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New 187Re-187Os, 87Rb-87Sr, triple O-isotope isotope, bulk rock highly siderophile- (HSE: Os, Ir, Ru, Pt, Pd, Re), major- and trace-element abundance data are reported for a variety of carbonaceous, ordinary and enstatite chondrite meteorites. In addition, new mineral chemical data are reported for the Chelyabinsk LL5 ordinary chondrite fall for comparison with existing chondrite data and to investigate element sequestration into metal and mineral phases within some chondrites. The focus of the study is to link the variations observed in the HSE abundances and Re-Os isotopes with other isotopic and elemental data to explore the relative roles of sample sizes, terrestrial alteration and parent body processes more fully on chondrite meteorite compositions. Trace element variations in Chelyabinsk silicate, oxide and metal grains highlight the importance of geochemical heterogeneity imparted by mineralogical variations and mode effects, as well as sample size. Using a range of sample powder aliquot sizes, it is possible to show that this becomes significant for the HSE at

International audience; Sedimentary records of superheavy pyrites in Phanerozoic and Proterozoic successions (i.e., extremely positive delta S-34(pyrite) values together with higher delta S-34(pyrite) than coeval delta S-34(CAS)) are mostly interpreted as resulting either from secondary postdepositional processes or from multiple redox reactions between sulfate and sulfide in stratified sulfate-poor environments. We report here the first observation of strongly positive delta S-34 values for both dissolved sulfate and sulfide (average delta S-34(diss.sulfate) value of 34.6 parts per thousand and delta S-34(diss.sulfide) values of 36.7 parts per thousand) compared to the present-day seawater delta S-34(diss).(sulfate) (similar to 21 parts per thousand), with a negative apparent fractionation between sulfate and sulfide (Delta S-34(diss.sulfate-diss.sulfide) similar to -2.1 +/- 1.4 parts per thousand), in the sulfate-poor (m) modern thalassohaline lacustrine system Dziani Dzaha (Mayotte, Indian Ocean). Overall, surface sediments faithfully record the water column isotopic signatures including a mainly negative Delta S-34(sed.sulfate-sed.sulfide) (-4.98 +/- 4.5 parts per thousand), corresponding to the definition of superheavy pyrite documented in the rock record. We propose that in the Dziani Dzaha this superheavy pyrite signature results from a two-stage evolution of the sulfur biogeochemical cycle. In a first stage, the sulfur cycle would have been dominated by sulfate from initially sulfate-rich marine waters. Overtime, Raleigh distillation by microbial sulfate reduction coupled with sulfide burial in the sediment would have progressively enriched in S-34 the water column residual sulfate. In a second still active stage, quantitative sulfate reduction not only occurs below the halocline during stratified periods but also in the whole water column during fully anoxic episodes. Sulfates are then regenerated by partial oxidation of sulfides as the oxic-anoxic interface moves downward. These results demonstrate that the atypical superheavy pyrite isotope signature does not necessarily require postdepositional or secondary oxidative processes and can result from primary processes in restricted sulfate-poor and highly productive environments analogous to the Dziani Dzaha.

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Particle-bound mercury (PBM) records the oxidation of elemental mercury, of which the main oxidation pathways (Brž/Clž/OHž/O3) remain unclear, especially in the Southern-Hemisphere. Here, we present latitudinal covariations of Hg and S-isotopic anomalies in cross-hemispheric marine aerosols that evidence an equator-to-poleward transition of Hg oxidants from OHž/O3 in tropics to Brž/Clž in polar regions highlighting thus the presence of distinct oxidation processes producing PBM. The correlations between Hg, S and O-isotopic compositions measured in PBM, sulfates and nitrates respectively within the aerosols highlight the implication of common oxidants in their formations at different latitudes. Our results open a new window to better quantify the present-day atmospheric Hg, S and N budgets and to evaluate the influences of aerosols on climate and ecosystems once the isotopic fractionations associated to each process have been determined.

