and paleoclimatologic research.

Investigating the geochemical behavior and exploration potential of lithium in brines; a case study of Bam salt plug, Zagros Zone, southern Iran.

Lithium (Li) is a scarce and technologically important element; the demand for which has recently increased due to its extensive consumption, particularly in manufacturing of Li-ion batteries, renewable energy, and electronics. Li is extracted from brines, pegmatite, and clay minerals; though extraction from brines is economically preferred. More than 200 salt plugs are in the Zagros Mountains which represent potential sources for Li exploration. This preliminary study collected first data on the abundance of Li in the salt plugs in southern Iran, and investigated Li distribution during evaporation of halite-producing brine ponds. The XRD analysis of powdered samples showed that gypsum and halite are the dominant solid phases in the ponds in which Li is concentrated in gypsum, while halite is depleted of Li. ICP-MS and ICP-OES analyses showed that Li in brines is concentrated during the evaporation by factors up to 28 with total contents up to 40 mg kg‒1. The Mg/Li ratio was higher than 70, which makes the brine unsuitable for conventional evaporation extraction techniques which require Mg/Li ratios of less than 6. Considering that 25 mg kg‒1 is a suitable concentration of Li for exploration purposes, the results of this study suggest that with the advancement of extraction techniques, the depletion of presently used high-grade Li reserves, the increasing demand for lithium, the need for extraction from diverse sources, and the exploration of new resources, the salt plug brines have an exploratory potential for Li in the future.

High diversity and isolated distribution of aquatic heterotrophic protists in salars of the Atacama Desert at different salinities.

The species richness of eukaryotes in the hypersaline environment is generally thought to be low. However, recent studies showed a high degree of phylogenetic novelty at these extreme conditions with variable chemical parameters. These findings call for a more thorough look into the species richness of hypersaline environments. In this study, various hypersaline lakes (salars, 1-348 PSU) as well as further aquatic ecosystems of northern Chile were investigated regarding diversity of heterotrophic protists by metabarcoding studies of surface water samples. Investigations of genotypes of 18S rRNA genes showed a unique community composition in nearly each salar and even among different microhabitats within one salar. The genotype distribution showed no clear connection to the composition of main ions at the sampling sites, but protist communities from similar salinity ranges (either hypersaline, hyposaline or mesosaline) clustered together regarding their OTU composition. Salars appeared to be fairly isolated systems with only little exchange of protist communities where evolutionary lineages could separately evolve.

Uniquely low stable iron isotopic signatures in deep marine sediments caused by Rayleigh distillation.

Dissimilatory iron reduction (DIR) is suggested to be one of the earliest forms of microbial respiration. It plays an important role in the biogeochemical cycling of iron in modern and ancient sediments. Since microbial iron cycling is typically accompanied by iron isotope fractionation, stable iron isotopes are used as tracer for biological activity. Here we present iron isotope data for dissolved and sequentially extracted sedimentary iron pools from deep and hot subseafloor sediments retrieved in the Nankai Trough off Japan. Dissolved iron (Fe(II)aq) is isotopically light throughout the ferruginous sediment interval but some samples have exceptionally light isotope values. Such light values have never been reported in natural marine environments and cannot be solely attributed to DIR. We show that the light isotope values are best explained by a Rayleigh distillation model where Fe(II)aq is continuously removed from the pore water by adsorption onto iron (oxyhydr)oxide surfaces. While the microbially mediated Fe(II)aq release has ceased due to an increase in temperature beyond the threshold of mesophilic microorganisms, the abiotic adsorptive Fe(II)aq removal continued, leading to uniquely light isotope values. These findings have important implications for the interpretation of dissolved iron isotope data especially in deep subseafloor sediments.

Iron assimilation by the clam Laternula elliptica: Do stable isotopes (δ56Fe) help to decipher the sources?

Iron stable isotope signatures (δ(56)Fe) in hemolymph (bivalve blood) of the Antarctic bivalve Laternula elliptica were analyzed by Multiple Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) to test whether the isotopic fingerprint can be tracked back to the predominant sources of the assimilated Fe. An earlier investigation of Fe concentrations in L. elliptica hemolymph suggested that an assimilation of reactive and bioavailable Fe (oxyhydr)oxide particles (i.e. ferrihydrite), precipitated from pore water Fe around the benthic boundary, is responsible for the high Fe concentration in L. elliptica (Poigner et al., 2013 b). At two stations in Potter Cove (King George Island, Antarctica) bivalve hemolymph showed mean δ(56)Fe values of -1.19 ± 0.34‰ and -1.04 ± 0.39 ‰, respectively, which is between 0.5‰ and 0.85‰ lighter than the pool of easily reducible Fe (oxyhydr)oxides of the surface sediments (-0.3‰ to -0.6‰). This is in agreement with the enrichment of lighter Fe isotopes at higher trophic levels, resulting from the preferential assimilation of light isotopes from nutrition. Nevertheless, δ(56)Fe hemolymph values from both stations showed a high variability, ranging between -0.21‰ (value close to unaltered/primary Fe(oxyhydr)oxide minerals) and -1.91‰ (typical for pore water Fe or diagenetic Fe precipitates), which we interpret as a "mixed" δ(56)Fe signature caused by Fe assimilation from different sources with varying Fe contents and δ(56)Fe values. Furthermore, mass dependent Fe fractionation related to physiological processes within the bivalve cannot be ruled out. This is the first study addressing the potential of Fe isotopes for tracing back food sources of bivalves.