Isotopic Characterization ( 2 H, 13 C, 37 Cl, 81 Br) of Abiotic Degradation of Methyl Bromide and Methyl Chloride in Water and Implications for Future Studies

International audienceMethyl bromide (CH 3 Br) and methyl chloride (CH 3 Cl) significantly contribute to stratospheric ozone depletion. The atmospheric budgets of both compounds are unbalanced with known degradation processes outweighing known emissions. Stable isotope analysis may be capable to identify and quantify emissions and to achieve a balanced budget. Degradation processes do, however, cause isotope fractionation in methyl halides after emission and hence knowledge about these processes is a crucial prerequisite for any isotopic mass balance approach. In the current study, triple-element isotope analysis (2 H, 13 C, 37 Cl/ 81 Br) was applied to investigate the two main abiotic degradation processes of methyl halides (CH 3 X) in fresh and seawater: hydrolysis and halide exchange. For CH 3 Br, nucleophilic attack by both H 2 O and Cl − caused significant primary carbon and bromine isotope effects accompanied by a secondary inverse hydrogen isotope effect. For CH 3 Cl only nucleophilic substitution by H 2 O was observed at significant rates causing large primary carbon and chlorine isotope effects and a secondary inverse hydrogen isotope effect. Observed dual-element isotope ratios differed slightly from literature values for microbial degradation in water and hugely from radical reactions in the troposphere. This bodes well for successfully distinguishing and quantifying degradation processes in atmospheric methyl halides using triple-element isotope analysis. ■ INTRODUCTION Methyl chloride (CH 3 Cl, chloromethane) and methyl bromide (CH 3 Br, bromomethane) together contribute about 30% to halogen induced ozone loss even though atmospheric concentrations are very low: 540 pptv and 7 pptv, respectively. 1 CH 3 Cl and CH 3 Br are emitted by both anthropogenic and natural sources such as fumigation for quarantine and preshipment treatment (for CH 3 Br), 2 marine macroalgae, 3 salt marshes, 4 soils, 5 biomass burning, 6 and tropical plants. 7 Main degradation processes for both of these compounds are reaction with OH and Cl radicals in the troposphere, 8 degradation in oceans 9 and soils. 10 The atmospheric budgets of both compounds are unbalanced with known degradation processes exceeding the best estimates of known emissions by approximately 20% for CH 3 Cl and 30% for CH 3 Br. 1,11 A better understanding of emission and degradation processes will be necessary in order to better quantify emission and degradation of CH 3 X and to improve budget estimates. Previous studies suggested that degradation in oceans is primarily driven by the abiotic processes hydrolysis and halide exchange as well as microbial degradation. 9,12,13 To a minor extent, hydrolysis may also contribute to degradation of CH 3 Br in soils. 14 Hydrolysis and halide exchange of CH 3 X (CH 3 Cl and CH 3 Br) are both nucleophilic substitution reactions (S N 2) following second order reaction kinetics. The attacking nucleophiles are either water (H 2 O), hydroxide ions (OH −), or halide ions such as Cl − and Br − (Y −): 15−1

A hydrothermal origin for isotopically anomalous cap dolostone cements from south China

The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan ‘snowball Earth’ ice age, ~635 Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ^(13)C_(PDB) down to −48‰; in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, ^(87)Sr/^(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the ^(13)C-depleted signatures crystallized more than 1.6 Myr after deposition of the cap dolostone. Our results indicate that highly ^(13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly ^(13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly ^(13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the ‘snowball’ state, it would not have left extreme carbon isotope signals in cap dolostones

Inter-laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca-10(PO4)(6)(F,Cl,OH)(2) solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for Cl-37/Cl-35 homogeneity using SIMS followed by delta Cl-37 characterisation by gas source mass spectrometry using both dual-inlet and continuous-flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than +/- 0.10% (1s) for the five samples with > 0.5% m/m Cl and +/- 0.19% (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38% between the mean Cl-37/Cl-35 ratios measured on three oriented apatite fragments. Furthermore, the results of GS-IRMS analyses show small but systematic offset of delta Cl-37(SMOC) values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10(3)delta Cl-37(SMOC) values between +0.09 and +0.42 and in all cases with 1s <= +/- 0.25

Calibration and applications of the dolomite clumped isotope thermometer to high temperatures

