Chemical Isotopic Fractionation Research Articles

Hg concentrations and stable isotope variations in tropical fish species of a gold-mining-impacted watershed in French Guiana.

The aim of the study was to determine if gold-mining activities could impact the mercury (Hg) concentrations and isotopic signatures in freshwater fish consumed by riparian people in French Guiana. Total Hg, MeHg concentrations, and Hg stable isotopes ratios were analyzed in fish muscles from different species belonging to three feeding patterns (herbivorous, periphytophagous, and piscivorous). We compared tributaries impacted by gold-mining activities (Camopi, CR) with a pristine area upstream (Trois-Sauts, TS), along the Oyapock River. We measured δ15N and δ 13C to examine whether Hg patterns are due to differences in trophic level. Differences in δ 15N and δ 13C values between both studied sites were only observed for periphytophagous fish, due to difference of CN baselines, with enriched values at TS. Total Hg concentrations and Hg stable isotope signatures showed that Hg accumulated in fish from both areas has undergone different biogeochemical processes. Δ199Hg variation in fish (-0.5 to 0.2‰) was higher than the ecosystem baseline defined by a Δ199Hg of -0.66‰ in sediments, and suggested limited aqueous photochemical MeHg degradation. Photochemistry-corrected δ202Hg in fish was 0.7‰ higher than the baseline, consistent with biophysical and chemical isotope fractionation in the aquatic environment. While THg concentrations in periphytophagous fish were higher in the gold-mining area, disturbed by inputs of suspended particles, than in TS, the ensemble of Hg isotope shifts in fish is affected by the difference of biotic (methylation/demethylation) and abiotic (photochemistry) processes between both areas and did therefore not allow to resolve the contribution of gold-mining-related liquid Hg(0) in fish tissues. Mercury isotopes of MeHg in fish and lower trophic level organisms can be complementary to light stable isotope tracers.

3-mm spectral line survey of two lines of sight towards two typical cloud complexes in the Galactic Centre

We present the results of two Mopra 3-mm spectral line surveys of the Lines of Sight (LOS) toward the Galactic Center (GC) molecular complexes Sgr B2 (LOS+0.693) and Sgr A (LOS-0.11). The spectra covered the frequency ranges of ~77-93 GHz and ~105-113 GHz. We have detected 38 molecular species and 25 isotopologues. The isotopic ratios derived from column density ratios are consistent with the canonical values, indicating that chemical isotopic fractionation and/or selective photodissociation can be considered negligible (<10%) for the GC physical conditions. The derived abundance and rotational temperatures are very similar for both LOSs, indicating very similar chemical and excitation conditions for the molecular gas in the GC. The excitation conditions are also very similar to those found for the nucleus of the starburst galaxy NGC 253. We report for the first time the detection of HCO and HOC+ emission in LOS+0.693. Our comparison of the abundance ratios between CS, HCO, HOC+ and HCO+ found in the two LOSs with those in typical Galactic photodissociation regions (PDRs) and starbursts galaxies does not show any clear trend to distinguish between UV and X-ray induced chemistries. We propose that the CS/HOC+ ratio could be used as a tracer of the PDR components in the molecular clouds in the nuclei of galaxies.

Sulfur four isotope NanoSIMS analysis of comet‐81P/Wild 2 dust in impact craters on aluminum foil C2037N from NASA’s Stardust mission

Abstract– We present NanoSIMS four‐isotope S analyses of 24 comet Wild 2 dust impact residues in craters on aluminum foil C2037N returned by NASA’s Stardust mission. Except for one sample, all impact residues have normal S isotopic compositions within 2σ uncertainties of at least two S isotope ratios. This implies that most S‐rich Wild 2 dust impactors formed in the solar system. Instrumental isotope fractionation due to sample topography is the main contribution to our analytical uncertainty. One impact crater residue shows small anomalies of δ33S = −57 ± 17‰, and δ34S = −41 ± 17‰ (1σ uncertainties). Although this could be simply a statistical outlier or the fingerprint of a chemical isotope fractionation it is also possible that the observed anomaly results from the mixture of a cometary FeS particle with a small (150 nm diam.) presolar FeS supernova grain. This would translate into a presolar sulfide abundance of approximately 200 ppm.

Experimental and Theoretical Investigation of Isotope Fractionation of Zinc between Aqua, Chloro, and Macrocyclic Complexes

This work reports on the chemical isotope fractionation of Zn(II) by a solvent extraction method with the crown ether dicyclohexano-18-crown-6. The (m)Zn/(64)Zn ratios (m = 66, 67, and 68) were analyzed by multiple-collector inductively coupled plasma mass spectrometry. The relative deviations of the (66)Zn/(64)Zn ratios relative to the unprocessed material (delta(66)Zn) was determined to be -0.51 to -0.32 in the acidity region 1.0-6.0 mol dm(-3) (M) HCl. The acidity dependence of delta(m)Zn was explained by the isotope exchange reactions between Zn(II) species (Zn(2+), ZnCl(+), ZnCl(2), ZnCl(3)(-), and ZnCl(4)(2-)) and the mole fractions of them. The magnitude of delta(m)Zn due to the related Zn(II) species estimated by quantum chemical calculations was in agreement with delta(m)Zn experimentally obtained. Contribution of nuclear field shift to the isotope fractionation was estimated to be less than 10% of delta(m)Zn by quantum chemical calculations.

