Komatiites constrain molybdenum isotope composition of the Earth's mantle

In order to estimate the Mo isotope composition and Mo abundance in the Bulk Silicate Earth (BSE), a total of thirty komatiite samples from five localities on three continents were analyzed using an isotope dilution double spike technique. Calculated Mo concentrations of the emplaced komatiite lavas range from 25±325±3 to 66±22 ng/g66±22 ng/g, and the inferred Mo concentrations in the deep mantle sources of the komatiites range between 17±417±4 and 30±12 ng/g30±12 ng/g, with an average value of 23±7 ng/g23±7 ng/g (2SE). This average value represents our best estimate for the Mo concentration in the BSE; it is identical, within the uncertainty, to published previous estimates of 39±16 ng/g39±16 ng/g, but is at least a factor of 2 more precise. The Mo isotope compositions of the komatiite mantle sources overlap within uncertainty and range from View the MathML sourceδMo98=−0.04±0.28 to 0.11±0.10‰0.11±0.10‰, with an average of 0.04±0.06‰0.04±0.06‰ (2SE). This value is analytically indistinguishable from published Mo isotope compositions of ordinary and enstatite chondrites and represents the best estimate for the Mo isotope composition of the BSE. The inferred δ98Mo for the BSE is therefore lighter than the suggested average of the upper continental crust (0.3 to 0.4‰). Thus, from the mass balance standpoint, a reservoir with lighter Mo isotope composition should exist in the Earth's mantle; this reservoir can potentially be found in subducted oceanic crust. The similarity of δ98Mo between chondritic meteorites and estimates for the BSE from this study indicates that during the last major equilibration between Earth's core and mantle, i.e., the one that occurred during the giant impact that produced the Moon, chemical and isotopic equilibrium of Mo between Fe metal of the core and the silicate mantle was largely achieved.

Pore-water squeezing from indurated shales

High-pressure mechanical squeezing was applied to sample pore waters from a sequence of highly indurated and overconsolidated sedimentary rocks in a drillcore from a deep borehole in NE Switzerland. The rocks are generally rich in clay minerals (28–71 wt.%), with low water contents of 3.5–5.6 wt.%, resulting in extremely low hydraulic conductivities of 10− 14–10− 13 m/s. First pore-water samples could generally be taken at 200 MPa, and further aliquots were obtained at 300, 400 and 500 MPa. Chemical and isotopic compositions of squeezed waters evolve with increasing pressure. Decreasing concentrations of Cl−, Br−, Na+ and K+ are explained by ion filtration due to the collapse of the pore space during squeezing. Increasing concentrations of Ca2 + and Mg2 + are considered to be a consequence of pressure-dependent solubilities of carbonate minerals in combination with sorption/desorption reactions. The pressure dependence was studied by model calculations considering equilibrium with carbonate minerals and the exchanger population on clay surfaces, and the trends observed in the experiments could be confirmed. The compositions of the squeezed waters were compared with results of independent methods, such as aqueous extraction and in-situ sampling of ground and pore waters. On this basis, it is concluded that the chemical and isotopic composition of pore water squeezed at the lowest pressure of 200 MPa closely represents that of the in-situ pore water. The feasibility of sampling pore waters with water contents down to 3.5 wt.% and possibly less opens new perspectives for studies targeted at palaeo-hydrogeological investigations using pore-water compositions in aquitards as geochemical archives.

