A 150-year Isotopic Record of Lead Deposition in Yancheng Coastal Wetland,China

Radioactive markers are useful in dating lead （Pb） deposition patterns from industrialization in sedimentary archives. As a well-known natural reserve in the world, Yancheng coastal wetland in Jiangsu Province is one of areas most sensitive to global sea level change and is located in the most developed and polluted region of China. Two cores were collected in Yancheng wetland in October 2013 and dated using 210pb and 137Cs radiometric techniques. Sediments in both cores were sectioned into depth bands and examined systematically for dry bulk density, water content, magnetic susceptibility and grain-size. Multiple elements including Pb were also measured using inductively coupled plasma systems. Unsupported 21~Pb activities decreased with depth in both of the two cores, and 21~pb chronologies were established （covering 150 years） using the constant rate of supply （CRS） model. The measured Pb contents ranged from 14.97 mg/kg to 29.40 mg/kg with average values of 17.17-22.79 mg/kg, and the Pb fluxes ranged from 41.70 mg/（m2·yr） to 172.70 mg/（m2·yr） with averages of 95.59-123.41 mg/（m2·yr）. Temporal variations of Pb flux, enrichment factors and Pb isotopes show a gradual and continuous increase over time and clearly reflect increased emissions from anthropogenic activities in the region. The Pb isotopic compositions show that most of Pb deposition in Yancheng wetland is input from natural sources by water flows and has the same levels of Pb as in the surface sediment of the Yangtze River and the Pacific mineral aerosol. We also stress the anthropogenic Pb contribution in Yangcheng wetland sediment and the reason of our Pb isotopes not showing anthropogenic signature is likely the insta- bility of anthropogenic Pb in high Fe/Mn oxide conditions. Therefore, more attention should be paid to current local pollution problems, and society should take action to seek a balance between economic development and environmental protection.

Cadmium isotopic constraints on metal sources in the Huize Zn–Pb deposit, SW China

The Sichuan–Yunnan–Guizhou(SYG)Zn–Pb metallogenic zone in SW China contains>400 carbonatehosted hydrothermal Zn–Pb deposits.Some of these,such as the Huize,Tianbaoshan,and Daliangzi deposits,are super-large deposits with significant reserves of Cd,Ge,and Ag.However,the sources of these metals remain controversial.This study investigated the Cd isotopic geochemistry of the Huize deposit,the largest Zn–Pb deposit in the SYG area.Sphalerites formed at three stages in the deposit have different colors:black or dark brown(Stage I),red(Stage II),and light-yellow(Stage III).The d^(114/110)Cd values of the sphalerites are in the order Stage III<Stage I<Stage II.Kinetic isotopic fractionation is likely the key factor causing the lower δ^(114/110)Cd values in the early formed Stage I sphalerites than in laterformed Stage II sphalerites,with cooling of ore-forming fluids being responsible for the still lower values of the Stage III sphalerites.In galena,the δ^(114/110)Cd values are inversely correlated with Cd contents and tend to be higher in high-Zn galena.We speculate that Cd isotopic fractionation was significant during the precipitation of sphalerite and galena,with light Cd isotopes being enriched in galena rather than sphalerite.Comparison of the Cd isotopic signatures and Zn/Cd ratios of different endmembers suggests that the δ^(114/110)Cd values and Zn/Cd ratios of sphalerite from the Huize deposit,as well as other largescale deposits from the SYG area,are lie in those range of Emeishan basalts and sedimentary rocks and the mean δ^(114/110)Cd values of these deposits show good negative correlation with 1/Cd,suggesting that the ore-forming materials of these deposits were derived from the mixing of Emeishan basalts and sedimentary rocks.This study demonstrates that Cd isotopes can be useful proxies in elucidating ore genesis in large Zn–Pb deposits.

One potential superlarge Pb-Zn ore occurrence with Himalayan thermal brine genesis——Wuqia Region, Xinjiang, China

The paper focuses on geological and geochemical evidence of thermal brine genesis of Pb Zn deposits in Wuqia district, Xinjiang. The results suggest that the known Pb Zn deposits, such as Wulagen, are thermal brine genesis, which is supported by the features of tectonic setting, magma and regional metamorphism, and the characteristics of trace element distribution in strata and redistribution in the ore forming process, the REE patterns and their main parameters of main type ores, the composition features and the source indicators of Pb, S isotopes. Ore forming conditions of superlarge Pb Zn deposits studies show that there exists tectonic and sources setting of Jinding type superlarge Pb Zn deposits in this area. Five Pb Zn ore belts and central uplift belts discovered lately have not only confirmed that the genesis of Wulagen Pb Zn deposits is thermal genesis, but also further proved that there exists tectonic and source setting of Jinding type superlarge Pb Zn deposit in the study area. Mineral deposit model was described and prospecting potentiality of superlarge Pb Zn deposit and their significance were discussed.