Isotope Separation of Te in Chemical Exchange System with Dyclohexano-18-crown-6

This work reports on chemical isotopic fractionation of Te in a liquid-liquid extraction system using a crown ether of dicyclohexano-18-crown-6. Te isotopic composition was measured by multi-collector inductively coupled plasma spectrometer. We demonstrated the existence of a 125Te anomaly in two experiments at different molarities of HCl. The results of the present experiments fit the nuclear field shift theory of Bigeleisen. We finally showed the importance of the isotope of normalization in the representation of the mass-independent term.

Isotope Fractionation of Iron(III) in Chemical Exchange Reactions Using Solvent Extraction with Crown Ether

This work reports on the chemical isotope fractionation of Fe(III) by a solvent extraction method with a crown ether of dicyclohexano-18-crown-6. The (56)Fe/(54)Fe and (57)Fe/(54)Fe ratios were analyzed by multiple-collector inductively coupled plasma mass spectrometry. We determined the dependence of the isotope enrichment factors (epsilon) on the strength of HCl. The relative deviation of the (56)Fe/(54)Fe ratios relative to the unprocessed material (10(4) epsilon(56)) increases from -15.3 to -6.3 with [HCl] increasing from 1.6 to 3.5 mol/L. Likewise, 10(4) epsilon(57) increases from -22.8 to -9.6 under the same conditions. The correlation between epsilon(56) and epsilon(57) is mass dependent within the errors. The observed fractionation was broken down into the effects of competing extraction reactions and of a reaction between Fe(III) species (FeCl(2)(+) and FeCl(3)) in the aqueous phase. We found that the isotope fractionation between the Fe(III) species is mass dependent, which we confirmed by calculating the reduced partition function ratios.

13C I in high-mass star-forming clouds

We report measurements of the 12C/13C abundance ratio in the three galactic regions G 333.0-0.4, NGC 6334 A and G 351.6-1.3 from observations of the 12Ci 3P_1 transition and the hyperfine components of the corresponding 13Ci transition near 809 GHz. These transitions were observed simultaneously with the CO 7-6 line emission at 806 GHz with the AST/RO telescope located at the South Pole. From a simultaneous fit to the 12Ci 3P_1 transition and the HF components of the corresponding 13Ci transition and an independent estimate of an upper limit to the optical depth of the 12Ci emission we determine intrinsic 12Ci/13Ci column density ratios of for G 333.0-0.4, for NGC 6334 A and for G 351.6-1.3. As the regions observed are photon dominated, we argue that the apparent enhancement in the abundance of 13C towards G 333.0-0.4 may be due to strong isotope-selective photodissociation of , outweighing the effects of chemical isotopic fractionation as suggested by models of PDRs. Towards NGC 6334 A and G 351.6-1.3 these effects appear to be balanced, similar to the situation for the Orion Bar region observed by Keene et al. (1998).

Origin of sulphur in minerals and fluids from Latium (Italy): isotopic constraints

Sulphur-bearing compounds from Latium are mainly Plio-Quaternary and occur in a variety of geological environments. Over 200 S isotope data (δ 34 S) are presented on a variety of mineral occurrences and aqueous species, both from the present work and from the literature. Results provide evidence of many successive phases of mineralization which occurred from depths of a few km to the surface. In the investigated area, the Messinian evaporites were involved in local phenomena. Triassic evaporites may have played an important role both in the subduction zone and at shallow depth. Anatectic and perpotassic magmas provided sulphur with δ 34 S higher than 0‰ to the mineralizing batches. On the basis of their isotopic characteristics and petrogenetic environment, four types of sulphide and five types of sulphates can be distinguished. Conditions are discussed under which equilibrium or disequilibrium reactions, chemical isotope fractionation and biological activity may have influenced the S isotope composition. For the overall volume of the mineralizations, the contribution of magmatic sulphur prevails over the sedimentary contribution. Isotope data suggest that mixing of deep' and meteoric fluids may have occurred in the crust

Interstellar molecules.

The study of interstellar molecules broadly includes two areas of interest. One area uses the unique ability of molecules to act as probes of the physical conditions in the cold, dense, visually opaque component of the interstellar medium. The physical properties of this and other components of the interstellar medium are summarized. The other area deals with the chemistry of interstellar molecules, recent aspects of which are emphasized in this review. Gas-phase chemistry, shock chemistry, and grain surface chemistry are discussed in the context of recent observations. No present observations suggest that surface reactions are relevant, but neither can they be ruled out. Ion-molecule reactions are clearly operative, at least for the simpler species. Chemical isotope fractionation is reviewed, and it is concluded that the complexities of the chemistry allow no cosmological conclusions to be drawn from observations of deuterium in interstellar molecules, while the presence of 13C in interstellar molecules permits an estimate of the 12C/13C ratio which is consistent with the current concepts of the nucleosynthesis history of the Galaxy. Possible connections between interstellar molecules and the early molecular history of the solar system are discussed.

Carbon Isotope Abundance in Meteoritic Carbonates

The C(13)/C(12) ratio in the carbonate minerals of Orgueil, a carbonaceous chondrite, is 6 percent greater than the ratio in any known terrestrial carbon. The effect may be produced by a chemical isotope fractionation involving processes not common on earth, or it may be the result of incomplete homogenization of substances with different histories of nucleosynthesis.