Carbonate clumped isotope paleothermometry is based on the temperature-dependent formation of ^(13)C^(18)O^(16)O_2 ^(2-) ion groups within solid carbonate minerals. This thermometer has now been calibrated for various synthetic and natural biogenic and abiogenic minerals (calcite, aragonite and carbonateapatites [e.g., 1, 2]) at temperatures below ~ 50°C. Here we extend the use of the carbonate clumped isotope thermometer to shallow crustal environments by determining the Δ_(47) values of CO_2 extracted from natural and synthetic dolomites grown at know temperatures from 25 to 350ºC. The experimental temperature dependance is not linear in the Δ_(47) vs T^(-2) plot and resembles the predicted theoretical temperature dependence, both in shape and absolute value [3]. These data for synthetic dolomites overlap the previous calibrations for inorganic calcite and some forms of biogenic carbonates between 25 and 50˚C, and are consistent with a single trend that also intersects data for synthetic calcite equilibrated at 1200˚C. These observations suggest that a single temperature dependant relationship reasonably approximates the calibration for both phases. Data from a variety of slowly-cooled (i.e., over geological timescales) natural marbles and rapid (i.e., laboratory timescales) heating experiments provide insights into the kinetics of solid-state ^(13)C-^(18)O bond reordering in carbonates and its closure temperature. More generally, our new calibration and constraints on high-temperature kinetics have implications for the application of this technique to burial and metamorphic processes. These issues will be illustrated through estimates of the thermal history and oxygen isotopic compositions and abundances of pore fluids for several suites of late Neoproterozoic carbonates [e.g., 4]

Calibration of the dolomite clumped isotope thermometer from 25 to 350°C, and implications for a universal calibration for all (Ca, Mg, Fe)CO_3 carbonates

Carbonate clumped isotope thermometry is based on the temperature-dependent formation of ^(13)C^(18)O^(16)O_2^(2-) ion groups within the lattice of solid carbonate minerals. At low temperatures the bonds between rare, heavy ^(13)C and ^(18)O isotopes are thermodynamically favored, and thus at equilibrium they are present in higher than random abundances. Here we calibrate the use of this temperature proxy in a previously uncalibrated carbonate phase — dolomite [CaMg(CO_3)_2] — over a temperature range that extends to conditions typical of shallow crustal environments, by determining the Δ_(47) values of CO_2 extracted from synthetic or natural (proto)dolomites grown at known temperatures from 25 to 350°C and analyzed in two different laboratories using different procedures for sample analysis, purification and post-measurement data treatment. We found that the Δ_(47) – 1/T^2 dependence for (proto)dolomite is linear between 25 and 350°C, independent of their Mg/Ca compositions or cation order (or the laboratory in which they were analyzed), and offset from, but parallel to, the theoretical predictions of the Δ_(63) dependence to temperature of the abundance of the ^(13)C^(18)O^(16)O_2 isotopologue inside the dolomite and calcite mineral lattices as expected from ab-initio calculations (Schauble et al., 2006). This suggests that neither the equilibrium constant for ^(13)C–^(18)O clumping in (proto)dolomite lattice, nor the experimental fractionation associated with acid digestion to produce CO_2, depend on their formation mechanism, degree of cation order and/or stoichiometry (ie., Mg/Ca ratio) and/or δ^(18)O and δ^(13)C compositions (at least over the range we explored). Thus, we suggest the following single Δ_(47) – 1/T^2 linear regression for describing all dolomite minerals: with T in kelvin and Δ_(47) in the Carbon Dioxide Equilibrium Scale (CDES) of Dennis et al. (2011) and referring to CO_2 extracted by phosphoric acid digestion at 90°C. The listed uncertainties on slope and intercept are 95% confidence intervals. The temperature sensitivity (slope) of this relation is lower than those based on low temperature acid digestion of carbonates, but comparable to most of those based on high temperature acid digestion (with however significantly better constraints on the slope and intercept values, notably due to the large range in temperature investigated and the large number of Δ_(47) measurements performed here, n = 67). We also use this dataset to empirically determine that the acid fractionation factor associated with phosphoric acid digestion of dolomite at 90°C (Δ∗_(dolomite90)) is about + 0.176‰. This is comparable to the Δ∗_(calcite90) experimentally obtained for calcite (Guo et al., 2009), suggesting that the acid fractionation Δ∗ for acid digestion of dolomite and calcite are the same within error of measurement, with apparently no influence of the cation identity. This hypothesis is also supported by the fact that our dolomite calibration data are indistinguishable from published calibration data for calcite, aragonite and siderite generated in similar analytical conditions (ie., carbonate digested at T ⩾ 70°C and directly referenced into CDES), demonstrating excellent consistency among the four (Ca,Mg,Fe)CO_3 mineral phases analyzed in seven different laboratories (this represents a total of 103 mean Δ_(47) values resulting from more than 331 Δ_(47) measurements). These data are used to calculate a composite Δ_(47)–T universal relation for those carbonate minerals of geological interest, for temperatures between -1 and 300°C, that is found to be statistically indistinguishable from the one described by dolomite only: Thus, in order to standardize the temperature estimates out of different laboratories running high temperature digestion of (Ca,Mg,Fe)CO_3 carbonate minerals, we recommend the use of this single Δ_(47)-T calibration to convert Δ_(47CDES) data into accurate and precise temperature estimates. More widely, this study extends the use of the Δ_(47) thermometry to studies of diagenesis and low-grade metamorphism of carbonates with unprecedented precision on temperature estimates based on Δ_(47) measurements — environments where many other thermometers are generally empirical or semi-quantitative