International audience; A study of five diamonds containing mineral and fluid inclusions, selected among forty-nine specimens from the Cullinan Mine, South Africa, was carried out to better document the origin and formation of N-absent B-poor (type IIb) diamonds. The combination of several in-situ non-destructive techniques was used to identify the mineralogy and the chemical composition of primary and secondary inclusions. These include breyite, larnite, graphite, Fe-Ni-Cu native metallic alloys, sulfides of the pyrrhotite group, Ni-rich oxide and potential hydrous ferric sulfates. A common and abundant hydrous fluid containing H2O + CH4 was also identified. From the various observations, we suggest that these type IIb diamonds grew in an aqueous oxidized fluid reacting with a reduced mantle characterized by low oxygen fugacity. Remnant pressures recorded in primary breyite by Raman shifts and XRD measurements enabled the calculation of minimal entrapment pressures of inclusions using elastic geothermobarometry. Applying pressure corrections caused by elastic relaxation, minimum trapping pressures from 4.9 GPa to 5.6 GPa were calculated, suggesting lithospheric depths consistent with the occurrence of numerous graphite inclusions. The association of breyite and larnite, which is often considered as an indicator of sublithospheric origin, also occurs at pressures of 6 GPa or lower in a H2O-rich and carbonate/Ca-rich environment. The B-poor and N-absent features of type IIb diamonds do not require the classic subduction-related model of their formation. Whereas high-pressure minerals would host boron in cold subducting slabs, slabs are also important carriers of nitrogen into the deep mantle, with this latter element mostly absent in these diamonds. In our alternative model, the mantle is proposed as an alternative source of boron, whereby metallic alloys or N speciation between fluid and melt would still prevent the incorporation of nitrogen, leading to the expression of the blue, boron-related and N-absent features of type IIb diamonds. The observed mineralogical assemblage neither proves sublithospheric origin nor does it exclude lithospheric depths of formation for these diamonds. Hence, we propose that type IIb diamonds form in a mantle continuum, from sublithospheric to lithospheric depths.

The sulfur cycle is driven by redox processes, among which sulfate reduction is of primary importance. Sulfate is reduced to sulfide either abiotically by Thermochemical Sulfate Reduction (TSR) or biotically by Microbial Sulfate Reduction (MSR). Although these two processes occur at different temperature regimes (>100 °C and δ 33 S, δ 34 S, δ 36 S) of natural TSR remains uncharacterized. Here, we performed multiple sulfur isotopes analyses of sulfates, sulfides, and elemental sulfur from six sites in the Alpine Triassic evaporites formation to better constrain the isotopic signatures of TSR. Unlike MSR, TSR can induce slight negative deviations ( Δ 33 S down to −0.08‰) relative to the initial sulfate Δ 33 S value, which significantly discriminates between these two processes. Isotopic equilibria between anhydrite and either elemental sulfur or sulfides (pyrite or chalcopyrite) were verified according to their mass-fractionation exponents ( θ 33 / 34 = 0.5140 and 0.5170, respectively). Using sulfate-elemental sulfur ( Δ 34 S SO 4 2−-S8) or sulfate-sulfide ( Δ 34 S SO 4 2−-S2−) fractionation pairs and respective fractionation factors ( α 34 ) for samples that fulfilled the criteria of isotopic equilibrium, we determined the precipitation temperatures of elemental sulfur and sulfides (pyrite or chalcopyrite) to be 194 ± 14 °C and 293–488 °C, respectively. Interestingly, the obtained temperature of elemental sulfur precipitation corresponds exactly to the solid-liquid phase transition of native sulfur. Using Δ 33 S vs. δ 34 S and Δ 33 S vs. Δ 36 S diagrams, we are able to fully explain the isotopic signatures of disequilibrium sulfides by the mixing of sulfate with either elemental or organic sulfur in the aqueous fluid. Mixing curves allow the determination of the relative proportions of sulfate and organic and elemental sulfur, the latter being formed by the recombination of polysulfides during cooling. It appears that the sulfides' signatures are best explained by a 33% contribution of polysulfides (i.e., elemental sulfur signatures), consistent with the relative proportion of dissolved polysulfides previously measured in fluid inclusions from this formation at >200 °C. Finally, no sulfur mass independent fractionation (S-MIF) is observed in this evaporitic formation, consistent with the TSR signature generated both at equilibrium and by mixing. This implies that TSR does not generate S-MIFs. Our results thus provide multiple sulfur isotopes signatures of TSR, which may be used to reliably identify this process in variable geological settings.

https://hal.archives-ouvertes.fr/hal-03252301; International audience; Summary In the past, highly productive (hyper)saline and alkaline environments have proved propitious for large accumulation of sedimentary OM that led to the formation of Type I kerogens, such as those of the Green River Formation. A sediment core that covers most of the history of Lake Dziani Dzaha, a hypereutrophic saline, alkaline and mostly anoxic crater lakewhich waspostulatedto be a modern analogue of such environments, has been investigated using several analytical approaches comprising bulk (Rock-Eval and C, N, S elemental analyses), isotopic (δ13,14C, δ15N, δ18O, δ33,34,36S), and sedimentological descriptions. This study revealed that, despite strong environmental changes undergone by the lake since its formation, the conditions prevailing in the lake supported by a continuous high primary production have led to an excellent preservation of OM and to early diagenetic reductive and sulfurization processes which have yielded an exceptionally reduced character of the OM with respect to its short diagenetic history (< 6 ky). The similarities observed between the sediments of Lake Dziani Dzaha and some source rocks associated to Type I kerogens suggest that early diagenetic processes can have a strong and rapid impact on the accumulation of OM in some (semi)closed and highly productive aquatic ecosystems.

