Vanessa Fichtner, Ferdinand Kirchner, Martin Kutzschbach, Harald Strauss, Mikael Tillberg, Martin Whitehouse, Henrik Drake
{"title":"重晶石的微尺度δ34S和δ18O变化作为火成岩含水层中流体混合和微生物硫代谢的档案。","authors":"Vanessa Fichtner, Ferdinand Kirchner, Martin Kutzschbach, Harald Strauss, Mikael Tillberg, Martin Whitehouse, Henrik Drake","doi":"10.1080/10256016.2024.2410293","DOIUrl":null,"url":null,"abstract":"<p><p>The stable isotope compositions of sulphur (δ<sup>34</sup>S) and oxygen (δ<sup>18</sup>O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely <sup>34</sup>S-enriched pyrite. What is less well-constrained is whether δ<sup>34</sup>S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ<sup>34</sup>S and δ<sup>18</sup>O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ<sup>18</sup>O<sub>sulfate</sub>, δ<sup>34</sup>S<sub>sulfate</sub>, and δ<sup>34</sup>S<sub>sulfide</sub> of the fracture fluids and with paragenetic pyrite with δ<sup>34</sup>S values reflecting closed system MSR. The δ<sup>18</sup>O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ<sup>34</sup>S (+14.5 to +28.6 ‰) than the pyrite (-47.2 to +53.3 ‰). This lack of extremely high δ<sup>34</sup>S<sub>barite</sub> values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ<sup>34</sup>S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ<sup>34</sup>S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ<sup>34</sup>S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.</p>","PeriodicalId":14597,"journal":{"name":"Isotopes in Environmental and Health Studies","volume":" ","pages":"557-584"},"PeriodicalIF":1.1000,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Microscale δ<sup>34</sup>S and δ<sup>18</sup>O variations of barite as an archive for fluid mixing and microbial sulphur metabolisms in igneous rock aquifers.\",\"authors\":\"Vanessa Fichtner, Ferdinand Kirchner, Martin Kutzschbach, Harald Strauss, Mikael Tillberg, Martin Whitehouse, Henrik Drake\",\"doi\":\"10.1080/10256016.2024.2410293\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The stable isotope compositions of sulphur (δ<sup>34</sup>S) and oxygen (δ<sup>18</sup>O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely <sup>34</sup>S-enriched pyrite. What is less well-constrained is whether δ<sup>34</sup>S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ<sup>34</sup>S and δ<sup>18</sup>O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ<sup>18</sup>O<sub>sulfate</sub>, δ<sup>34</sup>S<sub>sulfate</sub>, and δ<sup>34</sup>S<sub>sulfide</sub> of the fracture fluids and with paragenetic pyrite with δ<sup>34</sup>S values reflecting closed system MSR. The δ<sup>18</sup>O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ<sup>34</sup>S (+14.5 to +28.6 ‰) than the pyrite (-47.2 to +53.3 ‰). This lack of extremely high δ<sup>34</sup>S<sub>barite</sub> values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ<sup>34</sup>S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ<sup>34</sup>S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ<sup>34</sup>S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.</p>\",\"PeriodicalId\":14597,\"journal\":{\"name\":\"Isotopes in Environmental and Health Studies\",\"volume\":\" \",\"pages\":\"557-584\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2024-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Isotopes in Environmental and Health Studies\",\"FirstCategoryId\":\"93\",\"ListUrlMain\":\"https://doi.org/10.1080/10256016.2024.2410293\",\"RegionNum\":4,\"RegionCategory\":\"环境科学与生态学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/10/4 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Isotopes in Environmental and Health Studies","FirstCategoryId":"93","ListUrlMain":"https://doi.org/10.1080/10256016.2024.2410293","RegionNum":4,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/4 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Microscale δ34S and δ18O variations of barite as an archive for fluid mixing and microbial sulphur metabolisms in igneous rock aquifers.
The stable isotope compositions of sulphur (δ34S) and oxygen (δ18O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely 34S-enriched pyrite. What is less well-constrained is whether δ34S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ34S and δ18O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ18Osulfate, δ34Ssulfate, and δ34Ssulfide of the fracture fluids and with paragenetic pyrite with δ34S values reflecting closed system MSR. The δ18O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ34S (+14.5 to +28.6 ‰) than the pyrite (-47.2 to +53.3 ‰). This lack of extremely high δ34Sbarite values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ34S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ34S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ34S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.
期刊介绍:
Isotopes in Environmental and Health Studies provides a unique platform for stable isotope studies in geological and life sciences, with emphasis on ecology. The international journal publishes original research papers, review articles, short communications, and book reviews relating to the following topics:
-variations in natural isotope abundance (isotope ecology, isotope biochemistry, isotope hydrology, isotope geology)
-stable isotope tracer techniques to follow the fate of certain substances in soil, water, plants, animals and in the human body
-isotope effects and tracer theory linked with mathematical modelling
-isotope measurement methods and equipment with respect to environmental and health research
-diagnostic stable isotope application in medicine and in health studies
-environmental sources of ionizing radiation and its effects on all living matter