The chlorine isotopic composition of the Moon: Insights from melt inclusions

The Moon exhibits a heavier chlorine (Cl) isotopic composition compared to the Earth. Several hypotheses have been put forward to explain this difference, based mostly on analyses of apatite in lunar samples complemented by bulk-rock data. The earliest hypothesis argued for Cl isotope fractionation during the degassing of anhydrous basaltic magmas on the Moon. Subsequently, other hypotheses emerged linking Cl isotope fractionation on the Moon with the degassing during the crystallization of the Lunar Magma Ocean (LMO). Currently, a variant of the LMO degassing model involving mixing between two end-member components, defined by early-formed cumulates, from which mare magmas were subsequently derived, and a KREEP component, which formed towards the end of the LMO crystallization, seems to reconcile some existing Cl isotope data on lunar samples. To further ascertain the history of Cl in the Moon and to investigate any evolution of Cl during magma crystallization and emplacement events, which could help resolve the chlorine isotopic variation between the Earth and the Moon, we analysed the Cl abundance and its isotopic composition in 36 olivine- and pyroxene-hosted melt inclusions (MI) in five Apollo basalts (10020, 12004, 12040, 14072 and 15016). Olivine-hosted MI have an average of 3.3 ± 1.4 ppm Cl. Higher Cl abundances (11.9 ppm on average) are measured for pyroxene-hosted MI, consistent with their formation at later stages in the crystallization of their parental melt compared to olivines. Chlorine isotopic composition (δ37) of MI in the five Apollo basalts have weighted averages of +12 ± 2.4‰ and +10.1 ± 3.2‰ for olivine- and pyroxene-hosted MI, respectively, which are statistically indistinguishable. These isotopic compositions are also similar to those measured in apatite in these lunar basalts, with the exception of sample 14072, which is known to have a distinct petrogenetic history compared to other mare basalts. Based on our dataset, we conclude that, post-MI-entrapment, no significant Cl isotopic fractionation occurred during the crystallization and subsequent eruption of the parent magma and that Cl isotopic composition of MI and apatite primarily reflect the signature of the source region of these lunar basalts. Our findings are compatible with the hypothesis that in the majority of the cases the heavy Cl isotopic signature of the Moon was acquired during the earliest stages of LMO evolution. Interestingly, MI data from 14072 suggests that Apollo 14 lunar basalts might be an exception and may have experienced post-crystallization processes, possibly metasomatism, resulting in additional Cl isotopic fractionation recorded by apatite but not melt inclusions

Cycle du chlore terrestre (les échanges manteau-océan)

PARIS7-Bibliothèque centrale (751132105) / SudocSudocFranceF

Oxygen isotope composition of waters recorded in carbonates in strong clumped and oxygen isotopic disequilibrium

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Basin-scale thermal and fluid flow histories revealed by carbonate clumped isotopes (Δ 47 ) - Middle Jurassic carbonates of the Paris Basin depocentre