Ferrous oxide (FeO)-rich asteroid achondrites can be defined as asteroid-derived samples that experienced incipient partial melting processes in the early Solar System (>4.5 Ga) leading to melt-residues and cumulate and melt rocks that have high FeO in silicate grains (molar Mg/[Mg + Fe]

The origin of most major sulfide Ni-Cu deposits is attributed to the segregation of immiscible sulfide liquids from intraplate silicate melts, in response to assimilation of siliceous or sulfur-bearing rocks. The Algliden gabbroic dike in the Skellefte district (Sweden) contains Ni-Cu sulfide mineralization that is atypical because it formed in an arc setting and has a high Au content and low Ni/Cu ratio. This association led previously to a model in which the mineralization was linked to the assimilation of Cu-Au porphyry wall rocks. Based on new petrological, geochemical, and S isotope analyses of the dike and its wall rocks, we propose that assimilation of mineralized wall rocks was not instrumental in the formation of the deposit. Instead, we propose that the sulfides segregated during olivine crystallization from an evolved arc basalt and were injected into the dike in an olivine-rich crystal mush. This scenario explains the uniform dissemination of sulfide ores within norites, together with the high Au content and low Ni/Cu ratio of the ores. We propose that sulfide segregation from oxidized arc basalt was triggered by a decrease in the oxidation state of the melt, likely due to the cooling of the silicate melt or to the interaction with meta-sediments rich in organic matter, as proposed for other arc-related Cu-Ni sulfide deposits in Fennoscandia and elsewhere. At Algliden, melt reduction would have occurred relatively late during magma evolution, leading to the formation of an uneconomic deposit consisting of low Ni ores and lacking massive sulfides.

International audience; Ozone exhibits large and mass independent isotopic fractionations (MIF) in oxygen isotope ratios relative to molecular di-oxygen (O2) from which it is formed. An interpretation of this effect was proposed based on the behavior of the indistinguishable isotopes 16O in scattering processes. We report here an experiment aimed at testing one of the predictions of this model.O3 was formed by high frequency discharge in O2 with pressures ranging between 1.6 and 38 Torr. The isotopic evolution of the closed O2 reservoir was monitored during its distillation taking place during the continuous removal of ozone by condensation. Its composition evolves from a mass independent to a mass dependent fractionation along with the decrease in pressure. The isotopic pathways defined by this evolution in the 3 isotopes diagram are in quantitative agreement with the theoretical prediction of the disappearance of MIF with the increase of the complex lifetime stabilized as ozone.

https://hal.archives-ouvertes.fr/hal-03252301; International audience

During the first phase of the Messinian Salinity Crisis, massive amounts of sulfate (SO42-) have been sequestred in the form of up to 200m thick gypsum deposits (Primary Lower Gypsum) in Mediterranean marginal basins. The sulfur isotopic composition of the sulfate ion of this unit (δ34SSO4) (on average 22.3 ‰) strongly suggests that gypsum was formed by concentration of marine sulfate. Interestingly, the preservation of sulfide globules within the gypsum and marls interbeds suggests that the basin sulfate was not only involved in gypsum formation but a fraction was also reduced through microbial sulfate reduction. Moreover, filamentous fossils interpreted to be the remnants of sulfide oxidizing bacterias are entrapped in this gypsum and indicate, together with the occurrence of sulfide globules and dolomite, that an active biogeochemical sulfur cycling was active at the time of Primary Lower Gypsum deposition. To investigate the role of this active sulfur cycling in Mediterranean marginal basins, we analyzed the multiple sulfur isotopic composition of sulfate and sulfide minerals (δ34S andΔ33S)from Primary Lower Gypsum of the Vena del Gesso basin (Italy). Whereas the isotopic composition of gypsum (δ34SSO4 from 21 to 24‰ and Δ33SSO4 from -0.001 to 0.049‰) display very homogenous values that are close to those of the Messinian ocean (δ34SMSC ~22±0.2‰ and Δ33SMSC~0.039±0.015), the analyzed reduced sulfur compounds display a wide range of variability with -36 to +9‰ in δ34S and -0.017 to 0.125‰ in Δ33S. This suggests huge hydrologically-driven redox variations during Primary Lower Gypsum deposition in the Vena del Gesso basin, possibly involving intermittent stratification of the water column and an active microbial cycling of sulfur.

International audience

This paper explores the unusual sulphide–graphite association of a selection of Beni Bousera garnet clinopyroxenites that initially equilibrated within the diamond stability field. Compared with common graphite-free garnet pyroxenites analysed so far, these rocks display tenfold S enrichment with concentrations up to 5550 μg g–1. Fe–Ni–Cu sulphides (up to 1·5 wt%) consist of large (up to 3 mm across), low-Ni pyrrrhotite (

Roaldite (Fe4N) is one of the few nitride minerals found in meteorites. Their nitrogen (N) isotopic signatures carry important information for understanding the early N cycle in the proto-solar nebula. However, the lack of knowledge on the N isotopic effects from nitride formation to its survival from frictional heating during landing impedes the interpretation and application of N isotope compositions of nitride minerals in meteorites. Here, we carried out laboratory experiments under a recently proposed roaldite forming condition, i.e., NH3 (as starting N source) reacting with metallic Fe at medium temperatures. We observed Fe4N formation over a large range of temperatures from 300�����C to 700�����C. The formation of Fe4N was associated with equilibrium N isotope fractionations with ��Fe4N-NH3 values of 0.9907 (��0.0004) at 300�����C and 0.9936 (��0.0004) at 500�����C, respectively. In the experimental pressure conditions (initial PNH3���=���3.9���6.4���bar, PTotal���300���. Thus, great caution is needed when using N isotope composition of roaldite (and probably other nitride minerals as well) to trace source information.

