Neoarchean atmospheric chemistry and the preservation of S-MIF in sediments from the São Francisco Craton

Sulfur mass-independent fractionation(S-MIF)preserved in Archean sedimentary pyrite is interpreted to reflect atmospheric chemistry.Small ranges in Δ^(33)S that expanded into larger fractionations leading up to the Great Oxygenation Event(GOE;2.45–2.2 Ga)are disproportionately represented by sequences from the Kaapvaal and Pilbara Cratons.These patterns of S-MIF attenuation and enhancement may differ from the timing and magnitude of minor sulfur isotope fractionations reported from other cratons,thus obscuring local for global sulfur cycling dynamics.By expanding the Δ^(33)S record to include the relatively underrepresented São Francisco Craton in Brazil,we suggest that marine biogeochemistry affected S-MIF preservation prior to the GOE.In an early Neoarchean sequence(2763–2730 Ma)from the Rio das Velhas Greenstone Belt,we propose that low δ^(13)Corg(<-30‰)and dampened Δ^(33)S(-0.4‰to-0.7‰)in banded iron formation reflect the marine diagenetic process of anaerobic methane oxidation.The overlying black shale(TOC up to 7.8%)with higher δ^(13)Corg(-33.4‰to-19.2‰)and expanded Δ^(33)S(2.3‰±0.8‰),recorded oxidative sulfur cycling that resulted in enhance preservation of S-MIF input from atmospheric sources of elemental sulfur.The sequence culminates in a metasandstone,where concomitant changes to more uniform δCorg(-30‰to--25‰),potentially associated with the RuBisCO I enzyme,and near-zero Δ^(33)S(-0.04‰to 0.38‰)is mainly interpreted as evidence for local oxygen production.When placed in the context of other sequences worldwide,the Rio das Velhas helps differentiate the influences of global atmospheric chemistry and local marine diagenesis in Archean biogeochemical processes.Our data suggest that prokaryotic sulfur,iron,and methane cycles might have an underestimated role in pre-GOE sulfur minor isotope records.

Fractionation of rare earth and other trace elements in crabs,Ucides cordatus,from a subtropical mangrove affected by fertilizer industry

Fractionation of rare earth elements（REE） and other trace metal concentrations（Th, U, Cd,Cr, Cu, Ni, Pb, and Zn） between mangrove sediments and claw muscles and shells of male crabs（Ucides cordatus） from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms,and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers（contamination source）, which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint.