Variations In Isotope Ratios Research Articles

Tales from the Underground: Speleothem Records of Past Hydroclimate

Geochemical records from speleothems have significantly advanced our understanding of natural climate variability over the last ~600,000 years. Speleothems are sensitive recorders of past changes in hydroclimate because they can be precisely dated and contain multiple hydrologically sensitive geochemical proxies. Oxygen isotope records from speleothems tell us about the timing and mechanisms of past changes in precipitation amount, temperature, atmospheric circulation, and/or global monsoon intensity. Variations in speleothem carbon isotope ratios or trace element concentrations reflect changes in local water balance, vegetation, and karst hydrology. Speleothem paleoclimate records represent a window into the past that can provide crucial information for understanding how anthropogenic climate change and natural climate variability will impact future water resources on Earth.

Spatiotemporal dynamics of water sources in a mountain river basin inferred through δ2H and δ18O of water.

In mountainous river basins of the Pacific Northwest, climate models predict that winter warming will result in increased precipitation falling as rain and decreased snowpack. A detailed understanding of the spatial and temporal dynamics of water sources across river networks will help illuminate climate change impacts on river flow regimes. Because the stable isotopic composition of precipitation varies geographically, variation in surface water isotope ratios indicates the volume-weighted integration of upstream source water. We measured the stable isotope ratios of surface water samples collected in the Snoqualmie River basin in western Washington over June and September 2017 and the 2018 water year. We used ordinary least squares regression and geostatistical Spatial Stream Network models to relate surface water isotope ratios to mean watershed elevation (MWE) across seasons. Geologic and discharge data was integrated with water isotopes to create a conceptual model of streamflow generation for the Snoqualmie River. We found that surface water stable isotope ratios were lowest in the spring and highest in the dry, Mediterranean summer, but related strongly to MWE throughout the year. Low isotope ratios in spring reflect the input of snowmelt into high elevation tributaries. High summer isotope ratios suggest that groundwater is sourced from low elevation areas and recharged by winter precipitation. Overall, our results suggest that baseflow in the Snoqualmie River may be resilient to predicted warming and subsequent changes to snowpack in the Pacific Northwest.

Hydrogen isotopic exchange kinetics between organic matter and water: Implications for chemical evolution during meteorite parent body processing

AbstractThe large variations in hydrogen isotope ratios found in insoluble organic matter (IOM) in chondritic meteorites may be attributed to hydrogen isotopic exchange between IOM and water during aqueous alteration. We conducted D–H exchange experiments (1) during synthesis of IOM simulant (hereafter called chondritic organic analog, COA) from formaldehyde, glycolaldehyde, and ammonia with water, and (2) with the synthesized COA with a secondary reservoir of water. The changes in the D/H ratios obtained by infrared spectra of the COA suggest that most of the hydrogen in the COA is derived from water during synthesis. We further investigated the kinetics of D–H exchange between D‐rich COA and D‐poor water, as well as the opposite case, D‐poor COA and D‐rich water. To help assess understanding exchange kinetics, two‐dimensional isotope imaging obtained using isotope microscope revealed that no gradient D–H exchange profiles were present in the COA grains, indicating that the rate‐limiting step for D–H exchange is not diffusion. Thus, the changes in D/(D + H) ratios were fit by the first‐order reaction rate law. Apparent kinetic parameters—the rate constants, the activation energies, and the frequency factors—were obtained with the Arrhenius equation. Using these kinetic expressions, hydrogen isotopic exchange profiles were estimated for time and temperature behavior. The D–H exchange between organic matter and water is apparently relatively fast and this implies that the aqueous alteration temperatures should have been very low, likely close to 0 °C to maintain hydrogen isotopic disequilibrium between organic matter and liquid water for millions of years.