International audience; The deterioration of monument or building stone materials is mostly due to the growth of black crusts that cause blackening and disaggregation of the exposed surface. This study reports on new oxygen (δ17O, δ18O and Δ17O) and sulphur (δ33S, δ34S, δ36S, Δ33S and Δ36S) isotopic analyses of black crust sulphates formed on building stones in Sicily (Southern Italy). The measurements are used to identify the possible influence of volcanic emissions on black crust formation. Black crusts were mostly sampled on carbonate stone substrate in different locations subject to various sulphur emission sources (marine, anthropogenic and volcanic). Unlike atmospheric sulphate aerosols that mostly exhibit Δ33S > 0‰, here most of the analysed black crust sulphates show negative Δ33S. This confirms that black crust sulphates do not result from deposition of sulphate aerosols or of rainwater but mostly from the oxidation of dry deposited SO2 onto the stone substrate. The δ34S and δ18O values indicate that most of black crust sulphate originates from anthropogenic activities. Δ17O values are found to be related to the sampling location. The largest 17O-anomalies (up to ~4‰) are measured in black crust from areas highly influenced by volcanic emissions, which demonstrates the strong involvement of ozone in the formation of black crusts in volcanically influenced environments.

Impact-induced oxidation of Mars’ crust by water >4.4 Ga ago likely supplied enough atmospheric H2 to attain a warm climate., Despite the abundant geomorphological evidence for surface liquid water on Mars during the Noachian epoch (>3.7 billion years ago), attaining a warm climate to sustain liquid water on Mars at the period of the faint young Sun is a long-standing question. Here, we show that melts of ancient mafic clasts from a martian regolith meteorite, NWA 7533, experienced substantial Fe-Ti oxide fractionation. This implies early, impact-induced, oxidation events that increased by five to six orders of magnitude the oxygen fugacity of impact melts from remelting of the crust. Oxygen isotopic compositions of sequentially crystallized phases from the clasts show that progressive oxidation was due to interaction with an 17O-rich water reservoir. Such an early oxidation of the crust by impacts in the presence of water may have supplied greenhouse gas H2 that caused an increase in surface temperature in a CO2-thick atmosphere.

International audience; We compare the dynamic performance of two models of public intervention in the cultural sector : A centralized ministry’à la française’ and a so-called arm’s length bodies, more British. We study the solutions of a dynamic game where, by hypothesis, the agencies are likely to resist Wagner’s law better than a central regulator, because they can disengage from public funding projects and thus approach the optimal dynamic. The non-cooperative behavior of the agencies creates strategic biases that the center can partially correct. The problem of quality is also addressed.; Dans cet article, nous comparons les performances dynamiques de deux modèles d’intervention publique dans le secteur culturel : un ministère centralisé « à la française » et une organisation en agences dites du bras armé (arm’s length), d’inspiration britannique. Nous étudions les solutions d’un jeu dynamique où, par hypothèse, les agences sont susceptibles de mieux résister à la loi de Wagner qu’un régulateur central, car elles peuvent se désengager des projets de financement public et se rapprocher ainsi de la dynamique optimale. Le comportement non coopératif des agences crée des biais stratégiques mais le régulateur central peut partiellement les corriger. Le problème de la qualité est également abordé.

