Methane-Rich Plumes in the Suruga Trough (Japan) and Their Carbon Isotopic Characterization
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ELSEVIER Earth and Planetary Science Letters 160 (1998) 97±105 Methane-rich plumes in the Suruga Trough (Japan) and their carbon isotopic characterization U. Tsunogai a,Ł,J.Ishibashia, H. Wakita a,1,T.Gamob a Laboratory for Earthquake Chemistry, Faculty of Science, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan b Ocean Research Institute, University of Tokyo, Minami-dai, Nakano-ku, Tokyo 164, Japan Received 18 August 1997; accepted 27 April 1998 Abstract 13 The carbon isotopic compositions (Ž CCH4) of the methane-rich buoyant plumes, observed in the oxygenated hemipelagic sea waters of the Suruga Trough, Japan, are discussed in relation to their sources. During a survey made in May 1996, two layers of anomalous methane-rich plumes, both of which centred at the same station about a few tens of kilometres off the coast, were found in the Suruga Trough. The deeper plume (ca. 2100 m depth, with a maximum methane concentration of 13 nmol=kg) had already been detected by a previous survey in 1986 at the same station, whereas the shallower plume (ca. 1000 m depth, with a maximum methane concentration of 10 nmol=kg) was newly discovered. 13 The estimated end-member Ž CCH4 value (59 š 3½ PDB) for the deeper plume suggests a microbial origin of the methane, probably derived from some shallow (surface) layer of sediment. The plume could be supplied from a continuous cold ¯uid seepage on the sea ¯oor of the Suruga Trough. On the other hand, the shallower plume is characterized by more 13 13 C-enriched end-member methane (Ž CCH4 D38 š 2½ PDB), presumably produced by the thermogenic degradation of organic matter. Since thermogenic methane should originate from a deeper part (more than 1000 m) of the sedimentary layer, it is unlikely that the thermogenic methane reaches the sea water by normal transport processes. The shallower plume may be a result of some sudden, catastrophic event on the sea ¯oor, such as earthquakes. 1998 Elsevier Science B.V. All rights reserved. Keywords: methane; carbon; isotopes; Suruga Bay; earthquakes 1. Introduction front of the Philippine sea plate, subducting beneath the plates of the Japanese Islands (Fig. 1). During a 1.1. Suruga Trough and anomalous methane hydrographic survey in November 1986, anomalous enrichment methane enrichment (a methane plume) was detected in the bottom sea water at 34ë400N, 138ë360E (station The Suruga Trough, which is the northern exten- 18 in Fig. 1) in the Suruga Trough (Fig. 2). Methane sion of the Nankai Trough, is the northern convergent enrichment in sea water, together with heat, Fe, Mn, Ł Corresponding author. Present address: Department of Environmental Physics and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8502, Japan. Tel.: C81 (45) 924-5555; Fax: C81 (45) 924-5554; E-mail: [email protected] 1 Present address: Faculty of Intercultural Studies, Gakushuin Women's College, 3-20-1 Toyama, Shinjuku-ku, Tokyo 162-8650, Japan. 0012-821X/98/$19.00 1998 Elsevier Science B.V. All rights reserved. PII S0012-821X(98)00075-2 98 U. Tsunogai et al. / Earth and Planetary Science Letters 160 (1998) 97±105 Fig. 1. Map showing the locations of sampling stations (circle D November, 1986 and square D 29 May, 1996), bottom topography of the Suruga Trough, and the epicentre of a magnitude 4.7 earthquake on 27 May, 1996 (star). Sectional contour map of methane concentration in Fig. 3 is constructed along the central axis of the trough (line A±B). and 3He enrichment, are well known indicators for methane (maximum concentration: ca. 200 nmol=kg) sea-¯oor hydrothermal activity, because hydrother- on the southern slope of Funka Bay, Japan, at a depth mal ¯uids are highly enriched in these compounds of about 50 m. relative to background sea water (e.g. [1]). However, In order to study the geochemical cycle of in spite of an observed high methane concentration methane in the ocean, we must clarify the geo- of more than 15 nmol=kg, this plume did not show chemical, geological, geophysical, and hydrologi- any of the other hydrothermal signatures. The plume, cal characteristics of sources of such methane-rich therefore, may be caused by some cold venting ¯uids plumes. Thus on 29 May, 1996, we revisited the Su- other than hydrothermal ¯uids, a possibility indi- ruga Trough during the KT96-8 Expedition of R=V cated also by later discoveries of numerous methane- Tansei Maru (University of Tokyo) in order to bet- rich cold ¯uid seepage sites at the adjacent Nankai ter understand the origins of methane in the plume Trough (e.g. [2]). observed in 