Abstract
In this study, we analyzed stable calcium isotope results of authigenic carbonates from two cold seep areas of the Dongsha area and the Baiyun Sag in the northern South China Sea. The stable isotopes of carbon and oxygen as well as the mineral composition of authigenic carbonates were used to investigate control calcium isotope fractionation. The δ 44/40Ca ratios of the southwestern Dongsha area samples ranged from 1.21‰ to 1.52‰ and the ratio of the Baiyun Sag sample was 1.55‰ of the SRM915a isotope standard. X-ray diffraction analysis showed that the carbonate samples consisted of dolomite, calcite and aragonite, with small amounts of high-Mg calcite and siderite. The δ 13C values of the carbonates of the southwestern Dongsha area varied between −49.21‰ and −16.86‰ of the Vienna PeeDee Belemnite (VPDB) standard and the δ 18O values ranged from 2.25‰ to 3.72‰ VPDB. The δ 13C value of the Baiyun Sag sample was 2.36‰ VPDB and the δ 18O value was 0.44‰ VPDB. The δ 13C values of the carbonates of the southwestern Dongsha area revealed there is methane seeping into this area, with a variable contribution of methane-derived carbon. The sampled carbonates covered a range of δ 13C values suggesting a dominant methane carbon source for the light samples and mixtures of δ 13C values for the heavier samples, with possibly an organic or seawater carbon source. The δ 18O values indicated that there is enrichment in 18O, which is related to the larger oxygen isotope fractionation in dolomite compared to calcite. The results of the Baiyun Sag sample exhibited normal seawater carbon and oxygen isotopic values, indicating that this sample is not related to methane seepage but instead to precipitation from seawater. The relatively high δ 44/40Ca values indicated either precipitation at comparatively high rates in pore-water regimes with high alkalinity, or precipitation from an evolved heavy fluid with high degrees of Ca consumption (Raleigh type fractionation). The dolomite samples from the Dongsha area revealed a clear correlation between the carbon and calcium isotope composition, indicating a link between the amount and/or rate of carbonate precipitation and methane contribution to the bicarbonate source. The results of the three stable isotope systems, mineralogy and petrography, show that mineral composition, the geochemical environment of authigenic carbonates and carbon source can control the calcium isotope fractionation.
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References
Charlou J L, Donval J P, Fouquet Y, et al. Physical and chemical characterization of gas hydrates and associated methane plumes in the Congo-Angola Basin. Chem Geol, 2004, 205: 405–425
De Lange G, Mastalerz V, Dählmann A, et al. Geochemical composition and origin for fluid and gas fluxes at Eastern Mediterranean mud volcanoes. In: Fluid seepages/mud volcanism in the Mediterranean and adjacent domains. CIESM Workshop Monographs, 2006, 29: 103–110
Gontharet S, Stadnitskaia A, Bouloubassi I, et al. Palaeo methaneseepage history traced by biomarker patterns in a carbonate crust Nile deep-sea fan (Eastern Mediterranean Sea). Mar Geol, 2009, 261: 105–113
Michaelis W, Seifert R, Nauhaus K, et al. Microbial reefs in the Black Sea fueled by anaerobic oxidation of methane. Science, 2002, 297: 1013–1015
Niemann H, Duarte J, Hensen C, et al. Microbial methane turnover at mud volcanoes of the Gulf of Cadiz. Geochim Cosmochim Acta, 2006, 70: 5336–5355
