RESUMEN
Volatile element delivery and retention played a fundamental part in Earth's formation and subsequent chemical differentiation. The heavy halogens-chlorine (Cl), bromine (Br) and iodine (I)-are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth's silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth's surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth's dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.
RESUMEN
The reaction of Ca(CO3 ) with H3 BO3 in oleum (20 % SO3 ) yielded colorless single-crystals of CaB2 S4 O16 (monoclinic, P21 /c, a=5.5188(2), b=15.1288(6), c=13.2660(6)â Å, ß=92.88(1)°, V=1106.22(8)â Å3 ). X-ray single-crystal structure analysis revealed a phyllosilicate-analogue anionic sub-structure, forming 2D infinite anionic layers, which exhibit an unprecedented arrangement of condensed twelve-membered (zwölfer) and four-membered (vierer) rings of corner-shared (SO4 ) and (BO4 ) tetrahedra. Charge compensation is achieved by Ca2+ cations, residing exclusively above the centers of the twelve-membered rings. DFT investigations on the solid-state structure corroborate the experimental findings and allow for a detailed valuation of charge distribution within the anionic network and an assignment of vibrational frequencies.
RESUMEN
We report on the first thoroughly characterized molybdenum borate, which was synthesized in a high-pressure/high-temperature experiment at 12.3â GPa/1300 °C using a Walker-type multianvil apparatus. Mo2 B4 O9 incorporates tetrahedral molybdenum clusters into an anionic borate crystal structure-a structural motif that has never been observed before in the wide field of borate crystal chemistry. The six bonding molecular orbitals of the [Mo4 ] tetrahedron are completely filled with 12â electrons, which are fully delocalized over the four molybdenum atoms. This finding is in agreement with the results of the magnetic measurements, which confirmed the diamagnetic character of Mo2 B4 O9 . The two four-coordinated boron sites can be differentiated in the 11 B MAS-NMR spectrum because of the strongly different degrees of local distortions. Experimentally obtained IR and Raman bands were assigned to vibrational modes based on DFT calculations.
RESUMEN
Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth's mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F-Cl-Br-I-H2O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H2O (DClol/melt = 1.6 ± 0.9 × 10-4) to 0.33 (6) wt% H2O (DClol/melt = 2.2 ± 1.1 × 10-4). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65-78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F-Cl-Br-I-H2O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with (R2 = 0.99): [Formula: see text]. The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287-295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65-78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth's mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.
