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Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In. Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures. Most chondrites show a deficit in 115Sn/120Sn (typically −150 to −200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 11

Several studies have revealed small heterogeneities in the relative abundance of 182W, the radiogenic nuclide of short-lived 182Hf (t1/2 = similar to 9 Ma), in terrestrial rocks. Whereas the majority of Archean rocks display 182W excesses relative to bulk silicate Earth, many young ocean island basalts show small 182W deficits, in particular if they are sourced from deep-rooted mantle plumes. The origin of this anomaly is still ambiguous, proposed models focus on core-mantle interaction or the presence of reservoirs in the lower mantle that have been isolated since the Hadean. In order to evaluate the role of upper mantle reservoirs, we report the first 182W data for intraplate basalts where a deep plume origin is still debated (Ascension Island, Massif Central, Siebengebirge and Eifel) and intraplate volcanic rocks associated with either plume or subduction zone environments (Italian Magmatic Provinces) and compare them to new data for basalts that have a deep mantle plume origin (La Reunion and Baffin Island). The proto-Iceland plume basalts from Baffin Island have uniform and modern mantle-like mu 182W of around 0 despite extremely high (3He/4He). In contrast, basalts from both volcanic edifices from La Reunion span a range from modern upper mantle values to deficits as low as mu 182W = -8.8 ppm, indicating a heterogeneous source reservoir. The mu 182W in all other intraplate volcanic provinces overlap the composition of modern upper mantle to within 3 ppm. The absence of resolvable 182W anomalies in these intraplate basalts, which partially tap the lithospheric mantle, suggests that primordial components are neither present in the central and southern European lithosphere nor in the European asthenospheric reservoir (EAR). The general absence of 182W anomalies in European plume-related basalts can either be explained by a shallow mantle source or by the absence of isotopically anomalous and isolated domains in the deep mantle beneath the northern hemisphere, as

Etna volcano in Italy releases an exceptional amount of CO2 (9083 t/day) and contributes to 10% of global volcanic emission. The reasons for its extreme CO2 degassing are not yet understood. Using high-precision high field strength element (HFSE) concentrations in magmas from volcanoes in southern Italy, we show that the high Nb/Ta of Etna (up to 26) reveals a mantle source affected by carbonatite metasomatism, which is likely responsible for the large CO2 fluxes. As observed at Etna, carbon-rich mantle domains influence CO2 degassing also outside of continental rifts and therefore play a fundamental role in explaining volcanic CO2 fluxes in different geodynamic settings. Collectively, our study demonstrates that HFSE ratios in magmatic rocks are viable tracers for volcanic carbon degassing that can be used to study present-day settings and, possibly, past emissions.

The highly siderophile elements (HSE) include the economically critical platinum group elements (PGE; Os, Ir, Ru, Rh, Pt, Pd, Au and Re), gold and rhenium. The HSE are redox sensitive in mantle and seafloor environments and have a strong affinity to iron and sulphur, therefore their distribution within the subducted mantle lithosphere record changes to oxidation state and sulphidation. The mobility of the HSE during subduction has important implications for Re-Os isotopic signatures in the mantle, and the formation of Cu-Au arc-related ore deposits. In this study, subducted rock samples from Alpine Corsica are used to track the HSE in serpentinites and hybrid ultramafic-mafic rocks through the subduction cycle. A comparison of bulk-rock HSE concentrations with those in pre-subduction analogues provides insights into the transfer of the HSE throughout the subduction cycle. Serpentinites subducted to blueschist-eclogite-facies conditions have similar HSE concentrations to primitive upper mantle (PUM) concentrations, therefore it is concluded that the HSE are not mobilized from serpentinites on the scale of the whole-rock or greater. Therefore, as suggested in previous studies, crustal lithologies may be more important contributors of the HSE to the sub-arc mantle, particularly Pt, Pd and Re. In contrast, HSE concentrations in hybrid rocks (talc schist and chlorite schist) deviate from protolith concentrations. Rhenium is higher in the talc schist, and Ir and Ru are lower in the chlorite schist than in the PUM, or possible mafic protoliths. Mineral parageneses place temporal constraints on the growth of hosts to the HSE (sulphides, oxides and metal alloys), and record changes to the activities of oxygen and sulphur (aO(2)-aS(2)), and hence redox conditions, from pre-subduction to exhumation. Laser ablation inductively coupled plasma mass spectrometry was used to determine the HSE concentrations in sulphides and oxides, and the detection of small (similar to 2-25 mu m(2

