Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

IF 0.9 4区 地球科学 Q4 GEOCHEMISTRY & GEOPHYSICS
Alexey Kamyshny Jr, Gregory Druschel, Zahra F Mansaray, James Farquhar
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引用次数: 44

Abstract

The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling.

Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6?μmol?L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ34S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ34S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH?<?4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur–polysulfide – hydrogen sulfide system. Triple sulfur isotope (32S, 33S, 34S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ?33S among species and between pools are observed.

The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero–valent sulfur, as well as differences in ?33S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.

Abstract Image

黄石国家公园地热泉中与非生物硫转化相关的多重硫同位素分馏
本文对美国黄石国家公园(YNP)热液泉和池中的主要硫化氢和硫酸盐以及中间硫化物(零价硫、硫代硫酸盐、亚硫酸盐和硫氰酸盐)进行了定量分析。我们将这些测量结果与硫酸盐、硫化氢和零价硫的四重硫同位素组成测量结果相结合。本研究的主要目的是了解以复杂的非生物硫循环为主导的系统中多硫同位素分馏。从黄石国家公园的六个泉水和水池中提取的水样具有pH值、氯化物与硫酸盐的比值、硫化物和中间硫的浓度等特征。池中硫酸盐浓度表明,深层母水与浅层含氧水混合导致硫化物氧化,或表面硫化物与大气氧氧化。由于硫代硫酸盐快速歧化,低pH池中硫代硫酸盐浓度较低(约6 μmol - L-1)。在pH值较高的水塘中,硫代硫酸盐的浓度不同,这取决于硫代硫酸盐形成的不同地球化学途径。4个体系中硫酸盐的δ34S值与深层热母水体稀释沸腾模型的混合线计算值接近。在两个池中,硫酸盐的δ34S值与该模型计算的值有显著差异。ZVS与硫化氢之间的硫同位素分馏在pH = 4时接近于零。在较高的pH值下,由于硫-多硫化物-硫化氢体系中的平衡,零价硫比硫化氢稍重。热液池水体的三硫同位素(32S、33S、34S)分馏模式更符合涉及中间硫的氧化还原过程,而非细菌硫酸盐还原过程。在物种之间和池之间观察到微小但可解决的?33S差异。硫酸盐同位素组成的变化、硫化物和零价硫同位素组成差异的来源以及硫化物和硫酸盐- 33S的差异可能是由复杂的非生物氧化还原反应网络引起的,包括歧化途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Geochemical Transactions
Geochemical Transactions 地学-地球化学与地球物理
CiteScore
3.70
自引率
4.30%
发文量
2
审稿时长
>12 weeks
期刊介绍: Geochemical Transactions publishes high-quality research in all areas of chemistry as it relates to materials and processes occurring in terrestrial and extraterrestrial systems.
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