International audience; 16 Evaporites play a major role on the structuration of collisional orogens especially when they 17 act as décollement units. However, their exact pressure-temperature-deformation (P-T-d) paths 18 are poorly documented. In this study, the first direct P-T-d constraints of the "Nappe des 19 Gypses" formation (western French Alps) have been established. An innovative association of 20 structural geology, petrography, crystallochemistry, and detailed study of both fluid inclusions 21 and stable isotopes (C, O) analysis has been applied to this evaporitic facies. Geochemical 22 analysis shows that the "Nappe des Gypses" formation has recorded the three typical 23 metamorphic and deformational events of the Alps (namely D1, D2 and D3). These different 24 constraints allow the determination of the first determination of the P-T path for this unit. 25 Metamorphic peak conditions of the "Nappe des Gypses" are at 16.6 ± 2.3 kbars and 431°C ± 26 28°C. This formation was buried at similar conditions than the oceanic units. During the 27 exhumation path, the D1-D2 transition is reached at 350°C ± 20°C and 6.5 ± 1.8 kbars and the 28 D2-D3 transition is assumed to be at 259°C ± 24°C and 2.0 ± 1.0 kbars (Strzerzynski et al., 29 2012). Peak P-T conditions overlap those of the median Liguro-Piemontese units but are 30 different from those of the Briançonnais units. It implies 1) an active and crucial role of the 31 "Nappe des Gypses" during the exhumation of the Alpine oceanic complex. And 2) confirms the 32 allochthonous and more distal origin of the European Thetysian passive margin of the "Nappe 33 des Gypses" formation. Consideration of sulfates dehydration probably between 15.0 and 16.6 34 kbars and 200 and 300°C, allows to discuss pore pressure excess and its mechanical 35 consequences on the exhumation process. This process is very likely to amplify the 36 "décollement" effect of the evaporites and allow the nappe stack formation. 37 This illustrates the role of this formation as a décollement surface. This difference of 38 evolution highlights the major role of the evaporitic formations on the exhumation and 39 structuration of a collisional chain. Such methodology could contribute to decipher the role of 40 evaporites in the structural context of other collisional chains such as Himalaya, Pyrenees or 41 Zagros. 42

Sulfur is a key element to understand ocean biogeochemical processes. Since decades, numerous studies have explained sulfur isotopic variations registred in the geological record as reflecting changes in continental sulfur inputs, biogeochemical recycling of sulfur and the relative proportion of oxidized (gypsum) vs reduced (e.g. pyrite) sulfur burial fluxes. Geochemical and petrographic studies have showed that these processes were active during the formation of the Mediterranean Salt Giant (MSG), a giant salt deposit formed at the end of the Messinian period (5.9-5.33 Ma) following the restriction of hydrological exchanges between the Mediterranean Sea and the Atlantic Ocean. To date, the biogeochemical sulfur cycle during the formation of the MSG has been investigated by analyzing the sulfur and oxygen isotope composition (δ34S and δ18O, respectively) of the sulfate ion in gypsum accumulated in the deep and marginal Mediterranean basins. In the uppermost gypsum layers (Upper Gypsum unit), significantly higher δ18O isotopic ratios (averaging at 12,7‰) than Messinian marine values suggest implications of microbial sulfate reduction activity followed by complete re-oxidation of sulfide back to sulfate in evaporated marine waters. Nevertheless, these different microbial processes can overprint each other δ34S and δ18O isotopic signatures and could have been provoked by various type of microbial metabolisms, involving different hydrological and environmental conditions. Here we present for the first time a multiple sulfur isotope (δ34S, Δ33S, Δ36S) investigation of samples from the well-known sections of Vena del Gesso (Apennines) and Pollenzo (Piedmont basin) in order to identify and understand how microbial mechanisms were coupled during the MSG formation. We designed a simple steady-state, three-box model representing the analysed S-bearing fractions (SO42-, S0, FeS2) and the different hydrological and biogeochemical S fluxes involved in marginal basin S-cycling. This system of 18 equations allows us to explain the strong isotopic variations we measured (-40.2 to 25.4‰ in δ34S, -0.001 to 0.160‰ in Δ33S and -1.79 to 0.001 in Δ36S‰) as produced by a huge variability in sulfate reduction activity reflecting fluctuations in the availability of organic matter. Moreover, our results, with relatively high λ33net (0.513 to 0.516) suggest than more than 90% of the hydrogen sulfide produced was re-oxidized by disproportionation reactions. Large, cyclic fluctuations of the Mediterranean hydrological cycle, and the presence of easily accessible S-compounds with a variety of oxidation states, makes the MSG a key system to understand the dynamics of the S biogeochemical cycle in the geological past.