Mass fractions of Cu, Zn, Ga, Ag, Cd, In, Sn and Tl were determined via isotope dilution quadrupole ICP-MS in twenty-one geological reference materials (RMs) and the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3). The RMs comprise basaltic/mafic (BCR-2, BE-N, BHVO-1, BHVO-2, BIR-1, BRP-1, JB-2, OKUM, W-2, WS-E), intermediate/felsic (AGV-2, G-2, JA-2, RGM-1), ultramafic (DTS-2b, MUH-1, PCC-1, UB-N) and sedimentary (MAG-1, OU-6) rocks. Pressure digestion was applied for nonbasaltic samples to ensure effective sample digestion. For basaltic RMs, hot plate digestion was found to be sufficient for a quantitative recovery of the target elements. To minimise interferences and increase ion beam intensities during isotope ratio analyses by ICP-MS, separation of the target elements was carried out from single sample aliquots using a novel anion exchange procedure. The intermediate precision (2s) estimated from two to four replicate analyses was usually < 4% and results are in agreement with literature data, where available. Especially for Ag and Tl, the intermediate precision was compromised, likely due to low ion beam intensities and, hence, higher background and blank contributions. For ultramafic RMs, nugget effects and incomplete digestion might compromise the intermediate precision. Results for the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3) agree well with previously reported data.

Mass fractions of Sn and In were determined in sixteen geological reference materials including basaltic/mafic (BCR-2, BE-N, BHVO-1, BHVO-2, BIR-1, OKUM, W-2, WS-E), ultramafic (DTS-2b, MUH-1, PCC-1, UB-N) and felsic/sedimentary reference materials (AGV-2, JA-1, SdAR-M2, SdAR-H1). Extensive digestion and ion exchange separation tests were carried out in order to provide high yields (>90% for Sn, >85% for In), low total procedural blanks (similar to 1ng for Sn, <3pg for In) and low analytical uncertainties for the elements of interest in a variety of silicate sample matrices. Replicate analyses (n=2-13) of Sn-In mass fractions gave combined measurement uncertainties (2u) that were generally <3% and in agreement with literature data, where available. We present the first high-precision In data for reference materials OKUM (32.11.5ngg(-1)), DTS-2b (2.030.25ngg(-1)), MUH-1 (6.440.30ngg(-1)) and PCC-1 (3.550.35ngg(-1)) as well as the first Sn data for MUH-1 (0.057 +/- 0.010gg(-1)) and DTS-2b (0.623 +/- 0.018gg(-1)).

Two Fe-Ni sulfides, resembling the chemical composition of a typical mantle base metal sulfide (BMS), were synthesized and used to test micro-analytical procedures (sample digestion and chemical separation) to determine 187Os/188Os and highly siderophile element (HSE) mass fractions in single BMS grains. The bulk 187Os/188Os and HSE mass fractions of the synthetic sulfides were independently determined after high pressure asher (HPA) digestion and conventional HSE separation (Os solvent extraction and Ir, Ru, Pt, Pd, Re separation via anion exchange chromatography), while the homogenous distribution of HSE was assessed via LA-ICP-MS. Tests were performed following the protocol of Pearson et al. (1998), where sulfides are digested in H2SO4/CrO3 and Os is simultaneously extracted as OsO4. Additional tests were performed adding a pre-digestion step in HBr and/or HCl. The duration and the temperature of the pre-digestion and micro-distillation steps, as well as different chromatographic separations of the HSE were also evaluated. While the majority of the tests yielded 187Os/188Os in agreement with that obtained after HPA digestion, HSE mass fractions show large deviations from the reference content, depending on the used procedure. Such variations are interpreted as the result of incomplete sulfide digestion, Os spike loss, and the possible presence of undigested sub-micrometric platinum group minerals (PGM). Overall, the bulk sulfide HSE mass fractions obtained after HPA digestion are best reproduced (mean deviations ≤10%) using a pre-digestion step in HBr + HCl at 120 °C. This study highlights the need for matrix-matched sulfide reference materials for routine use in laboratories determining HSE mass fractions and Os isotope ratios on single BMS grains. Such an approach is fundamental for comparing and compiling Re-Os ages collected on BMS in many different laboratories. This study also demonstrates that there is need for further testing and for methodological develo, SCOPUS: ar.j, info:eu-repo/semantics/published

The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low lg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 degrees C and show that the prominent mineralogical difference between IPGE (+ Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 degrees C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt-and Pd-ligand associations lead to PGE fractionation. (C) 2017 Elsevier Ltd. All rights reserved.

Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic Os-187/Os-188 signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at th

Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic 187Os/188Os signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at the, SCOPUS: ar.j, info:eu-repo/semantics/published