Cultivation of the Acidophilic Microalgae Galdieria phlegrea with Wastewater: Process Yields

Algal based wastewater treatment offers the opportunity to recover, in the form of biomass, the nutrients and internal chemical energy of wastewater. Recently, there has been a growing interest in the use of extremophilic microalgae, as they can easily adapt to difficult and often pollutant-rich environments. The thermo-acidophilic microalga Galdieria phlegrea is a species of recent discovery and great metabolic versatility, but it has still been poorly studied. Here, G. phlegrea was cultivated using raw municipal wastewater in 1 L Erlenmeyer flasks with 700 mL working volume at 37 °C for up to nine days. During the cultivation phase, biomass growth, phycocyanin content, ammonium and phosphate removal from the wastewater, lipid fraction, total carbon and nitrogen in the biomass, and variation in δ13C and δ15N isotopic ratios (a novel analytical contribution in these experiments) were monitored. Results indicated that G. phlegrea was able to grow in raw effluent, where it removed more than 50% ammonium and 20% phosphate in 24 h; total lipid content was in the range of 11–22%, while average C-N content was of 45% and 6%, respectively; isotopic analyses proved to be a useful support in identifying C and N metabolic pathways from effluent to biomass. Overall, G. phlegrea showed consistent performance with similar Cyanidiophyceae and is a potentially viable candidate for municipal wastewater valorization from a circular economy perspective.

Detrital zircon petrochronology of central Australia, and implications for the secular record of zircon trace element composition

Abstract Hafnium (Hf) isotope composition of zircon has been integrated with U-Pb age to form a long-term (>4 b.y.) record of the evolution of the crust. In contrast, trace element compositions of zircon are most commonly utilized in local- or regional-scale petrological studies, and the most noteworthy applications of trace element studies of detrital zircon have been in “fingerprinting” potential source lithologies. The extent to which zircon trace element compositions varied globally over geological time scales (as, for example, zircon U-Pb age abundance, O isotope composition, and Hf isotope composition seem to have varied) has been little explored, and it is a topic that is well suited to the large data sets produced by detrital zircon studies. In this study we present new detrital zircon U-Pb ages and trace element compositions from a continent-scale basin system in Australia (the Centralian Superbasin) that bear directly on the Proterozoic history of Australia and which may be applicable to broader interpretations of plate-tectonic processes in other regions. U-Pb ages of detrital zircon in the Centralian Superbasin are dominated by populations of ca. 1800, 1600, 1200, and 600 Ma, and secular variations of zircon Hf isotope ratios are correlated with some trace element parameters between these major age populations. In particular, elevated εHf(i) (i.e., radiogenic “juvenile” Hf isotope composition) of detrital zircon in the Centralian Superbasin tends to correspond with relatively high values of Yb/U, Ce anomaly, and Lu/Nd (i.e., depletion of light rare earth elements). These correlations seem to be fundamentally governed by three related factors: elemental compatibility in the continental crust versus mantle, the thickness of continental crust, and the contributions of sediment to magmas. Similar trace element versus εHf(i) patterns among a global zircon data set suggest broad applicability. One particularly intriguing aspect of the global zircon data set is a late Neoproterozoic to Cambrian period during which both zircon εHf(i) and Yb/U reached minima, marking an era of anomalous zircon geochemistry that was related to significant contributions from old continental crust.

Direct U–Pb dating of carbonates from micron-scale femtosecond laser ablation inductively coupled plasma mass spectrometry images using robust regression