This study reports on measurements of Δ17O (derived from the triple oxygen isotopes) in sulphate from black crust sampled in Sicily. Atmospheric oxidants, such as O3, H2O2, OH and O2 carry specific 17O-anomalies, which are partly transferred to the sulphate during sulphur gas (e.g. SO2) oxidation. Hence, the Δ17O in sulphate can be used as a tracer of sulphur oxidation pathways. So far, this method has been mostly applied on sulphate from aerosols, rainwaters, volcanic deposits and ice cores. Here we propose a new approach, that aims to investigate the dominant oxidants of gaseous sulphur precursors into sulphate extracted from black crust material. Black crusts are mostly found on building/monument/sculpture and are the result of the reaction between sulphur compounds (SO2, H2SO4) and carbonate (CaCO3) from the substrate, which leads to the formation of gypsum (CaSO4, 2H2O). Sicilian black crust from sites under different emission influences (anthropogenic, marine and volcanic) were collected. Multi oxygen and sulphur isotope analyses were performed to better assess the origins of black crust sulphate in these different environments. This is crucial for both a better understanding of the sulphur cycle and the preservation of historical monument.Multi sulphur isotopes show mostly negative values ranging from -0.4 ‰ to 0.02 ‰ ± 0.01 and from -0.59 ‰ to 0.41‰ ± 0.3 for Δ33S and Δ36S respectively. This is unique for natural samples and different from sulphate aerosols measured around the world (Δ33S > 0‰). This tends to indicate that sulphate from black crust is not generated by the same processes as sulphate aerosols in the atmosphere. Instead of SO2 oxidation in the atmosphere, dry deposition of SO2 and its oxidation on the substratum is preferred. The multi oxygen isotopes show a clear dependence with the geographical repartition of the samples. Indeed, black crusts from Palermo (the biggest Sicilian city) show small 17O-anomalies ranging between -0.16 ‰ to 1.02 ‰ with an average value of 0.45 ‰ ± 0.26 (n=12; 2σ). This is consistent with Δ17O values measured in black crust from the Parisian Basin (Genot et al., 2020), which are also formed in an environment influenced by anthropogenic and marine emissions. On the other hand, samples from the eastern part of the Mount Etna region, which are downwind of the volcanic emissions, show the highest 17O-anomalies ranging from 0.48 ‰ to 3.87 ‰ with an average value of 2.7 ‰ ± 0.6 (n=11; 2σ).These results indicate that volcanic emissions influence the oxygen isotopic signature of black crust sulphate. In standard urban areas, SO2 deposited on the substratum is mostly oxidised by O2-TMI and H2O2 to generate the black crust. Yet, under the influence of volcanic emissions, O3 may play the main role in the SO2 oxidation.

Modern anthropogenic aerosols usually exhibit low but significant Δ33S signatures (−0.6 to 0.5‰) whose origin still remains unclear. While isotope fractionation factors associated with the oxidation of SO2 by O2+TMI (Transition Metal Ion), H2O2 or OH cannot lead to such extreme Δ33S-values, an increasing number of studies points to the significant role of NO2 as a contributing oxidant, especially in the urban environment. To address the possible relation between atmospheric NO2 and observed Δ33S-values in aerosols, we carried out laboratory experiments oxidizing SO2 by NO2 at temperatures ranging between −7 and 52 °C. Our results show that at temperatures ≥10 °C SO2 oxidation by NO2 is characterized by 1) a 34α-value whose temperature dependence (0.2437/T+0.0457) is distinct from those related to oxidation by O2+TMI, H2O2 and OH oxidation pathways and 2) 33β (0.514 ± 0.0003) and 36β (1.90 ± 0.002) values that are closer to the mass dependent values (0.515 and 1.89 respectively) than those reported for the other oxidation pathways. This implies that the NO2 oxidation pathway cannot explain the extreme Δ33S-values measured in urban aerosols. Our data show that if atmospheric SO2 oxidation by NO2 is neglected, both the O2+TMI and OH oxidation pathways would be overestimated in urban areas. Finally, we conclude that another oxidation reaction is responsible for the high Δ33S-values measured in urban aerosol samples.

In order to establish the role and expression of silicate-metal fractionation in early planetesimal bodies, we have conducted a highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundance and 187 Re- 187 Os study of acapulcoite-lodranite meteorites. These data are reported with new petrography, mineral chemistry, bulk-rock major and trace element geochemistry, and oxygen isotopes for Acapulco, Allan Hills (ALHA) 81187, Meteorite Hills (MET) 01195, Northwest Africa (NWA) 2871, NWA 4833, NWA 4875, NWA 7474 and two examples of transitional acapulcoite-lodranites, Elephant Moraine (EET) 84302 and Graves Nunataks (GRA) 95209. These data support previous studies that indicate that these meteorites are linked to the same parent body and exhibit limited degrees ( 2 × CI chondrite) HSE abundances in transitional acapulcoite-lodranite meteorites (EET 84302, GRA 95209). All of the meteorites have chondritic Re/Os with measured 187 Os/ 188 Os ratios of 0.1271 ± 0.0040 (2 St. Dev.). These geochemical characteristics imply that the precursor material of the acapulcoites and lodranites was broadly chondritic in composition, and were then heated and subject to melting of metal and sulfide in the Fe-Ni-S system. This resulted in metallic melt removal and accumulation to form lodranites and transitional acapulcoite-lodranites. There is considerable variation in the absolute abundances of the HSE, both among samples and between aliquots of the same sample, consistent with both inhomogeneous distribution of HSE-rich metal, and of heterogeneous melting and incomplete mixing of silicate material within the acapulcoite-lodranite parent body. Oxygen isotope data for acapulcoite-lodranites are also consistent with inhomogeneous melting and mixing of accreted components from different nebular sources, and do not form a well-defined mass-dependent fractionation line. Modeling of HSE inter-element fractionation suggests a continuum of melting in the Fe-Ni-S system and partitioning between solid metal and sulfur-bearing mineral melt, where lower S contents in the melt resulted in lower Pt/Os and Pd/Os ratios, as observed in lodranites. The transitional meteorites, EET 84302 and GRA 95209, exhibit the most elevated HSE abundances and do not follow modelled Pt/Os and Pd/Os solid metal-liquid metal partitioning trends. We interpret this to reflect metal melt pooling into domains that were sampled by these meteorites, suggesting that they may originate from deeper within the acapulcoite-lodranite parent body, perhaps close to a pooled metallic ‘core’ region. Petrographic examination of transitional samples reveals the most extensive melting, pooling and networking of metal among the acapulcoite-lodranite meteorites. Overall, our results show that solid metal-liquid metal partitioning in the Fe-Ni-S system in primitive achondrites follows a predictable sequence of limited partial melting and metal melt pooling that can lead to significant HSE inter-element fractionation effects in proto-planetary materials.

