This study examines the use of intact samples as an alternative to powder in conventional batch sorption studies to determine the distribution coefficient(K_d).Stable cesium(^(133)Cs) and strontium(^(87)Sr) were used ...This study examines the use of intact samples as an alternative to powder in conventional batch sorption studies to determine the distribution coefficient(K_d).Stable cesium(^(133)Cs) and strontium(^(87)Sr) were used under specified geochemical conditions to compare the Kdvalues of powder and block pumice tuff samples. The aim of the study was to infer any Kddifference under laboratory and field conditions. Kdvalues for block samples were found to be less than one order of magnitude lower than powder materials for both Cs and Sr on fresh tuff, and more than one order of magnitude lower in oxidized tuff. Destruction of micropores in oxidized tuff was estimated to be mainly responsible for reducing Kdvalues in oxidized tuff. However, approximately one order of magnitude difference in Kdvalues indicates that homogenously prepared intact samples can be used for sorption coefficient measurement at closer to in situ conditions. Pore size distribution analysis using mercury intrusion porosimetry revealed that lower Kdvalues on block samples result from lower surface area available as sorption sites due to inaccessible closed pores in the intact solid.展开更多
Most economically important tungsten(W)deposits are of magmatic-hydrothermal origin.The species and partitioning of W during fluid exsolution,considered to be the controlling factors for the formation of ore deposits,...Most economically important tungsten(W)deposits are of magmatic-hydrothermal origin.The species and partitioning of W during fluid exsolution,considered to be the controlling factors for the formation of ore deposits,are thus of great significance to investigate.However,this issue has not been well addressed mainly due to the significant difference in reported partition coefficients(e.g.,from strongly incompatible to strongly compatible)between fluid and melt(D_(W)^(fluid/melt)).Here,we used an in situ Raman spectroscopic approach to describe the W speciation,and to quantitatively determine the Dfluid/melt of individual and total W species in granite melts and coexisting Na2WO4 solutions at elevated temperatures(T;700–800C)and pressures(P;0.35–1.08 GPa).Results show that WO_(4)^(2-)and HWO4are predominant W species,and the fractions of these two species are similar in melt and coexisting fluid.The partitioning behaviors of WO_(4)^(2-)and HWO4are comparable,exhibiting strong enrichment in the fluid.The total DW fluid/melt ranges from 8.6 to 37.1.Specifically,DW fluid/melt decreases with rising T–P,indicating that shallow exsolution favors enrichment of W in evolved fluids.Furthermore,Rayleigh fractionation modeling based on the obtained D_(W)^(fluid/melt)data was used to describe the fluid exsolution processes.Our results strongly support that fluid exsolution can serve as an important mechanism to generate W-rich oreforming fluids.This study also indicates that in situ approach can be used to further investigate the geochemical behavior of ore-forming elements during the magmatic-hydrothermal transition,especially for rare metals associated with granite and pegmatite.展开更多
文摘This study examines the use of intact samples as an alternative to powder in conventional batch sorption studies to determine the distribution coefficient(K_d).Stable cesium(^(133)Cs) and strontium(^(87)Sr) were used under specified geochemical conditions to compare the Kdvalues of powder and block pumice tuff samples. The aim of the study was to infer any Kddifference under laboratory and field conditions. Kdvalues for block samples were found to be less than one order of magnitude lower than powder materials for both Cs and Sr on fresh tuff, and more than one order of magnitude lower in oxidized tuff. Destruction of micropores in oxidized tuff was estimated to be mainly responsible for reducing Kdvalues in oxidized tuff. However, approximately one order of magnitude difference in Kdvalues indicates that homogenously prepared intact samples can be used for sorption coefficient measurement at closer to in situ conditions. Pore size distribution analysis using mercury intrusion porosimetry revealed that lower Kdvalues on block samples result from lower surface area available as sorption sites due to inaccessible closed pores in the intact solid.
基金supported by the National Natural Science Foundation of China(41922023,41830428,42173038,41973055,and 42130109)the Research Funds for the Frontiers Science Center for Critical Earth Material Cycling(Nanjing University,China)the Fundamental Research Funds for the Central Universities,China(2022300192).
文摘Most economically important tungsten(W)deposits are of magmatic-hydrothermal origin.The species and partitioning of W during fluid exsolution,considered to be the controlling factors for the formation of ore deposits,are thus of great significance to investigate.However,this issue has not been well addressed mainly due to the significant difference in reported partition coefficients(e.g.,from strongly incompatible to strongly compatible)between fluid and melt(D_(W)^(fluid/melt)).Here,we used an in situ Raman spectroscopic approach to describe the W speciation,and to quantitatively determine the Dfluid/melt of individual and total W species in granite melts and coexisting Na2WO4 solutions at elevated temperatures(T;700–800C)and pressures(P;0.35–1.08 GPa).Results show that WO_(4)^(2-)and HWO4are predominant W species,and the fractions of these two species are similar in melt and coexisting fluid.The partitioning behaviors of WO_(4)^(2-)and HWO4are comparable,exhibiting strong enrichment in the fluid.The total DW fluid/melt ranges from 8.6 to 37.1.Specifically,DW fluid/melt decreases with rising T–P,indicating that shallow exsolution favors enrichment of W in evolved fluids.Furthermore,Rayleigh fractionation modeling based on the obtained D_(W)^(fluid/melt)data was used to describe the fluid exsolution processes.Our results strongly support that fluid exsolution can serve as an important mechanism to generate W-rich oreforming fluids.This study also indicates that in situ approach can be used to further investigate the geochemical behavior of ore-forming elements during the magmatic-hydrothermal transition,especially for rare metals associated with granite and pegmatite.