Abstract. Uranium–lead (U–Pb) dating of carbonates by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot analysis is an increasingly used method in the field of geosciences, as it brings very strong constraints over the geological history of basins, faults or reservoirs. Most ages currently published are based on the measurement of U and Pb ratios on spot ablations, using nanosecond lasers coupled to sector field or multi-collector ICP-MS. Here, we test a new strategy for the U–Pb dating of carbonates from 2D isotopic ratio maps, based on the use of a robust regression approach in the data reduction workflow. The isotopic maps, with a minimum area of 0.65 mm2 (∼ 1000 pixels of 13×25 µm resolution), are obtained using a 257 nm femtosecond laser ablation system at a high repetition rate (500 Hz) coupled to a high-resolution ICP-MS. The maps commonly show significant variations in isotope ratios at the pixel scale, allowing the plotting of pixel U–Pb ratios in concordia or isochron diagrams and the calculation of U–Pb ages. Due to the absence of individual ratio uncertainties, the ages are calculated using MM-robust linear regression rather than the more commonly used York-type regression. The goodness of fit to the data is assessed by the calculation of the residual standard error (RSE) of the regression and by the calculation of a mean square of weight deviates (MSWD) on discretised data. Several examples are provided that compare the ages calculated by robust regression with those obtained by other techniques (e.g. isotope dilution, LA-ICP-MS spot analyses and the pixel-pooling approach). For most samples, characterised by high U concentrations (> 1 ppm), robust regression allows for the calculation of ages and uncertainties similar to those obtained with the other approaches. However, for samples with lower U concentrations (< 0.5 ppm), the ages obtained are up to 10 % too young due to pixels with high U ∕ Pb acting as leverage points for the regression. We conclude that the U–Pb ages calculated by the regression method tested here, although statistically robust, should be critically analysed before validation, especially for samples with low U concentrations.

Architectural and Tectonic Control on the Segmentation of the Central American Volcanic Arc

Central America has a rich mix of conditions that allow comparisons of different natural experiments in the generation of arc magmas within the relatively short length of the margin. The shape of the volcanic front and this margin's architecture derive from the assemblage of exotic continental and oceanic crustal slivers, and later modification by volcanism and tectonic activity. Active tectonics of the Cocos-Caribbean plate boundary are strongly influenced by oblique subduction, resulting in a narrow volcanic front segmented by right steps occurring at ∼150-km intervals. The largest volcanic centers are located where depths to the slab are ∼90–110 km. Volcanoes that develop above deeper sections of the subducting slab are less voluminous and better record source geochemical heterogeneity. Extreme variations in isotopic and trace element ratios are derived from different components of thesubducted oceanic lithosphere. However, the extent that volcanoes sample these signatures is also influenced by lithospheric structures that control the arc segmentation. ▪ The architecture of Central America derives from the assemblage of exotic continental and oceanic crustal slivers modified by arc magmatism and tectonic processes. ▪ Active tectonics in Central America are controlled by oblique subduction. ▪ The lithospheric architecture and tectonics define the segmentation of the volcanic front, and thus the depth to the slab below a volcanic center. ▪ The composition of the subducted material is the main control of the along arc geochemical variations observed in Central American volcanoes. ▪ Geochemical heterogeneity in each segment is highlighted by extreme compositions representing the smaller centers with variations up to 65% of the total observed range.

Size‐based differences in isotopic niche width (δ13C and δ15N) of green turtles (Chelonia mydas) nesting on Príncipe Island, Gulf of Guinea

AbstractWithin the same population, nesting green turtles (Chelonia mydas) might exploit different niches by exhibiting polymorphic foraging strategies and/or inhabiting geographically distinct foraging areas. This is crucial information for the conservation of this species. Here, we used stable carbon and nitrogen isotope ratios (δ13C and δ15N) to test for differences in a population of green turtles nesting on Príncipe Island (1°37′N; 7°24҆′E), Central Africa. A total of 60 nesting females were sampled on the two main nesting beaches of the island in December 2012. Minimum curved carapace length (CCL) was recorded, and δ13C and δ15N values were measured in the epidermis of each individual. Overall, CCL varied from 87.0 to 108.0 cm (mean ± SD =100.0 ± 5.1), δ13C values from −19.4 to −8.6‰ (−17.3 ± 1.8) and δ15N values from 7.9 to 17.3‰ (13.6 ± 1.5). Despite the large variation in both isotopic ratios, their distributions were unimodal, showing an absence of polymorphic foraging strategies and isotopically distinct foraging areas. However, smaller females (< median, 100.8 cm) occupied a much larger isotopic niche (i.e., four times greater) than larger females. These results suggest that nesting green turtles may forage opportunistically on the resources available in each of their foraging home ranges, with smaller females venturing to more isotopic‐diversified areas and/or exhibiting broader foraging strategies than larger females. In addition, and in accordance with other studies, findings suggest that the foraging grounds used by the Príncipe green turtle nesting females are distributed mainly throughout the Gulf of Guinea.

