The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solutio...The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solution with varyingδ^(18)O_(H_(2)O) value at initial neutral pH for different lengths of time(15-300 days).The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined.The sulfur isotope fractionation factor(△^(34)S_(SO4-stibnite))values decreased from 0.8‰to-2.1‰during the first 90 days,and increased to 2.6‰at the 180 days,indicating the dominated intermediate sulfur species such as S_(2)O_(3)^(2-),S0,and H_(2)S(g)involved in Sb2S3 oxidation processes.The incorporation of O into sulfate derived from O_(2)(~100%)indicated that the dissociated O_(2)was only directly adsorbed on the stibnite-S sites in the initial stage(0-90 days).The proportion of O incorporation into sulfate from water(27%-52%)increased in the late stage(90-300 days),which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O_(2)on stibnite-Sb sites.The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-.The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.展开更多
基金supported by the National Natural Science Foundation of China(No.41672245)the National Key Research and Development Program of China(No.2022YFC3702201).
文摘The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solution with varyingδ^(18)O_(H_(2)O) value at initial neutral pH for different lengths of time(15-300 days).The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined.The sulfur isotope fractionation factor(△^(34)S_(SO4-stibnite))values decreased from 0.8‰to-2.1‰during the first 90 days,and increased to 2.6‰at the 180 days,indicating the dominated intermediate sulfur species such as S_(2)O_(3)^(2-),S0,and H_(2)S(g)involved in Sb2S3 oxidation processes.The incorporation of O into sulfate derived from O_(2)(~100%)indicated that the dissociated O_(2)was only directly adsorbed on the stibnite-S sites in the initial stage(0-90 days).The proportion of O incorporation into sulfate from water(27%-52%)increased in the late stage(90-300 days),which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O_(2)on stibnite-Sb sites.The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-.The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.