Greinert J, Bohrmann G, Suess E. Gas hydrate-associated carbonates and methane-venting at Hydrate Ridge: Classification, distribution, and origin of authigenic lithologies. In: Paull C K, Dillon W P, eds. Natural Gas Hydrates: Occurrence, Distribution, and Detection. Geophys Monogr, 2001, 124: 99–113
Feng D, Chen D, Qi L, et al. Petrographic and geochemical characterization of seep carbonate from Alaminos Canyon, Gulf of Mexico. Chin Sci Bull, 2008, 53: 1716–1724
Feng D, Chen D, Roberts H H. Petrographic and geochemical characterization of seep carbonate from Bush Hill (GC185) gas vent and hydrate site of the Gulf of Mexico. Mar Petrol Geol, 2009, 26: 1190–1198
Heuser A, Eisenhauer A, Böhm F, et al. Calcium isotope (δ 44/40Ca) variations of Neogene planktonic foraminifera. Paleoceanography, 2005, 20: PA2013, doi:10.1029/2004PA001048
Fantle M S, DePaolo D J. Variations in the marine Ca cycle over the past 20 million years. Earth Planet Sci Lett, 2005, 237: 102–117
Sime N G, De La Rocha C L, Tipper E T, et al. Interpreting the Ca isotope record of marine biogenic carbonates. Geochim Cosmochim Acta, 2007, 71: 3979–3989
Gussone N, Eisenhauer A, Tiedemann R, et al. δ 44Ca, δ 18O and Mg/Ca reveal Caribbean sea surface temperature and salinity fluctuations during the Pliocene closure of the Central American Gateway. Earth Planet Sci Lett, 2004, 227: 201–214
Immenhauser A, Nägler T F, Steuber T, et al. A critical assessment of mollusk 18O/16O, Mg/Ca, and 44Ca/40Ca ratios as proxies for Cretaceous seawater temperature seasonality. Palaeogeogr Palaeoclimatol Palaeoecol, 2005, 215: 221–237
Hippler D, Eisenhauer A, Nägler T F. Tropical Atlantic SST history inferred from Ca isotope thermometry over the last 140 ka. Geochim Cosmochim Acta, 2006, 70: 90–100
Clementz M T, Holden P, Koch P L. Are calcium isotopes a reliable monitor of trophic level in marine settings? Int J Osteo, 2003, 13: 29–36
Heuser A, Tütken T, Gussone N, et al. Calcium isotopes in fossil bones and teeth-Diagenetic versus biogenic origin. Geochim Cosmochim Acta, 2011, 75: 3419–3433
Böhm F, Gussone N, Eisenhauer A, et al. Calcium isotope fractionation in modern Scleractinian corals. Geochim Cosmochim Acta, 2006, 70: 4452–4462
Gussone N, Langer G, Geisen M, et al. Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa. Earth Planet Sci Lett, 2007, 260: 505–515
Gussone N, Hönisch B, Heuser A, et al. A critical evaluation of calcium isotope ratios in tests of planktonic foraminifers. Geochim Cosmochim Acta, 2009, 73: 7241–7255
Gussone N, Filipsson H L. Calcium isotope ratios in calcitic tests of benthic Foraminifers. Earth Planet Sci Lett, 2010, 290: 108–117
Langer G, Gussone N, Nehrke G, et al. Calcium isotope fractionation during coccolith formation in Emiliania huxleyi: Independence of growth and calcification rate. Geochem Geophys Geosys, 2007, 8: Q05007
Teichert B M A, Gussone N, Eisenhauer A, et al. Clathrites: Archives of near-seafloor pore-fluid evolution (δ 44/42Ca,δ 13C,δ 18O) in gas hydrate environments. Geology, 2005, 33: 213–216
Fantle M S, DePaolo D J. Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca2+(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments. Geochim Cosmochim Acta, 2007, 71: 2524–2546
Teichert B M A, Gussone N, Torres M E. Control on calcium isotope fractionation in sedimentary porewater. Earth Planet Sci Lett, 2009, 279: 373–382