Genesis of the Maoping carbonate-hosted Pb–Zn deposit,northeastern Yunnan Province,China:evidences from geology and C–O–S–Pb isotopes

The Maoping Pb-Zn deposit(~3 Mt Pb+Zn reserves with grades of 12-30 wt%)is one of the largest Pb-Zn deposits in the Sichuan-Yunnan-Guizhou(SYG)metallogenic province,which has contributed a tremendous amount of lead and zinc resources for China.To obtain a further understanding of the sources of ore-forming materials and ore genesis of the deposit,S-Pb isotopes of sulfides and C-O isotopes of ore-stage calcites were systematically collected from representative orebodies at different elevations with a Finnigan MAT-253 mass spectrometer.The calcites separated from the sulfides of the NoⅠand NoⅡorebodies shared identical b13 CPDB values(-5.3 to-0.8‰)andδ18OSMOW values(+14.5 to+21.8‰)with those of the calcites in the SYG region,suggesting that CO2 in regional ore-forming fluids possibly had a homologous C-O source that originated from a ternary mixture of the dissolution of marine carbonate rocks,degassing process of the Emeishan mantle plume,and dehydroxylation of sedimentary organic matter.The No.Ⅰ-1 and No.Ⅰ-2 orebody was hosted in the same strata,but the sulfur source of No.Ⅰ-1 orebody(+13.1 to+19.0‰)with equilibrated sulfur fractionation(δ34Sspbaierite-<δ34Sgalena)and No.Ⅰ-2 orebody(+18.0 to+21.8‰)with sulfur equilibrium fractionation(δ34Sspnaierite>δ34-Sgalena)were different.They were derived from the allopatry thermochemical sulfate reduction(TSR)of overlying Carboniferous sulfates in the ore-hosting strata and local TSR of sulfates in the ore-bearing Upper Devonian Zaige Formation,respectively.The narrow and uniform Pb isotopic ratios of single galena grains collected from sulfides with 206Pb/204Pb of 18.713-18.759,207Pb/204Pb of 15.772-15.776 and 208Pb/204Pb of39.383-39.467 indicate a well-mixed metal source(s)that consist of Proterozoic Kunyang and Huili Group basement rocks and Devonian to Middle Permian ore-hosting sedimentary rocks.Besides,the late Permian Emeishan basalts are difficult to contribute metals for regional Pb-Zn mineralization despite a closely spatial relationship with the distribution of the Pb-Zn deposit.This is supported by Pb isotopic ratios plotting above the average upper crustal Pb evolution curves and staying far away from that of the agecorrected Emeishan basalts.Hence,taking into account of the similarities in tectonic setting,ore-hosting rock,ore assemblage,wall rock alteration,ore-controlling structure,and ore-forming materials and the differences in relationship with regional magmatism,fluid inclusion characteristic and ore grade between the Maoping deposit and typical MVT Pb-Zn deposit,the ore genesis of the Maoping deposit should be an MVT like Pb-Zn deposit.

Rare earth element(REE) geochemistry of different colored fluorites from the Baoshan Cu–Pb–Zn deposit, Southern Hunan,South China

The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.

Sources of the Laoxiongdong carbonate-hosted Pb–Zn deposit in Southwest China:constraints from S–Pb–Zn isotopic compositions