AN ASSESSMENT OF THE SPATIAL VARIATION OF ISOTOPIC RATIOS IN A CANDU REACTOR FOR NUCLEAR TREATY MONITORING

A 3-D Quarter-Core CANDU-6 is modeled using Serpent 2 for nuclear treaty monitoring. The spatial variation of flux spectra and isotopic concentrations is analyzed to determine the potential isotopic distribution of key radionuclides from standard reactor operations relevant to non-proliferation. The initial results of the model show a 46% difference in overall flux magnitude throughout the core as well as a 2-30% difference in discrete energy flux. The coupled production rate (magnitude) and spectral differences can contribute to significant spatial variations in isotope ratios throughout the core. Initial results indicate 239Pu/240Pu ratios vary by as much as 51% across a single CANDU-6 fuel bundle at final burnup. The model is currently being used to develop an accurate representation of spent fuel to perform spatial isotopic analysis across the entire CANDU-6 core.

Combining Models of Environment, Behavior, and Physiology to Predict Tissue Hydrogen and Oxygen Isotope Variance Among Individual Terrestrial Animals

Variations in stable hydrogen and oxygen isotope ratios in terrestrial animal tissues are used to reconstruct origin and movement. An underlying assumption of these applications is that tissues grown at the same site share a similar isotopic signal, representative of the location of their origin. However, large variations in tissue isotopic compositions often exist even among conspecific individuals within local populations, which complicates origin and migration inferences. Field-data and correlation analyses have provided hints about the underlying mechanisms of within-site among-individual isotopic variance, but a theory explaining the causes and magnitude of such variance has not been established. Here we develop a mechanistic modeling framework that provides explicit predictions of the magnitude, patterns, and drivers of isotopic variation among individuals living in a common but environmentally heterogeneous habitat. The model toolbox includes isoscape models of environmental isotopic variability, an agent-based model of behavior and movement, and a physiology-biochemistry model of isotopic incorporation into tissues. We compare model predictions against observed variation in hatch-year individuals of the songbird Spotted Towhee (Pipilo maculatus) in Red Butte Canyon, Utah, and evaluate the ability of the model to reproduce this variation under different sets of assumptions. Only models that account for environmental isotopic variability predict a similar magnitude of isotopic variation as observed. Within the modeling framework, behavioral rules and properties govern how animals nesting in different locations acquire resources from different habitats, and birds nesting in or near riparian habitat preferentially access isotopically lighter resources than those associated with the meadow and slope habitats, which results in more negative body water and tissue isotope values. Riparian nesters also have faster body water turnover and acquire more water from drinking (vs. from food), which exerts a secondary influence on their isotope ratios. Thus, the model predicts that local among-individual isotopic variance is linked first to isotopic heterogeneity in the local habitat, and second to how animals sample this habitat during foraging. Model predictions provide insight into the fundamental mechanisms of small-scale isotopic variance and can be used to predict the utility of isotope-based methods for specific groups or environments in ecological and forensic research.

Repeated convergent evolution of parthenogenesis in Acariformes (Acari).