Benchmarking the simulation of Cr isotope fractionation

A benchmark problem set consisting of four problem levels was developed for the simulation of Cr isotope fractionation in 1D and 2D domains. The benchmark is based on a recent field study where Cr(VI) reduction and accompanying Cr isotope fractionation occurs abiotically by an aqueous reaction with dissolved Fe 2+ (Wanner et al., 2012., Appl. Geochem., 27, 644–662). The problem set includes simulation of the major processes affecting the Cr isotopic composition such as the dissolution of various Cr(VI) bearing minerals, fractionation during abiotic aqueous Cr(VI) reduction, and non-fractionating precipitation of Cr(III) as sparingly soluble Cr-hydroxide. Accuracy of the presented solutions was ensured by running the problems with four well-established reactive transport modeling codes: TOUGHREACT, MIN3P, CRUNCHFLOW, and FLOTRAN. Results were also compared with an analytical Rayleigh-type fractionation model. An additional constraint on the correctness of the results was obtained by comparing output from the problem levels simulating Cr isotope fractionation with the corresponding ones only simulating bulk concentrations. For all problem levels, model to model comparisons showed excellent agreement, suggesting that for the tested geochemical processes any code is capable of accurately simulating the fate of individual Cr isotopes.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a Western Central European cave (NW Switzerland)

Deuterium (δD) and oxygen (δ18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of δ17O excess derived from precise measurement of δ17O and δ18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17O excess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (δD,δ17O and δ18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean δD,δ18O and δ17O are -71.0‰, -9.9‰, -5.2‰ for precipitation, -60.3‰, -8.7‰, -4.6‰ for cave drip water and -61.3‰, -8.3‰, -4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17O excess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (Δ of ~ + 10‰ for δD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8 - 10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first δ17O measurement in speleothem fluid inclusions, as well as the first comparison of the δ17 O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.

Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica

Stable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleoatmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotoperatios at Dome C, Antarctica, during the austral summer of 2011/2012. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10-day frequency. At the end of the season, acomparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm) attributed to mixing with the surrounding snow. After excluding samples impacted by the mixing process, we derived an average apparent nitrogen isotopic fractionation (15" app/of role in driving the isotopic fractionation of nitrate in snow.We have estimated a purely photolytic nitrogen isotopic fractionation (15"photo) of -55.8 12.0 ‰ from the difference in the derived apparent isotopic ractionations of the two experimental fields, as both pits were exposed to similar physical processes except exposure to solar UV. This value is in close agreement with the 15" photo value of -47.9 6.8 ‰ derived in a laboratory experiment simulated for Dome C conditions (Berhanu et al., 2014). We have also observed an insensitivity of 15" with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15" is strongly dependent on the spectral distribution of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the stable isotope ratios of snow nitrate at low-accumulation sites, where many deep ice cores are drilled. Nevertheless, modeling the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided.

Qualitative Distinction of Autotrophic and Heterotrophic Processes at the Leaf Level by Means of Triple Stable Isotope (C–O–H) Patterns

Foliar samples were harvested from two oaks, a beech, and a yew at the same site in order to trace the development of the leaves over an entire vegetation season. Cellulose yield and stable isotopic compositions (δ13C, δ18O, and δD) were analyzed on leaf cellulose. All parameters unequivocally define a juvenile and a mature period in the foliar expansion of each species. The accompanying shifts of the δ13C-values are in agreement with the transition from remobilized carbohydrates (juvenile period), to current photosynthates (mature phase). While the opponent seasonal trends of δ18O of blade and vein cellulose are in perfect agreement with the state-of-art mechanistic understanding, the lack of this discrepancy for δD, documented for the first time, is unexpected. For example, the offset range of 18 permil (oak veins) to 57 permil (oak blades) in δD may represent a process driven shift from autotrophic to heterotrophic processes. The shared pattern between blade and vein found for both oak and beech suggests an overwhelming metabolic isotope effect on δD that might be accompanied by proton transfer linked to the Calvin-cycle. These results provide strong evidence that hydrogen and oxygen are under different biochemical controls even at the leaf level.

