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Method Article
Analyses of the sulfur isotopic composition (δ34S) of pyrite from methane-bearing sediments have typically focused on bulk samples. Here, we applied secondary ion mass spectroscopy to analyze the δ34S values of various pyrite generations to understand the diagenetic history of pyritization.
Different sulfur isotope compositions of authigenic pyrite typically result from the sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organiclastic sulfate reduction (OSR) in marine sediments. However, unravelling the complex pyritization sequence is a challenge because of the coexistence of different sequentially formed pyrite phases. This manuscript describes a sample preparation procedure that enables the use of secondary ion mass spectroscopy (SIMS) to obtain in situ δ34S values of various pyrite generations. This allows researchers to constrain how SO4-AOM affects pyritization in methane-bearing sediments. SIMS analysis revealed an extreme range in δ34S values, spanning from -41.6 to +114.8‰, which is much wider than the range of δ34S values obtained by the traditional bulk sulfur isotope analysis of the same samples. Pyrite in the shallow sediment mainly consists of 34S-depleted framboids, suggesting early diagenetic formation by OSR. Deeper in the sediment, more pyrite occurs as overgrowths and euhedral crystals, which display much higher SIMS δ34S values than the framboids. Such 34S-enriched pyrite is related to enhanced SO4-AOM at the sulfate-methane transition zone, postdating OSR. High-resolution in situ SIMS sulfur isotope analyses allow for the reconstruction of the pyritization processes, which cannot be resolved by bulk sulfur isotope analysis.
Methane emissions from sediments are common along continental margins1,2. However, most of the methane in areas of diffusive seepage is oxidized at the expense of sulfate within the sediments, a process known as SO4-AOM (Equation 1)3,4. The production of sulfide during this process commonly results in the precipitation of pyrite. Also, OSR also drives the formation of pyrite by releasing sulfide (Equation 2)5.
CH4 + SO42– → HS– + HCO3– + H2O (1)
2CH2O + SO42– → H2S + 2HCO3– (2)
It has been found that authigenic sulfide in the sulfate-methane transition zone (SMTZ) reveals high δ34S values, which was suggested to be caused by enhanced SO4-AOM in areas of seepage6,7,8. In contrast, pyrite induced by OSR commonly displays lower δ34S values9. However, it is challenging to identify different pyrite generations induced by these processes (i.e., OSR and SO4-AOM) if only a bulk sulfur isotope measurement is used, since the successively formed interfingering pyrite generations are characterized by different isotopic compositions. Therefore, microscale in situ sulfur isotope analysis is required to improve our understanding of the actual mineralizing processes10,11,12. As a versatile technique for in situ isotope analysis, SIMS requires only a few nanograms of sample, which sparked its designation as a nondestructive technique. A primary ion beam sputters the target, causing the emission of secondary ions that are subsequently transported to a mass spectrometer for measuring13. In an early in situ sulfur isotope analysis application of SIMS, Pimminger et al. successfully analyzed the δ34S values in galena by using a 10 - 30 µm-diameter beam14. This approach has been increasingly applied to the microanalysis of sulfur isotopic compositions in sulfides, with significant improvements in both measurement precision and resolution11,12,13,14,15,16,17,18,19,20. Pyrite with various morphologic attributes and distinct sulfur stable isotope patterns has been reported from seep and non-seep environments21,22,23,24. However, to the best of our knowledge, prior to our recent SIMS study6, only one study used the in situ sulfur isotope analysis of pyrite from seep environments and revealed large sulfur isotope variability in biogenic pyrite25.
In this study, we applied SIMS to analyze the δ34S values of different generations of authigenic pyrite from a seepage site in the South China Sea, which allowed for microscale discrimination of OSR- and SO4-AOM-derived pyrite.
1. Collection of Samples from a Sediment Core
Note: The core HS148 was obtained from a site near the gas hydrate drilling zone in the Shenhu area, South China Sea, during a cruise of the R/V Haiyang Sihao in 2006.
2. Observation of Variable Morphologies
3. Bulk Sulfur Isotope Analyses
Note: The total sulfur (as sulfide) was extracted as hydrogen sulfide via wet chemical sequential extraction26,27 at the Institut für Geologie und Paläontologie, Westfälische Wilhelms-Universität Münster.
4. In Situ SIMS Analysis
Data Expression - Bulk Sulfur Isotopes:
The bulk sulfur isotope ratio is expressed in relation to the Vienna Canyon Diablo Troilite (V-CDT) standard, and the analytical precision is better than ±0.3‰. The sulfur isotope measurements were calibrated with international reference materials: IAEA-S1 (δ34S = -0.30‰), IAEA-S2 (δ34S = -21.55‰), IAEA-S3 (δ34S = -31.4...
The sulfur isotope analysis of pyrite is a useful approach and can help in identifying the biogeochemical processes that impact pyritization. However, if bulk sulfur isotope analysis is applied, the obtained sulfur isotope signatures commonly represent mixed signals, as sedimentary pyrite aggregates typically consist of multiple, closely interfingering generations. Here, we present a method (i.e., SIMS analysis) for analyzing the in situ sulfur isotopic compositions of various pyrite generations on the ...
The authors have nothing to disclose.
This research was jointly funded and supported by the Natural Science Foundation of China (No. 91128101, 41273054, and 41373007), the China Geological Survey Project for South China Sea Gas Hydrate Resource Exploration (No. DD20160211), Fundamental Research Funds for the Central Universities (No. 16lgjc11), and Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (No. 2011). Zhiyong Lin acknowledges the financial support provided by the China Scholarship Council (No. 201506380046). Yang Lu thanks the Guangzhou Elite Project (No. JY201223) and the China Postdoctoral Science Foundation (No. 2016M592565). We are grateful to Dr. Shengxiong Yang, Guangxue Zhang, and Dr. Jinqiang Liang of the Guangzhou Marine Geological Survey for providing samples and valuable suggestions. We thank Dr. Xianhua Li and Dr. Lei Chen of the Institute of Geology and Geophysics (Beijing), Chinese Academy of Sciences, for help with the SIMS analysis. Dr. Xiaoping Xia is thanked for making available the SIMS Lab of the Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, for the filming of this article. The manuscript benefited from comments from Dr. Alisha Dsouza, review editor of JoVE, and two anonymous referees.
Name | Company | Catalog Number | Comments |
secondary ion mass spectroscopy | Cameca | IMS-1280 | |
thermal field emission scanning electron microscopy | Quanta | Quanta 400F | |
elemental analyser - isotope ratio mass spectrometry | ThermoFinnigan | ThermoFinnigan Delta Plus | |
binocular microscope | any | NA | |
reflected light microscope | Carl Zeiss | 3519001617 | |
polishing machicine | Struers | 60210535 | |
cutting machicine | Struers | 50110202 | |
carbon/gold coating machicine | any | NA | |
ethanol | any | NA | |
acetic acid | any | NA | |
zinc acetate solution (3%) | any | NA | |
HCl solution (25%) | any | NA | |
1 M CrCl2 solution | any | NA | |
0.1 M AgNO3 solution | any | NA | |
V2O5 powder | any | NA | |
pure nitrogen | any | NA | |
syringe | any | NA | |
filter(<0.45 µm) | any | NA | |
tin cups | any | NA | |
round bottom flasks | any | NA | |
epoxy | Struers | 41000004 |
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