The existence of old species‐rich parthenogenetic taxa is a conundrum in evolutionary biology. Such taxa point to ancient parthenogenetic radiations resulting in morphologically distinct species. Ancient parthenogenetic taxa have been proposed to exist in bdelloid rotifers, darwinulid ostracods, and in several taxa of acariform mites (Acariformes, Acari), especially in oribatid mites (Oribatida, Acari). Here, we investigate the diversification of Acariformes and their ancestral mode of reproduction using 18S rRNA. Because parthenogenetic taxa tend to be more frequent in phylogenetically old taxa of Acariformes, we sequenced a wide range of members of this taxon, including early‐derivative taxa of Prostigmata, Astigmata, Endeostigmata, and Oribatida. Ancestral character state reconstruction indicated that (a) Acariformes as well as Oribatida evolved from a sexual ancestor, (b) the primary mode of reproduction during evolution of Acariformes was sexual; however, species‐rich parthenogenetic taxa radiated independently at least four times (in Brachychthonioidea (Oribatida), Enarthronota (Oribatida), and twice in Nothrina (Oribatida), (c) parthenogenesis additionally evolved frequently in species‐poor taxa, for example, Tectocepheus, Oppiella, Rostrozetes, Limnozetes, and Atropacarus, and (d) sexual reproduction likely re‐evolved at least three times from species‐rich parthenogenetic clusters, in Crotonia (Nothrina), in Mesoplophora/Apoplophora (Mesoplophoridae, Enarthronota), and in Sphaerochthonius/Prototritia (Protoplophoridae, Enarthronota). We discuss possible reasons that favored the frequent diversification of parthenogenetic taxa including the continuous long‐term availability of dead organic matter resources as well as generalist feeding of species as indicated by natural variations in stable isotope ratios.

Chlorine and Bromine Isotope Analysis of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers Using Gas Chromatography-Quadrupole Mass Spectrometry

A compound-specific chlorine/bromine isotope analysis (Cl-/Br-CSIA) method was developed using gas chromatography-quadrupole mass spectrometry for polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), which are toxic to human health and are frequently detected in various abiotic and biotic media. For PCB congeners, the molecular ion method for a concentration of 0.5–10.0 ppm, a dwell time of 20–100 ms, a relative EM voltage of 200 V, an electric current of 34 μA, and an ionization energy of 70 eV was determined as the most suitable scheme, which obtained standard deviations (SDs) of chlorine isotope ratios ranging from 0.00008 to 0.00068. As for the PBDE congeners, the lowest SDs, ranging from 0.00050 to 0.00172, were determined using the top four ion method with a concentration of 5–10 ppm and a dwell time of 20–50 ms. Both the chlorine and bromine isotope ratios showed strong concentration dependencies. Therefore, external standardization or detecting chlorine and bromine isotope ratios at a uniform concentration level is necessary to eliminate the concentration effect. In addition, 13C-correction is critical to remove interference from carbon isotopes. This newly developed Cl-/Br-CSIA method successfully determined the chlorine/bromine isotope ratios of PCBs/PBDEs in technical mixtures and traced the chlorine/bromine isotope ratio variations of PCBs/PBDEs in photodegradation experiments, thereby suggesting that it is a promising tool for assessing the sources and transformation processes of PCBs and PDBEs in the environment.

Natural abundance carbon isotope ratio analysis and its application in the study of diet and metabolism.

Due to differences in carbon assimilation pathways between plants, there are subtle but distinct variations in the carbon isotope ratios of foods and animal products throughout the food supply. Although it is well understood that the carbon isotope ratio composition of the diet influences that of the consumers' tissues, the application of natural abundance carbon isotope ratio analysis in nutrition has long been underappreciated. Over the past decade, however, several studies have investigated the utility of carbon isotope ratio analysis for evaluation of nutritional biomarker status, primarily focusing on its application as an objective indicator of sugar and animal protein intake. More recently, research investigating the application of natural abundance measurements has been extended to study fatty acid metabolism and has yielded encouraging results. Collectively, data from large-scale observational studies and experimental animal studies highlight the potential for carbon isotope ratio analysis as an additional and effective tool to study diet and metabolism. The purpose of this review is to provide an overview of natural abundance carbon isotope ratio analysis, its application to studying nutrition, and an update of the research in the field.

The blood copper isotopic composition is a prognostic indicator of the hepatic injury in Wilson disease.