International audienceThe reconstruction of past diagenetic conditions in sedimentary basins is often under‐constrained. This results from both the analytical challenge of performing the required analyses on the minute sample amounts available from diagenetic mineral phases and the lack of tracers for some of the diagenetic parameters. The carbonate clumped isotope thermometry (Δ47) opens new perspectives for unravelling the temperatures of diagenetic phases together with the source of their parent fluids, two parameters that are otherwise impossible to constrain in the absence of exploitable fluid inclusions. Here is reported the study of a large number of sedimentary and diagenetic carbonate phases (from Middle Jurassic reservoirs of the Paris Basin depocentre) by combining detailed petrographic observations with a large number of Δ47 data (n > 45) on a well‐documented paragenetic sequence, including calcite and dolomite burial cements. The data reveal carbonate crystallization at temperatures between 29°C and 98°C from fluids with δ18Owater values between −7‰ and +2‰, in response to the progressive burial and uplift of the Paris Basin, throughout 165 Myr of basin evolution. Coupled with the time–temperature evolution previously estimated from thermal maturity modelling, these temperatures allow determining the timing of four successive cementation episodes. The overall data set indicates a history of complex water mixing with a significant contribution of hypersaline waters from the Triassic aquifers migrated upward along faults during the Cretaceous subsidence of the basin. Subsequent large‐scale infiltrations of meteoric waters induced a dilution of these pre‐existing brines in response to the Paris Basin uplift in the Tertiary. Overall, the data presented here allow proposing an integrated approach to characterize the cementation events affecting the studied carbonate reservoir units, based on temperature, oxygen isotope composition and salinity of the parent fluids as well as on petrographic grounds

Experimental determination of stable chlorine and bromine isotope fractionation during precipitation of salt from a saturated solution

International audienceIn order to better understand the chlorine and bromine stable isotope fractionation that occurs when chloride and bromide salts precipitate from their saturated solutions, we determined experimentally the equilibrium fractionation factors between precipitating pure salt minerals and their coexisting saturated brine at 22 °C. Fractionation factors (expressed as 103lnα(37Cl/35Cl)salt-brine and 103lnα81Br/79Brsalt-brine) obtained for 11 chloride and 7 bromide salts of geological and industrial interest show a relatively largerange of variation (from − 0.31 to + 0.41), with the salt that precipitates having either a lower or a higher isotope ratio than the brine from which they precipitate. A negative fractionation factor indicates that the brine has a larger isotope ratio than the precipitate, a positive factor that the precipitate has a larger isotope ratio. The results of the chlorine and bromine isotope fractionation measurements (103lnα) for the various salts at a temperature of 22 ± 2 °C are: LiCl: + 0.03 ± 0.05, NaCl: + 0.35 ± 0.08, KCl: − 0.12 ± 0.05, NH4Cl: + 0.09 ± 0.03, RbCl: − 0.31 ± 0.05, CsCl: − 0.23 ± 0.02, MgCl2: − 0.02 ± 0.02, CaCl2: + 0.04 ± 0.02, SrCl2: + 0.15 ± 0.02, BaCl2: + 0.41 ± 0.03, FeCl3: − 0.23 ± 0.05, LiBr: − 0.03 ± 0.09, NaBr: − 0.07 ± 0.05, KBr: 0.00 ± 0.01, NH4Br: + 0.11 ± 0.05, MgBr2: + 0.06 ± 0.06, CaBr2: − 0.06 ± 0.04 and SrBr2: + 0.05 ± 0.06. In these measurements the uncertainty is defined as the 1σ standard deviation of replicate determinations. We compare the results to previous theoretical calculations based on reduced partition coefficients as well as with thermodynamic properties of precipitated salts. Though most of our experimental fractionation data qualitatively agree with theoretical predictions (e.g., larger isotope fractionation for Cl than for Br species), it remains difficult to directly and finely compare those estimations which is likely due to the complexness of the processes that take place in saturated solutions. We use the data to predict the δ37Cl evolution of the Earth's oceans' through geological time under the condition that solely isotope fractionation during evaporation and salt precipitation took place, together with erosion of evaporite deposits. Under these conditions, we calculate a δ37Cl decrease of at most 0.25‰ for the Earth's oceans during the last 1 billion years. Such a trend is not observed in old evaporite deposits, in part because δ37Cl variations in most evaporite deposits are larger than the expected trend, and we conclude that δ37Cl may also be influenced by other processes such as chloride exchange with the deep Earth. We only observed very small bromine isotope fractionation during precipitation of bromide salts from brine. This small fractionation cannot explain the large deviation of δ81Br of dissolved evaporite samples from precipitation of seawater with a modern bromine isotope composition, and suggests large bromine isotope variations in the oceans through time