Gussone N, Eisenhauer A, Heuser A, et al. Model for kinetic effects on calcium isotope fractionation (δ 44Ca) in inorganic aragonite and cultured planktonic foraminifera. Geochim Cosmochim Acta, 2003, 67: 1375–1382
Tang J, Dietzel M, Köhler S J, et al. Sr2+/Ca2+ and 44Ca/40Ca fractionation during inorganic calcite formation: II. Ca isotopes. Geochim Cosmochim Acta, 2008, 72: 3733–3745
Allemand D, Ferrier-Pagès C, Furla P, et al. Biomineralisation in reef-building corals: From molecular mechanisms to environmental control. C R Palevol, 2004, 3: 453–467
Gussone N, Böhm F, Eisenhauer A, et al. Calcium isotope fractionation in calcite and aragonite. Geochim Cosmochim Acta, 2005, 69: 4485–4494
Gussone N, Nehrke G, Teichert B M A. Calcium isotope fractionation in ikaite and vaterite. Chem Geol, 2011, 285: 194–202
Henderson G M, Chu N C, Bayon G, et al. δ 44/42Ca in gas hydrates, porewaters and authigenic carbonates from Niger Delta sediments. Geochim Cosmochim Acta, 2006, 70, doi: 10.1016/j.gca.06.493
Teichert B M A, Gussone N, Eisenhauer A. Processes influencing the Ca isotopes in porewaters of the Cascadia margin (ODP Leg 204). Eur Geosci Union, 2006, 8: 08875
Lemarchand D, Wasserburg G J, Papanastassiou D A. Rate-controlled calcium isotope fractionation in synthetic calcite. Geochim Cosmochim Acta, 2004, 68: 4665–4678
Marriott C S, Henderson G M, Belshaw N S, et al. Temperature dependence of δ 7Li, δ 44Ca and Li/Ca during growth of calcium carbonate. Earth Planet Sci Lett, 2004, 222: 615–624
Berner U, Faber E. Hydrocarbon gases in surface sediments of the South China Sea. In: Jin X, Kudrass H R, Pautot G, eds. Marine Geology and Geophysics of the South China Sea. Beijing: China Ocean Press, 1992. 199–211
Wu S G, Liu Z, Wang W Y, et al. Late Cenozoic neotectonics in the Dongsha Islands region and its responds to collusion between Chinese continental margin and Luzon (in Chinese). Oceanol Limnol Sin, 2004, 35: 481–490
Chen Z, Yan W, Chen M H, et al. Discovery of seep carbonate nodules as new evidence for gas venting on the northern continental slope of South China Sea. Chin Sci Bull, 2006, 51: 1228–1237
Yao B C. The gas hydrate in the South China Sea (in Chinese). J Trop Ocea, 2001, 20: 20–28
Zhu Y H, Huang Y Y, Matsumoto R, et al. Geochemical and stable isotopic compositions of pore fluids and authigenic siderite concretions from site 1146, ODP Leg 184: Implication for gas hydrate. In: Prell W L, Wang P, Rea D K, et al., eds. Proceedings of the ODP Scientific Results, 184, 2002. 1–15
Wu S G, Zhang G X, Huang Y Y, et al. Gas hydrate occurrence on the continental slope of the northern South China Sea (in Chinese). Mar Petrol Geol, 2005, 22: 403–412
Pu X Q, Zhong S J, Yu W Q, et al. Authigenic sulfide minerals and their suflur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation. Chin Sci Bull, 2007, 52: 401–407
Yang T, Jiang S Y, Ge L, et al. Geochemical characteristics of pore water in shallow sediments from Shenhu area of South China Sea and their significance for gas hydrate occurrence. Chin Sci Bull, 2010, 55: 752–760
Ge L, Jiang S Y, Yang T, et al. Glycerol ether biomarkers and their carbon isotopic compositions in a cold seep carbonate chimney from the Shenhu area, northern South China Sea. Chin Sci Bull, 2011, 56: 1700–1707
McDonnell S L, Max M D, Cherkis N Z, et al. Tectono-sedimentary controls on the likelihood of gas hydrate occurrence near Taiwan. Mar Petrol Geol, 2000, 17: 929–936