Wilson disease (WD) is an autosomal recessive disorder of copper (Cu) metabolism. The gene responsible for WD, ATP7B, is involved in the cellular transport of Cu, and mutations in the ATP7B gene induce accumulation of Cu in the liver and ultimately in the brain. In a pilot study, the natural variations of copper stable isotope ratios (65Cu/63Cu) in the serum of WD patients have been shown to differ from that of healthy controls. In the present study, we challenged these first results by measuring the 65Cu/63Cu ratios in the blood of treated (n = 25), naïve patients (n = 11) and age matched healthy controls (n = 75). The results show that naïve patients and healthy controls exhibit undistinguishable 65Cu/63Cu ratios, implying that the Cu isotopic ratio cannot serve as a reliable diagnostic biomarker. The type of treatment (d-penicillamine vs. triethylenetetramine) does not affect the 65Cu/63Cu ratios in WD patients, which remain constant regardless of the type and duration of the treatment. In addition, the 65Cu/63Cu ratios do not vary in naïve patients after the onset of the treatment. However, the 65Cu/63Cu ratios decrease with the degree of liver fibrosis and the gradient of the phenotypic presentation, i.e. presymptomatic, hepatic and neurologic. To get insights into the mechanisms at work, we study the effects of the progress of the WD on the organism by measuring the Cu concentrations and the 65Cu/63Cu ratios in the liver, feces and plasma of 12 and 45 week old Atp7b-/- mice. The evolution of the 65Cu/63Cu ratios is marked by a decrease in all tissues. The results show that 63Cu accumulates in the liver preferentially to 65Cu due to the preferential cellular entry of 63Cu and the impairment of the 63Cu exit by ceruloplasmin. The hepatic accumulation of monovalent 63Cu+ is likely to fuel the production of free radicals, which is potentially an explanation of the pathogenicity of WD. Altogether, the results suggest that the blood 65Cu/63Cu ratio recapitulates WD progression and is a potential prognostic biomarker of WD.

Cu and Zn isotope ratio variations in plasma for survival prediction in hematological malignancy cases

We have examined potential changes in the isotopic compositions of Fe, Cu and Zn (using multi-collector inductively coupled plasma-mass spectrometry) and the corresponding concentrations (using inductively coupled plasma-atomic emission spectrometry) in plasma from hematological malignancy (HM) patients and assessed their prognostic capability. Together with clinical laboratory test values, data were examined in view of a 5-years survival prediction. Plasma Cu and Zn isotope ratios and their concentrations were significantly different in HM patients compared to matched controls (P < 0.05). Both δ65Cu and δ66Zn values showed significant mortality hazard ratios (HRs) in HM. The group of patients with decreased δ65Cu and increased δ66Zn values showed significantly poorer survival from the early phase (HR 3.9; P = 0.001), forming a unique cohort not identified based on laboratory test values. Well-known prognostic factors for HM, such as the creatinine level, and anemia-related values were highly correlated with the δ66Zn value (P < 0.05). Time-dependent ROC curves based on the δ65Cu or δ66Zn value were similar to that based on the creatinine concentration (a well-known prognostic factor in HM), indicating that δ65Cu or δ66Zn values are useful for prognosis of HM. Variations in stable isotope ratios of essential mineral elements have thus been shown to reflect alterations in their homeostasis due to physiological changes in malignancies with higher sensitivity than concentrations do.

Variation of lead isotopic composition and atomic weight in terrestrial materials (IUPAC Technical Report)