A rapid and efficient ion-exchange chromatography for Lu–Hf, Sm–Nd, and Rb–Sr geochronology and the routine isotope analysis of sub-ng amounts of Hf by MC-ICP-MS

The development and improvement of MC-ICP-MS instruments have fueled the growth of Lu–Hf geochronology over the last two decades, but some limitations remain. Here, we present improvements in chemical separation and mass spectrometry that allow accurate and precise measurements of 176Hf/177Hf and 176Lu/177Hf in high-Lu/Hf samples (e.g., garnet and apatite), as well as for samples containing sub-nanogram quantities of Hf. When such samples are spiked, correcting for the isobaric interference of 176Lu on 176Hf is not always possible if the separation of Lu and Hf is insufficient. To improve the purification of Hf, the high field strength elements (HFSE, including Hf) are first separated from the rare earth elements (REE, including Lu) on a first-stage cation column modified after Patchett and Tatsumoto (Contrib. Mineral. Petrol., 1980, 75, 263–267). Hafnium is further purified on an Ln-Spec column adapted from the procedures of Münker et al. (Geochem., Geophys., Geosyst., 2001, DOI: 10.1029/2001gc000183) and Wimpenny et al. (Anal. Chem., 2013, 85, 11258–11264) typically resulting in Lu/Hf < 0.0001, Zr/Hf < 1, and Ti/Hf < 0.1. In addition, Sm–Nd and Rb–Sr separations can easily be added to the described two-stage ion-exchange procedure for Lu–Hf. The isotopic compositions are measured on a Thermo Scientific Neptune Plus MC-ICP-MS equipped with three 1012 Ω resistors. Multiple 176Hf/177Hf measurements of international reference rocks yield a precision of 5–20 ppm for solutions containing 40 ppb of Hf, and 50–180 ppm for 1 ppb solutions (=0.5 ng sample Hf 0.5 in ml). The routine analysis of sub-ng amounts of Hf will facilitate Lu–Hf dating of low-concentration samples.

Eclogitic diamonds from variable crustal protoliths in the northeastern Siberian craton: trace elements and coupled δ13C – δ18O signatures in diamonds and garnet inclusions

Diamonds of eclogitic assemblages are dominant in the placer diamond deposits of the northeastern Siberian platform. In this study we present new trace elements and stable isotopes (δ13C and δ18O) data for alluvial diamonds and their garnet inclusions from this locality. Cr-rich garnets of peridotitic affinity in the studied diamonds have a narrow range of δ18O values from 5.7‰ to 6.2‰, which is largely overlapping with the accepted mantle range. This narrow range suggests that the garnet inclusions showing different REE patterns and little variations in oxygen isotopes may have formed by different processes involving fluid/melts that, however, were in oxygen isotopic equilibrium with the mantle. The trace element composition of the eclogitic garnet inclusions supports a crustal origin for at least the high-Ca garnets, which show flat HREE patterns and in some cases a positive Eu-anomaly. High-Ca eclogitic garnets generally show heavier oxygen isotope compositions (δ18O 6.5–9.6‰) than what is observed in low-Ca garnets (δ18O 5.7–7.4‰). The variability in oxygen isotopes and trace elements is suggested to be inherited from contrasting crustal protoliths. The relationship between the high δ18O values of inclusions and the low δ13C values of the host diamonds implies that the high-Ca garnet inclusions were derived from intensely hydrated (e.g., δ18O > 7‰) and typically oxidised basaltic rock close to the seawater interface, and that the carbon for diamonds was closely associated with this protolith.

Bryozoan stable carbon and hydrogen isotopes: relationships between the isotopic composition of zooids, statoblasts and lake water

We explored the extent to which δ13C and δD values of freshwater bryozoan statoblasts can provide information about the isotopic composition of zooids, bryozoan food and surrounding water. Bryozoan samples were collected from 23 sites and encompassed ranges of nearly 30‰ for δ13C and 100‰ for δD values. δ13C offsets between zooids and statoblasts generally ranged from −3 to +4.5‰, with larger offsets observed in four samples. However, a laboratory study with Plumatella emarginata and Lophopus crystallinus demonstrated that, in controlled settings, zooids had only 0–1.2‰ higher δ13C values than statoblasts, and 1.7‰ higher values than their food. At our field sites, we observed a strong positive correlation between median δ13C values of zooids and median δ13C values of corresponding statoblasts. We also observed a positive correlation between median δD values of zooids and statoblasts for Plumatella, and a positive correlation between median δD values of statoblasts and δD values of lake water for Plumatella and when all bryozoan taxa were examined together. Our results suggest that isotope measurements on statoblasts collected from flotsam or sediment samples can provide information on the feeding ecology of bryozoans and the H isotopic composition of lake water.

