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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.

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.

To better understand the formation and the oxidation pathways leading to gypsum-forming “black crusts” and investigate their bearing on the whole atmospheric SO2 cycle, we measured the oxygen (δ17O, δ18O and ∆17O) and sulfur (δ33S, δ34S, δ36S, ∆33S and ∆36S) isotopic compositions of black crust sulfates sampled on carbonate building stones along a NW-SE cross-section in the Parisian basin. The δ18O and δ34S, ranging between 7.5 and 16.7 ± 0.5 ‰ (n = 27, 2σ) and between −2.6 and 13.9 ± 0.2 ‰ respectively, show anthropogenic SO2 as the main sulfur source (from 2 to 81 %, in average ~30 %) with host-rock sulfates making the complement. This is supported by ∆17O-values (up to 2.6 ‰, in average ~0.86 ‰), requiring > 60 % of atmospheric sulfates in black crusts. Both negative ∆33S-∆36S-values between −0.34 and 0.00 ± 0.01 ‰ and between −0.7 and −0.2 ± 0.2 ‰ respectively were measured in black crusts sulfates, that is typical of a magnetic isotope effect that would occur during the SO2 oxidation on the building stone, leading to 33S-depletion in black crust sulfates and subsequent 33S-enrichment in residual SO2. Given that sulfate aerosols have mostly ∆33S > 0 ‰ and no processes can yet explain this enrichment, resulting in a non-consistent S-budget, black crust sulfates could well represent the complementary negative ∆33S-reservoir of the sulfate aerosols solving the atmospheric SO2 budget.

Sulfates present in urban aerosols collected worldwide usually exhibit significant non-zero Δ33S signatures (from −0.6 to 0.5 ‰) whose origin still remains unclear. To better address this issue, we recorded the seasonal variations of the multiple sulfur isotope compositions of PM10 aerosols collected over the year 2013 at five stations within the Montreal Island (Canada), each characterized by distinct types and levels of pollution. The δ34S-values (n = 155) vary from 2.0 to 11.3 ‰ (± 0.2 ‰, 2σ), the Δ33S-values from −0.080 to 0.341 ‰ (± 0.01 ‰, 2σ) and the Δ36S-values from −1.082 to 1.751 ‰ (± 0.2 ‰, 2σ). Our study evidences a seasonality for both the δ34S and Δ33S, which can be observed either when considering all monitoring stations or, to a lesser degree, when considering them individually. Among them, the monitoring station located at the most western end of the island, upstream of local emissions, yields the lowest mean δ34S coupled to the highest mean Δ33S-values. The Δ33S-values are higher during both summer and winter, and are