The Sichuan-Yunnan-Guizhou(SYG)Pb-Zn mineral province,which has significant Pb-Zn repositories in China,is situated in the western Yangtze Block.Despite decades of research,the Pb-Zn source of deposits is still disputed between the basement rocks,sedimentary wall rocks,or the Emeishan flood basalts.The newly-discovered Laoxiongdong Pb-Zn deposit is hosted by the Late Ediacaran Dengying Formation in the SYG province.Moreover,the Laoxiongdong orebodies lie between regional deep faults and close to the Proterozoic basement and Emeishan basalts.Hence,this deposit represents a good case study on the ore-forming material source for the regional Pb-Zn mineralization.The Laoxiongdong Pb-Zn ores are massive,vein,or disseminated and have mainly sphalerite,galena,pyrite,quartz,and calcite.In this paper,we present new sulfide S-Pb-Zn isotope data of the deposit.The sulfideδ34SCDT values(+11.8 to+16.5‰)suggest that the reduced sulfur was mainly sourced from evaporites in the Late Ediacaran-Cambrian sequences.Pb isotopic ratios(206Pb/204Pb=18.004-18.107,207Pb/204Pb=15.652-15.667,and 208Pb/204Pb=38.037-38.248)suggest that the lead metal was primarily originated from the basement rocks.The sphaleriteδ66Zn values(+0.16 to+0.37‰)are also highly similar(within error)to those of basement rocks(+0.10 to+0.34‰),suggesting a basement-rocks zinc source with minor contributions from the carbonate host rocks and Emeishan flood basalts.The narrow sphalerite Zn isotopic range(0.21‰)also indicates that the Zn isotopic fractionation between the sphalerite and initial fluid was limited during the sphalerite ore precipitation.Therefore,we propose that both the Late Ediacaran Dengying Formation rocks and Proterozoic basement rocks were important ore-forming material source for the Laoxiongdong deposit,whereas the Emeishan flood basalts represent only a minor ore-material source.

Restructuring of 4H Phase Au Nanowires and its Catalytic Behavior toward CO Electro-oxidation

Au nanowires in 4H crystalline phase(4H Au NWs)are synthesized by colloid solution methods.The crys-talline phase and surface structure as well as its performance toward electrochemical oxidation of CO be-fore and after removing adsorbed oleylamine molecules(OAs)intro-duced from its synthesis are evaluat-ed by high-resolution transmission electron microscopy(HR-TEM),X-ray diffraction(XRD),underpoten-tial deposition of Pb(Pb-upd)and cyclic voltammetry.Different methods,i.e.acetic acid cleaning,electrochemical oxidation cleaning,and diethylamine replacement,have been tried to remove the adsorbed OAs.For all methods,upon the removal of the adsorbed OAs,the morphology of 4H gold nanoparticles is found to gradually change from nanowires to large dumbbell-shaped nanoparticles,accompanying with a transition from the 4H phase to the face-centered cubic phase.On the other hand,the Pb-upd results show that the sample sur-faces have almost the same facet composition before and after removal of the adsorbed OAs.After electrochemical cleaning with continuous potential scans up to 1.3 V,CO electro-oxida-tion activity of the 4H Au sample is significantly improved.The CO electro-oxidation activi-ty is compared with results on the three basel Au single crystalline surfaces reported in the lit-erature,possible origins for its enhancement are discussed.

Anthropogenic,detritic and atmospheric soil-derived sources of lead in an alpine poor fen in northeast China

Ombrotrophic bogs are faithful archive of atmospheric metal deposition, but the potential for fens to reconstruct environmental change is often underestimated. In this study, some new data on the Pb depositional history in northeast China were provided using two ^210Pb-dated peat sequences from a poor fen in the Fenghuang Mountain of Heilongjiang province. Anthropogenic, detritic and atmospheric soil sources were discriminated using a two-step sequential digestion （weak acid leaching to liberate mobile Pb which is often regarded as anthropogenic Pb, especially for recent samples） and a ratio of unsupported ^210Pb and supported ^210Pb with the logic of that the ^214Pb mainly represents the residual detritus （constant throughout the core） and the unsupported ^210Pb arises from atmospheric fallout. A higher ^210Pb/^214Pb suggests more contributions from atmospheric deposition to the Pb content in the peat, and a ratio of 10 was defined to indicate the boundary between detrific input and atmospheric deposition. The detritic Pb was estimated to be 10-13 mg·kg^-1, the anthropogenic Pb ranged from 10-80 mg·kg^-1, and the atmospheric soil-derived Pb ranged from 〈 5 mg·kg^-1 to 30 mg·kg^-1. The history of anthropogenic Pb pollution over the last 150 years was reconstructed, and the calculated Pb deposition rate （AR Pb） ranged from 5 to 56 mg·m^-2·yr^-1. Using Ti as a reliable reference, the enrichment factor of Pb （EF Pb） relative to the upper continental crust was calculated. Both AR Pb and EF Pb increased with time, especially after the foundation of the People＇s Republic of China. This is consistent with increasing industrialization and coal burning in the last 60 years in northeast China. The present record of anthropogenic Pb deposition was consistent with the previous reports and an increasing trend of environmental pollution due to anthropogenic activities, in contrasts to Europe and North America which have experienced a major environmental cleanup. For the first time, this work estimates atmospheric Pb deposition via a minerotrophic peat core in China. This will enhance the use of peat archives for studies of environmental change.