TIMS measurements of full range of natural Ca isotopes with internally consistent fractionation correction

This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus™ thermal ionization mass spectrometer with a specially developed Faraday cup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept < 1 µg. With this setup the measurement uncertainties were 0.06 ‰ for 40Ca/44Ca and 0.12 ‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature. The exponential law was observed to correct incompletely instrumental mass fractionation. An improved fractionation correction based on the exponential law is proposed. It changes the 40Ca/44Ca ratio of SRM 915a (corrected relative to 42Ca/44Ca = 0.31221; 48Ca/44Ca = 0.08871) from 47.1635 ± 0.0028 to 47.1649 ± 0.0047. The measurements of SRM 915b were performed with different analytical conditions (runs were prolonged till complete filament load depletion). Even if the 40Ca/44Ca ratio of SRM 915b, when corrected with the simple exponential law, appears different (47.1532 ± 0.0038) from that of SRM 915a, it becomes coincident (47.1613 ± 0.0028) when corrected with a second-order refinement. This supports the use of the improved exponential law to obtain internally consistent Ca isotope ratio for natural samples.

Geochronology and isotope geochemistry of Eocene dykes intruding the Ladakh Batholith

In order to determine the extent and timing of dyke formation in the Ladakh Batholith we examined about 30 mostly andesitic dykes intruding the Ladakh batholith in a ca. 50 km wide area to the west of Leh (NW India). The dykes in the east of the area trend E-NE and those in the west trend N-NW. The difference in orientation is also evident in the petrography and isotopic signatures. The eastern dykes contain corroded quartz xenocrysts and show negative ε0(Nd) and positive ε0(Sr) values, where as the western dykes do not contain quartz xenocrysts and exhibit positive ε0(Nd) and near-zero ε0(Sr) values. The variability in Sr-Nd isotopes (ε0(Nd) = 3.6 to −9.6, ε0(Sr) = 0.4 to 143) and the quartz xenocrysts can best be explained by (differing degrees of) crustal assimilation of the parent magma of the dykes. Separated minerals from five dykes were dated by 40Ar-39Ar incremental heating: amphibole ages range between 50 and 54 Ma, and one biotite dated both by Rb-Sr and by 40Ar-39Ar gave an age of 45 Ma. One dated pseudotachylyte sample attests to brittle faulting at ca. 54 Ma. The combination of structural field evidence with petrographic, isotopic and geochronological analyses demonstrates that the dykes did not form from a single, progressively differentiating magma chamber, despite having formed in the same tectonic setting around the same time, and that processes such as crustal assimilation and magma mixing/mingling also played a significant role in magma petrogenesis.

Cool Glacial Temperatures and Changes in Moisture Source Recorded in Oman Groundwaters

Concentrations of atmospheric noble gases (neon, argon, krypton, and xenon) dissolved in groundwaters from northern Oman indicate that the average ground temperature during the Late Pleistocene (15,000 to 24,000 years before present) was 6.5° ± 0.6°C lower than that of today. Stable oxygen and hydrogen isotopic groundwater data show that the origin of atmospheric water vapor changed from a primarily southern, Indian Ocean source during the Late Pleistocene to a dominantly northern, Mediterranean source today. The reduced northern water vapor source is consistent with a drier Last Glacial Maximum through much of northern Africa and Arabia.