International audience; We report new δ 13 C data and N content and aggregation state values for microdiamonds recovered from peridotites and chromitites of the Luobusa ophiolite (Tibet) and chromitites of the Ray-Iz ophiolite in the Polar Urals (Russia). All analyzed microdiamonds contain significant nitrogen contents (from 108 to 589 atomic ppm ± 20%) with a consistently low aggregation state and show identical infrared spectra dominated by strong absorption between 1130 cm –1 and 1344 cm –1 , and therefore characterize type Ib diamond. Microdiamonds from the Luobusa peridotites have δ 13 C (PDB) values ranging from −28.7‰ to −16.9‰, and N contents from 151 to 589 atomic ppm. The δ 13 C and N content values for diamonds from the Luobusa chromitites are −29‰ to −15.5‰ and 152–428 atomic ppm, respectively. Microdiamonds from the Ray-Iz chromitites show δ 13 C values varying from −27.6‰ to −21.6‰ and N contents from 108 to 499 atomic ppm. The carbon isotopes values have features similar to previously analyzed metamorphic diamonds from other worldwide localities, but the samples are characterized by lower N contents. In every respect, they are different from diamonds occurring in kimberlites and impact craters. Our samples also differ from the few synthetic diamonds we analyzed, in that they show enhanced δ 13 C variability and less advanced aggregation state than synthetic diamonds. Our newly obtained N aggregation state and N content data are consistent with diamond formation over a narrow and rather cold temperature range (i.e.

A collection of 61 xenocrystic and 12 eclogite xenolith-derived diamonds from the 600 Ma Lahtojoki kimberlite in central Finland has been investigated. Calculated pressure and temperature conditions for the diamondiferous eclogites are in excess of 5.5 GPa and 1300 °C, suggesting residence depths greater than 180 km, near the base of the Karelian cratonic mantle lithosphere. Geochemically, the eclogite xenoliths have gabbroic compositions showing positive Eu and Sr anomalies, relatively low ΣREE and elevated Al2O3 contents, yet garnets have ambiguous δ18O values of 5.7‰ and 5.9‰. Gabbroic eclogite formation could therefore be linked to either subduction processes during the 1.9 Ga Svecofennian orogeny or to cumulate processes during 2.1 Ga rift-induced magmatism. Determination of the oxygen fugacity of Lahtojoki eclogite xenoliths from both this work and previous studies suggests that diamond-bearing eclogites may be more reduced (ΔFMQ-3.5) compared to barren eclogites (ΔFMQ-1.7). While recycled oceanic crust protoliths for the eclogites remain a possibility, the carbon isotopic compositions and nitrogen abundances of the Lahtojoki diamonds indicate mantle-derived volatile sources. All diamonds (i.e., loose and eclogite xenolith-derived) display a restricted range of δ13C values from −7.8‰ to −3.7‰ that overlaps with the carbon isotopic composition of Earth’s mantle. The Lahtojoki diamond δ13C values form a negatively skewed distribution, indicating diamond growth from reduced mantle-derived carbon sources such as methane- (CH4) bearing fluids. Nitrogen contents of the Lahtojoki diamonds range from 40 to 1830 atomic ppm with a mean of ∼670 atomic ppm; these elevated nitrogen contents combined with the close association to eclogites suggest an eclogitic or crustal volatile source. However, the Karelian craton was periodically intruded by ultramafic alkaline magmas since at least 1.8 Ga, noting in particular the occurrence of phlogopite-rich kimberlites and olivine lamproites between 1200 and 700 Ma. We argue that this punctuated volatile-rich magmatism simultaneously metasomatised the cratonic mantle lithosphere, forming nitrogen enriched phlogopite-bearing metasomes. We propose that reduced, carbon-bearing and nitrogen-rich fluids were remobilized to form the Lahtojoki diamonds. The diamond-forming event(s) most probably occurred during or shortly prior to the entraining kimberlite magmatism as indicated by the diamond nitrogen aggregation systematics. Involvement of reduced diamond-forming fluids is supported by both the negative skewness of Lahtojoki diamond δ13C values and the more reduced nature of the diamondiferous Lahtojoki eclogites compared with their more oxidized barren counterparts. Our results from the diamondiferous eclogites derived from the deepest parts of the Karelian cratonic mantle root are in support of methane being the stable carbon volatile species at the base of thick continental lithosphere.