Schnurle P, Liu C S, Hsiuan T H, et al. Characteristics of gas hydrate and free gas offshore southwestern Taiwan from a combined MCS/OBS data analysis. Mar Geophy Res, 2004, 25: 157–180
Zhang M, Sun X M, Xu L, et al. Nano-sized graphitic carbon in authigenic tube pyrites from offshore southwest Taiwan, South China Sea, and its implication for tracing gas hydrate. Chin Sci Bull, 2011, 56: 2037–2043
Chen D F, Huang Y Y, Yuan X L, et al. Seep carbonates and preserved methane oxidizing archaea and sulfate reducing bacteria fossils suggest recent gas venting on the seafloor in the Northeastern South China Sea. Mar Petrol Geol, 2005, 22: 613–621
Huang C J, Zhou D, Sun Z, et al. Deep crustal structure of Baiyun Sag, northern South China Sea revealed from deep seismic reflection profile. Chin Sci Bull, 2005, 50: 1131–1138
Lu H F, Liu J, Chen F, et al. Mineralogy and stable isotopic composition of authigenic carbonates in bottom sediments in the offshore area of southwest Taiwan, South China Sea: Evidence for gas hydrate occurrence (in Chinese). Earth Sci Front, 2005, 12: 268–276
Huang C Y, Chen C W, Zhao M X, et al. Geological study of active cold seeps in the syn-collision accretionary prism Kaoping slope off SW Taiwan. Terretrial Atmos Oceanic Sci, 2006, 17: 679–702
Arning E T, Luückge A, Breuer C, et al. Genesis of phosphorite crusts off Peru. Mar Geol, 2009, 262: 68–81
Heuser A, Eisenhauer A, Gussone N, et al. Measurement of calcium isotopes (δ 44Ca) using a multicollector TIMS technique. Int J Mass Spectrom, 2002, 220: 385–399
Compston W, Oversby V M. Lead isotopic analysis using a double spike. J Geophys Res, 1969, 74: 4338–4348
Rosenbaum J, Shenppard S M F. An isotopic study of siderites, dolomites and ankerites at high temperatures. Geochim Cosmochim Acta, 1986, 50: 1147–1150
Bayon G, Pierre C, Etoubleau J, et al. Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Mar Geol, 2007, 241: 93–109
Magalhães V H. Authigenic Carbonates and Fluid Escape Structures in the Gulf of Cadiz. Aveiro: University of Aveiro, 2007. 1–373
Cavagna S, Clari P, Martire L. The role of bacteria in the formation of cold seep carbonates: Geological evidence from Monfer rato (Tertiary, NW Italy). Sediment Geol, 1999, l26: 253–270
Meister P, McKenzie J A, Vasconcelos C, et al. Dolomite formation in the dynamic deep biosphere, results from the Peru Margin, OPD Leg 201. Sedimentology, 2007, 54: 1007–1032
Takeuchi R, Machiyama H, Matsumoto R. Methane seep, chemosynthetic communities, and carbonate crusts on the Kuroshima Knoll, offshore Ryukyu islands. In: Proceedings of the Fourth International Conference on Gas Hydrate. Yokohama, 2002, 97–101
Lim D, Choi J, Xu Z, et al. Methane-derived authigenic carbonates from the Ulleung basin sediments, East Sea of Korea. Cont Shelf Res, 2009, 29: 1588–1596
Feng D, Chen D F, Peckmann J, et al. Authigenic carbonates from methane seeps of the northern Congo fan: Microbial formation mechanism. Mar Petrol Geol, 2009, 27: 748–756
DePaolo D J. Calcium isotopic variations produced by biological, kinetic, radiogenic and nucleosynthetic processes. Rev Mineral Geochem, 2004, 255–288
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Wang, S., Yan, W., Magalhães, H.V. et al. Calcium isotope fractionation and its controlling factors over authigenic carbonates in the cold seeps of the northern South China Sea. Chin. Sci. Bull. 57, 1325–1332 (2012). https://doi.org/10.1007/s11434-012-4990-9
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DOI: https://doi.org/10.1007/s11434-012-4990-9