High-precision double-spike Cd isotopic measurements of seawater by MC-ICP-MS and its application to seawater affected by hydrothermal vent fluids

Cadmium(Cd)isotopes in seawater have been proven as an important geochemical tool for tracing ocean Cd circulation in the modern ocean.In this study,we evaluated a new method to separate Cd(*60 ng)from seawater using Chelex resin(1.0 g)coupled with AG-MP-1M resin.The results show that the Chelex resin is suffi-cient to remove Cd from Na and Mg matrix with Cd recoveries at 98.3±3.5%(2SD,N=6);while AG-MP-1M resin could separate Cd from the residual Na,Mg,and isobaric inferences.The total Cd recoveries of the method are 96.3±1.5%(2SD;N=4)and the salinity of the samples has no significant impacts on Cd recovery.Cd isotope ratios were measured using a Nu PlasmaⅢMC-ICP-MS and^(111)Cd–^(110)Cd double spike technique.By comparing theδ^(114/110)Cd values(0.00±0.06%)of synthetic seawaters doped with Cd isotope standard(NIST-3108;treated by Chelex+AG-MP-1M resin)and the reference value(-0.00%),no variations were observed.We also analyzed the Cd isotope compositions of three deep seawaters from a column at the Southwest Indian Ocean Ridges(SWIR).Theδ^(114/110)Cd values of the col-umn are decreased from 1.05±0.05%at 3200 m to 0.36±0.05%at 2800 m,differing from reportedδ^(114/110)Cd values of deep seawater in other oceans.Considering the spatial distance between the column and active hydrothermal vents in SWIR(-13 km),we propose that such positiveδ^(114/110)Cd values of deep seawater were likely contaminated by vent fluids,which could provide heavy Cd isotope to deep seawaters.This study demon-strates that Cd isotope is more sufficient to distinguish the impact of plumes on deep seawater.

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.