Ureilite meteorites are partially melted asteroidal-peridotite residues, or more rarely, cumulates that can contain greater than three weight percent carbon. Here we describe an exceptional C-rich lithology, composed of 34 modal % large (up to 0.8 mm long) crystalline graphite grains, in the Antarctic ureilite meteorite Miller Range (MIL) 091004. This C-rich lithology is embedded within a silicate region composed dominantly of granular olivine with lesser quantities of low-Ca pyroxene, and minor FeNi metal, high-Ca pyroxene, spinel, schreibersite and troilite. Petrological evidence indicates that the graphite was added after formation of the silicate region and melt depletion. Associated with graphite is localized reduction of host olivine (Fo88–89) to nearly pure forsterite (Fo99), which is associated with FeNi metal grains containing up to 11 wt.% Si. The main silicate region is typical of ureilite composition, with highly siderophile element (HSE) abundances ∼0.3 × chondrite, 187Os/188Os of 0.1260–0.1262 and Δ17O of −0.81 ± 0.16‰. Mineral trace-element analyses reveal that the rare earth elements (REE) and the HSE are controlled by pyroxene and FeNi metal phases in the meteorite, respectively. Modeling of bulk-rock REE and HSE abundances indicates that the main silicate region experienced ∼6% silicate and >50% sulfide melt extraction, which is at the lower end of partial melt removal estimated for ureilites. Miller Range 091004 demonstrates heterogeneous distribution of carbon at centimeter scales and a limited range in Mg/(Mg + Fe) compositions of silicate grain cores, despite significant quantities of carbon. These observations demonstrate that silicate rim reduction was a rapid disequilibrium process, and came after silicate and sulfide melt removal in MIL 091004. The petrography and mineral chemistry of MIL 091004 is permissive of the graphite representing late-stage C-rich melt that pervaded silicates, or carbon that acted as a lubricant during anatexis and impact disruption in the parent body. Positive correlation of Pt/Os ratios with olivine core compositions, but a wide range of oxygen isotope compositions, indicates that ureilites formed from a compositionally heterogeneous parent body that experienced variable sulfide and metal melt-loss that is most pronounced in relatively oxidized ureilites with Δ17O between −1.5 and ∼0‰.

International audience; This study is aimed to evaluate the role played by the sulfur radical ions (S3− and S2−) and molecular sulfur (S0) on sulfur isotope fractionation and to investigate if these species may leave an isotope fingerprint in hydrothermal systems. For this purpose, we combined (i) experiments using a hydrothermal reactor with aqueous S3−(S2−)-S0-sulfate-sulfide fluids and pyrite across a wide range of temperatures (300–450 °C), pressures (300–800 bars), fluid acidity (4

The geochemical behavior of N during seawater-oceanic crust alteration remains poorly constrained. Yet, it is a central parameter to assess the flux of N to subduction zones. Most studies proposed that hydrothermally altered basaltic rocks are enriched in N relative to fresh basalts. However, published data from DSDP/ODP Hole 504B, a reference site for the composition of the oceanic crust, suggest that seawater alteration leads to the N depletion of the upper ocean crust. To better address this issue, we analyzed N concentration and isotope composition of 21 altered basalts from the lavas and sheeted dikes sampled by Hole 504B. These new analyses show significant N enrichment (up to 14.1 ppm) relative to fresh degassed MORB (∼1 ppm). The differences observed between earlier and modern data are interpreted as resulting from analytical artifact due to the earlier use of a molybdenum crucible for N extraction. Furthermore, our new data show a progressive decrease of N concentration with depth, from 14.1 to 1.4 ppm. Nitrogen isotope compositions display a large range, with δ15N values from −0.9 to +7.3‰, and most likely reflect multiple stages of alteration with fluids of various compositions. In contrast to N concentration, δ15N values do not show a global depth trend but oscillate around a mean value of 3.0 ± 2.2‰ (1SD). The N concentration shows a positive correlation with bulk rock δ18O values, suggesting that N behavior during alteration process is mainly controlled by temperature. We propose that N speciation in the hydrothermal fluid is dominated by NH3/NH4 at low temperature (2, associated with H2, at higher temperature (>200 °C). These new data are used to re-evaluate the global flux of N input into Central American subduction zone, showing that the upper basaltic crust represent about 20% of the total N buried in subduction zone. A comparison with previous results obtained on N degassed in volcanic arc illustrates that, in “warm” subduction zone like Central America, up to 50% of the subducted N may be transferred to the deep mantle. This contrasts with “cold” subduction environments, where >80% of the N inputs escape sub-arc slab devolatilization and supports that the geothermal gradient plays a major role in determining the N fate in subduction zones.