Hopanoid Acids and Their Geochemistry Significance Detected in Seep Carbonates from the South China Sea Continental Slope
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摘要: 对南海东沙海域九龙甲烷礁冷泉碳酸盐岩的藿烷酸系列化合物进行了研究, 结果显示冷泉碳酸盐岩中含有17β(H), 21β(H)-30-藿烷酸至17β(H), 21β(H)-33-藿烷酸系列化合物. 其中site1样品TVG3-C2(ANME-2古菌种群为主)中的17β(H), 21β(H)-32-藿烷酸化合物亏损13C(-69.8‰), 且其同位素值较接近iso-/aiso-C15:0脂肪酸(-75.2‰~-90.0‰), 说明其母质摄入了甲烷来源的碳.尽管site2(TVG13-C3和TVG14-C2)和site3(TVG8-C5)自生碳酸盐岩中藿烷酸化合物都表现出了非渗漏特征(-30.7‰~-40.3‰, ANME-1古菌种群为主), 但这些样品中藿烷酸的δ13C值同样较接近硫酸盐还原菌来源的iso-/anteiso-C15:0的δ13C值(-32.5‰~-49.8‰).由此说明大多数存在于以ANME-1种群为主的渗漏环境中的硫酸盐还原菌并没有参与到甲烷厌氧氧化作用中, 而导致藿烷酸化合物和硫酸盐还原菌来源的生物标志物并不明显亏损13C, 并且δ13C值相近.Abstract: The lipid biomarkers of hopanoid acids in cold seep carbonates from the South China Sea continental slope are investigated. In the hopanoid acids, 17β(H), 21β(H)-30-hopanoid acid-17β(H), 21β(H)-33-hopanoid acid are identified with 17β(H), 21β(H)-32-hopanoid acid being the most aboundant. The 17β(H), 21β(H)-32-hopanoic acid depleted in 13C and the δ13C value(-69.8‰) fall close to the range of SRB (sulfate-reducing bacteria)-derived iso-/anteiso-C15:0 (-75.2‰ to -90.0‰) in site1 seep carbonate(TVG3-C2, ANME-2 dominated), suggesting the incorporation of methane-derived carbon. Although they show non-seep isotopic signatures (-30.7‰ to -40.3‰, ANME-1 dominated) in site3 (TVG8-C5) and site2 seep carbonates (TVG13-C3 and TVG14-C2), hopanoids δ13C values fall close to the range of SRB-derived iso-/anteiso-C15:0 (-32.5‰ to -49.8‰). The majority of SRB are not involved in AOM (anaerobic oxidization of methane) possibly because ANME-1 cells often occur as monospecific aggregates.
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Key words:
- hopanoic acids /
- methanotrophy /
- seep carbonates /
- Jiulong methane reef /
- microorganisms /
- geochemistry
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图 1 采样点位置
样品TVG3采自1号站位；TVG13和TVG14采自2号站位；TVG8采自3号站位
Fig. 1. Bathymetry of portion of the northern slope of the South China Sea
图 2 TVG8-C5酸类化合物总离子流(a)、m/z191离子流(b)和样品中ββ-32-藿烷酸化合物质谱(c)
31-Δ17(21)为C31Δ17(21)藿烯酸，ββ-32-acid为17β(H)，21β(H)-32-藿烷酸
Fig. 2. Total ion chromatogram (TIC) of the carboxylic acid fraction of TVG8-C5 (a); the m/z 191 chromatograms of methyl esters of hopanoic acids in sample TVG8-C5 (b); the mass spectrum of 17β(H), 21β(H)-32-hopanoic acid (c)
图 3 C30Δ17(21)藿烯酸，C31Δ17(21)藿烯酸和C32Δ17(21)藿烯酸系列化合物质谱图
Fig. 3. The mass spectrum of C30Δ17(21)-, C31Δ17(21)- and C32Δ17(21)- hopenoic acid
图 4 藿烷酸化合物及iso-/aiso-C15:0碳同位素组成及主导微生物种群特征
Fig. 4. The carbon composition of the hopanoic acids, iso-/aiso-C15:0 and the dominated consortia in cold seep settings
表 1 南海北部陆坡冷泉碳酸盐岩采样信息
Table 1. Locations of seep carbonates from the northern slope of the South China Sea
位置 年份－航次编号 纬度N 经度E 水深(m) site1 TVG3-C2 2004-SO-177-1 22°08.98′ 118°52.34′ 473 site3 TVG13- C3 2004-SO-177-2 22°08.54′ 118°43.45′ 555 TVG14-C2 2004-SO-177-1 22°08.63′ 118°43.39′ 533 site2 TVG8-C5 2004-SO-177-1 22°02.85′ 118°46.55′ 769 
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表 2 藿烷酸化合物碳同位素组成及环境中主导种群
Table 2. The carbon composition of the hopanoid acids and the dominant archaeal consortia consortium in cold seep settings
样品编号 αβ-C32-hopanoic acid ββ-C32-hopanoic acid iso-C15:0 aiso-C15:0 主导微生物种群 参考文献 δ13C(‰)(V-PDB) δ13C(‰)(V-PDB) δ13C(‰)(V-PDB) δ13C(‰)(V-PDB) TVG3-C2 tr -69.8 -90 -75.2 ANME-2 TVG8-C5 tr -40.3 -38.9 -41.5 ANME-1 TVG13-C3 tr -30.7 -45.2 -49.8 ANME-1 TVG14-C2 tr -32.9 -32.5 -35.5 ANME-1 Cozzo Disi -87 -83 -53 ANME-2 Ziegenbalg et al.(2012) Gaspa-1 -52 -77 -80 -68 ANME-2 Ziegenbalg et al.(2012) Monticino -31 -33 -27 ANME-1 Ziegenbalg et al.(2012)
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