Constraints on the Archean atmospheric oxygen and sulfur cycle from mass-independent sulfur records from Anshan-Benxi BIFs, Liaoning Province, China

The Archean atmospheric oxygen concentration and sulfur cycle was long debated. The banded iron formation (BIF) is a special type of the sedimentary formation, which has truly recorded the atmospheric and oceanic conditions at that time. In this study, the composition of multiple sulfur isotope (δ 34S/δ 33S/δ 32S) for sulfides bedded in the Archean (~2.7 Ga) BIFs, in Anshan-Benxi area of Liaoning Province has been measured. The value of △33S varies from -0.89‰ to +1.21‰, which shows very obvious mass-independent fractionation (MIF) signatures. These non-zero △33S values indicate that the Archean sulfur cycles are different from what it is today, which have been deeply influenced by gas phase photochemical reactions. Algoma-type BIFs which are closely related to the volcanic activity have negative △33S value, however, Superior-type BIFs which are far away from the volcanic center have positive △33S value. The δ 34S varies in a large range from -22.0‰ to +11.8‰, which indicates that the bacteria reduction activity has already existed at that time, and that the oceanic sulfate concentration has at least reached 1 mmol/L in local areas. Combined with the contemporaneous existence of the hematite, magnetite and the occurrence and preservation of the sulfur MIF, it can be inferred that the Archean atmospheric oxygen level must be at 10-2―10-3 of the present atmospheric level (PAL).

Mercury accumulation,distribution,and isotopic composition in tissues of the Collared Scops Owl(Otus lettia)

Mercury is a ubiquitous contaminant known to accumulate in wildlife,particularly bird species at higher trophic levels.Knowledge of tissue-specific Hg distributions aids our understanding of Hg bioaccumulation in organisms.In this study,one adult and three juvenile Collared Scops Owls(Otus lettia)were studied to elucidate the bioaccumulation of Hg in body tissues.Six tissues and organs(feathers,nails,heart,liver,gizzard,and muscle),as well as gastric contents,were examined for total Hg(THg)and methylmercury(MeHg)contents,Hg isotopic compositions including mass-dependent fractionation(MDF;δ202Hg)and mass-independent fractionation(MIF;Δ199Hg andΔ201Hg),and C(δ13C)and N(δ15N)isotopic compositions.Tissue-specific THg and MeHg concentrations in the adult were in the ranges of 150–1360 ng/g and17–1060 ng/g,and lower in the juveniles at 91–419 ng/g and 67–350 ng/g,respectively.Theδ^(202)Hg values in the adult were strongly negative at-1.75‰±0.17‰compared with the juveniles at-0.99‰±0.25‰.The adult exhibited lower MIF values than the juveniles,at0.23‰±0.07‰forΔ^(199)Hg and 0.2‰±0.11‰forΔ^(201)Hg,comparedwith0.81‰±0.09‰and0.66‰±0.07‰,respectively.The lower adult MDF and MIF values suggest that the adult tended to accumulate negative Hg isotopes but the juvenile's positive Hg isotopes.Differences between adult and juvenile tissue Hg concentrations indicate that metabolic processes play an important role in Hg accumulation.

Discovery of Mass Independent Oxygen Isotopic Compositions in Superscale Nitrate Mineral Deposits from Turpan-Hami Basin,Xinjiang,China and Its Significance

The Turpan-Hami Basin in eastern Xinjiang is one of the driest regions on Earth and a premier environment to form and preserve nitrate.A large nitrate ore field in this basin was found recently.It is estimated there are about 2.5 billion tons of resources of nitrate,and the amount is as much as the Atacama Desert super-scale nitrate deposit in Chile.Nitrate is one of a few minerals with mass-independent fractionation（MIF）,and the oxygen isotope MIF is an effective method to determine the source of nitrate.Theδ^（17）O,δ^（18）O of nitrate were measured by fluorination and thermal decomposition method.The date indicated that this is the first time that oxygen isotope MIF has been located in inland nitrate minerals.The results obtained by two methods are similar,⊿^（17）=δ^（17）O-0.52×δ^（18）O=12‰-17‰.The experiment and observation data proved that oxygen isotope MIF of nitrate are the result of photochemical reactions in the troposphere and stratosphere.Thus, evidence from MIF oxygen isotopic compositions indicate that long term atmospheric deposition of nitrate aerosol particles produced by photochemical reactions is the source of the deposits.

Mercury isotope constraints on the genesis of late Mesozoic Sb deposits in South China

The late Mesozoic antimony(Sb)mineralization belt in South China hosts a large portion of the world’s Sb reserves.However,the source and mineralization processes of these Sb deposits remain controversial.Here,we measured mercury(Hg)concentrations and isotopic compositions of stibnite in the Banpo Sb-only and Woxi Sbpolymetallic ore deposits,as well as associated rocks in the Yangtze Block in order to constrain the metal sources and ore formation processes in the South China Sb mineralization belt.Stibnite samples from both deposits exhibit significant enrichment in Hg(4.23–50.6 ppm)and have higher δ^(202)Hg values(−0.47‰to 2.03‰)than the studied Precambrian basement rocks(−1.42‰to 0.59‰),Paleozoic sedimentary rocks(−2.40‰to−0.32‰),and other natural Hg reserves(e.g.,marine and continental systems).This indicates that significant mass-dependent fractionation of Hg isotopes occurred during hydrothermal processes.Negative to slightly positive Δ^(199)Hg values of−0.17‰to 0.02‰were obtained for stibnite from the studied deposits,similar to values for the Precambrian basement rocks,but different from those of the Paleozoic sedimentary rocks and data previously reported for mantle materials.This suggests that Precambrian basement rocks were the source of Hg and associated metals.Our data and the tectonic evolution of South China indicate that late Mesozoic asthenospheric upwelling,in response to the Paleo-Pacific oceanic slab foundering,generated heat that drove the circulation of fluids in the basement and crustal basinal rocks.These fluids leached Sb,Hg,and other metals from the Precambrian basement rocks and formed the world-class Sb mineralization belt in South China.