Abstract The isotopic composition and atomic weight of lead are variable in terrestrial materials because its three heaviest stable isotopes are stable end-products of the radioactive decay of uranium (238U to 206Pb; 235U to 207Pb) and thorium (232Th to 208Pb). The lightest stable isotope, 204Pb, is primordial. These variations in isotope ratios and atomic weights provide useful information in many areas of science, including geochronology, archaeology, environmental studies, and forensic science. While elemental lead can serve as an abundant and homogeneous isotopic reference, deviations from the isotope ratios in other lead occurrences limit the accuracy with which a standard atomic weight can be given for lead. In a comprehensive review of several hundred publications and analyses of more than 8000 samples, published isotope data indicate that the lowest reported lead atomic weight of a normal terrestrial materials is 206.1462 ± 0.0028 (k = 2), determined for a growth of the phosphate mineral monazite around a garnet relic from an Archean high-grade metamorphic terrain in north-western Scotland, which contains mostly 206Pb and almost no 204Pb. The highest published lead atomic weight is 207.9351 ± 0.0005 (k = 2) for monazite from a micro-inclusion in a garnet relic, also from a high-grade metamorphic terrain in north-western Scotland, which contains almost pure radiogenic 208Pb. When expressed as an interval, the lead atomic weight is [206.14, 207.94]. It is proposed that a value of 207.2 be adopted for the single lead atomic-weight value for education, commerce, and industry, corresponding to previously published conventional atomic-weight values.

Trace element fractionation and isotope ratio variation during melting of a spatially distributed and lithologically heterogeneous mantle

The source region of basalts in the mantle is chemically and lithologically heterogeneous. During decompression melting of a spatially distributed and lithologically heterogeneous mantle, mineral modes of distinct mantle sources vary continuously, resulting in spatial and temporal variations in the bulk partition coefficient of a trace element in different lithologies in the melting column, which in turn affects the fractionation of the trace element in partial melt and residual solid. This problem can be quantified by following the motion of solid in the melting column. This study presents a new melting model that can be used to keep track of spatial and temporal variations of mineral mode, melting reaction, bulk partition coefficient, and trace element concentration in the lithologically heterogeneous melting column. Simple analytical solutions for a time-dependent perfect fractional melting model are obtained. Essential features of the new model are elucidated through case studies of melting a two-lithology mantle that consists of blobs of orthopyroxene-rich lithology in the upwelling lherzolitic mantle; and an application to Sr-Nd-Hf isotope ratio variations in basalts from the Mid-Atlantic Ridge is presented. Fractional melting of the two-lithology mantle results in large temporal variations in incompatible trace element concentrations and Sr-Nd-Hf isotope ratios in the pooled melt. Mixing of fractional melts derived from different lithologies in the melting column produces enriched and depleted melts that form mixing loops in Sr-Nd-Hf isotope ratio correlation diagrams. These mixing loops rotate away from mixing lines defined by the binary mixing model and are a unique feature of melting a spatially heterogeneous mantle. Formation of the mixing loop can be traced to the location and spacing of the enriched lithological units in the melting column. The role of lithological heterogeneity is to change the bulk partition coefficient of a trace element from its values in the lherzolitic mantle to new values in the pyroxenitic mantle, which alters the extent of depletion of the trace element in the melting column. Changing bulk partition coefficient with time and space through lithological heterogeneity can result in greater variabilities in Sr-Nd-Hf isotope ratios and highly incompatible trace element concentrations in the pooled melt. Results from this study establish a framework for systematic studies of trace element fractionation and isotope ratio variation during decompression melting of a spatially distributed and lithologically heterogeneous mantle.

Tectonic Fragmentation and Geodynamic Regime of Elbrus and Kazbek Volcanoes (Central Caucasus, Russia): Results of the Deep Geophysical Research

A comprehensive analysis of instrumental data was carried out to establish indicators of the geodynamic conditions of interaction between the Scythian Plate and the collage of southern plates; and to determine the type and kinematics of the Main Caucasian Thrust and the nature of volcanoes in the North Caucasus. In terms of structure and tectonics, the studies were conducted within the alpine structure of the Greater Caucasus, and they equally characterize both of its first-order structures: the folded-block uplift of the Main Range and the North Caucasian regional massif. In the kinematics of the Main Caucasian Thrust and volcanoes of the North Caucasus, there are no subduction elements. The absence of correspondence of the Main Thrust to the Benioff zone, and, conversely, its similarity to listric faults and shallow-focus volcanic centers are more consistent with a collisional geodynamic situation. Geological and geophysical sections along the network of regional profiles of deep geophysical studies in Ciscaucasia and the central part of the Greater Caucasus are characterized by similarity in the elements of the deep structure and semithrust kinematics of interaction with the consolidated crust of the southern microplates–terranes framing the Arabian Plate from the north. The volcanoes of the Central Caucasus arose in a collisional setting and a relationship between Elbrus volcano and the Main Caucasian Thrust as a collision compression structure is assumed. Data were obtained on the results of geophysical studies using the earthquake converted-wave method (ECWM), microseismic sounding method (MSM), magnetotelluric sounding (MTS), and gravimagnetic measurements in combination with data obtained from processing of satellite images of the specific length of lineaments of tectonic fragmentation for different depths of lithospheric sections. Laboratory determination of radiocarbon dating of volcanic complexes, distribution of the thermal field in surface and deep thermal springs, as well as isotopic assessment of the ratios of indicator elements of Elbrus volcano, which make it possible to confidently identify a magma chamber at depth of ~5 km and a magma chamber at depth of ~30–40 km. Our studies allow us to consider the main characteristics as an increased thermal field, variations in the helium isotope ratios, a seismic gap under the volcanic structure, and insignificant energy unloadings occurring on gentle low-power tectonic zones on the northeastern and eastern slopes, where periodic fumarole gas emissions are inherent to the active volcano.

Geographical Origin Classification of Chinese Wines Based on Carbon and Oxygen Stable Isotopes and Elemental Profiles

Wines from different regions have different qualities due to the impact of geographical location and climate. The sale of inferior wines seriously violates the fair-trade rights of consumers. This article provides an elemental analysis classification method for verifying the geographical origin of wines in the People's Republic of China. Inductively coupled plasma mass spectrometry, liquid chromatography isotope ratio mass spectrometry, and an isotope ratio mass spectrometer were used to analyze 142 wine samples collected from Helan Mountain, Xinjiang, Yunchuanzang, the Yanhuai Valley, and the Hexi Corridor regions. The data included elemental profiles, carbon isotope ratios (δ13C), and oxygen isotope ratios (δ18O). The results of multivariate analysis revealed that the geographical origin of wine is closely related to variations in elemental profiles and isotope ratios. Introducing δ18O and the elements Li, Mn, Ag, In, Th, Ta, and Re into the discriminant model yielded correct classification rates of the linear discriminant model of 90.8% for the training set and 87.3% for the test set.

Isotopic and morphologic proxies for reconstructing light environment and leaf function of fossil leaves: a modern calibration in the Daintree Rainforest, Australia.

Within closed-canopy forests, vertical gradients of light and atmospheric CO2 drive variations in leaf carbon isotope ratios, leaf mass per area (LMA), and the micromorphology of leaf epidermal cells. Variations in traits observed in preserved or fossilized leaves could enable inferences of past forest canopy closure and leaf function and thereby habitat of individual taxa. However, as yet no calibration study has examined how isotopic, micro- and macromorphological traits, in combination, reflect position within a modern closed-canopy forest or how these could be applied to the fossil record. Leaves were sampled from throughout the vertical profile of the tropical forest canopy using the 48.5 m crane at the Daintree Rainforest Observatory, Queensland, Australia. Carbon isotope ratios, LMA, petiole metric (i.e., petiole-width2 /leaf area, a proposed proxy for LMA that can be measured from fossil leaves), and leaf micromorphology (i.e., undulation index and cell area) were compared within species across a range of canopy positions, as quantified by leaf area index (LAI). Individually, cell area, δ13 C, and petiole metric all correlated with both LAI and LMA, but the use of a combined model provided significantly greater predictive power. Using the observed relationships with leaf carbon isotope ratio and morphology to estimate the range of LAI in fossil floras can provide a measure of canopy closure in ancient forests. Similarly, estimates of LAI and LMA for individual taxa can provide comparative measures of light environment and growth strategy of fossil taxa from within a flora.