1986. Observations of such anomalous, probably non- hydrothermal plumes in sea water have also been 1.2. Stable carbon isotopic composition of methane reported elsewhere. At a depth of several hundred metres in the Northwest Caribbean Sea, Brooks [3] The stable carbon isotopic composition of found methane-rich plumes (at a maximum concen- methane offers useful information for discerning the tration of more than 100 nmol=kg), possibly supplied origin of methane. The methane emitted by sea- from the Jamaica Ridge. Horibe et al. [4] have found ¯oor hydrothermal systems in sediment-poor envi- a methane-rich plume (at a maximum concentra- ronments is extremely enriched in 13C with a carbon 13 tion of ca. 3 nmol=kg) at a depth of approximately isotopic ratio (Ž CCH4) ranging from 25 to 8 3000 m in an open-ocean water column in the Mari- ½PDB, indicating an inorganic origin [7,8]. On the ana Trough, western Paci®c, of unknown origin [5]. other hand, organic-rich marine sediments produce Watanabe et al. [6] have found a large source of extremely 13C-depleted methane with a Ž13Cof50 U. Tsunogai et al. / Earth and Planetary Science Letters 160 (1998) 97±105 99 residual methane [17]) is suf®ciently slow relative to the diffusion of methane in sea water, we can study the origin of methane in methane-rich plumes by 13 Ž CCH4 measurements. Except for some recent works [18±21], how- ever, previous studies of the marine geochemistry of methane have lacked carbon isotopic data because they have dealt with oxygenated sea water which has 13 insuf®cient CH4 for traditional Ž CCH4 determina- tion. New isotope-ratio-monitoring gas chromatog- raphy=mass spectrometry (irm±GC=MS) systems re- quire much smaller samples for isotopic analyses (e.g. [22]). We have developed an analytical sys- tem which is capable of on-line simultaneous anal- yses of concentration and Ž13C values of low-level methane in sea water using irm±GC=MS, similar to the method developed by Popp et al. [19]. 2. Experiment Water was sampled on 29 May 1996 at stations 10, 11, 18, 19, and 20 (Fig. 1), which are located al- Fig. 2. Vertical CH4 pro®les at station 18 in the Suruga Trough most on the axis (deepest line) of the Suruga Trough. measured in 1986 (circle) and 1996 (square). The samples were collected with a 12-port Rosette multisampler (10-l Niskin bottles) attached to a Neil to 110½ PDB, as a result of microbial production Brown Mark III CTD system with a sonar pinger. Se- in the anoxic sedimentary layer (e.g. [9]). Methane- rial hydrographic measurements were made with the 13 rich cold seep ¯uids show similar Ž CCH4 values CTD system. The sampling was focused on depths as marine sediments, which are the main source of below 1000 m, because the methane plume was pre- methane in the ¯uids [10±13]. Sediment-rich hy- viously observed at depths below 1500 m (Fig. 2). drothermal systems supply methane with intermedi- Discrete sample analyses of salinity and dissolved ate Ž13C values, ranging from 30 to 50½ PDB oxygen were made using a salinometer (Autolab [7,14], due to thermogenic degradation of organic Industries) and the standard Winkler method. matter in the sediment. Methane in deeply buried ma- For CH4 content and isotopic analysis, a water rine sediments sometimes show similar Ž13Cvalues sample was slowly transferred into a ca. 530-ml as sediment-rich hydrothermal ¯uids for two possi- glass vial, which contained a Te¯on coated magnetic ble reasons: (1) thermal degradation of organic mat- stirrer of 5 cm length. After an approximately 2-fold ter under the in¯uence of elevated temperature (e.g. volume over¯ow to prevent air contamination, 3 [11,15]); (2) microbial production using extremely ml of saturated HgCl2 solution (6%wt) was slowly 13 C-enriched CO2 [16]. In the Nankai Trough, the added as a preservative. The vial was then sealed southern extension of the Suruga Trough, one may with a grey butyl rubber stopper and stored in the ®nd such 13C-enriched thermogenic methane in the dark at room temperature until analysis. In order to sedimentary layer about 1000 m below the sea ¯oor prevent seal breakage due to increases in volume [15]. If we can assume that some secondary alter- caused by temperature increases after sealing, about 13 nation of Ž CCH4 in the seawater column (i.e. bio- 1 ml of sample in each bottle was discarded without logical consumption in oxygenated seawater which contact with air, using a needle syringe through the 13 may result in enhancement of Ž CCH4 values of rubber stopper within an hour after sealing. 100 U. Tsunogai et al. / Earth and Planetary Science Letters 160 (1998) 97±105 The analytical system consisted sequentially of Table 1 a He-sparging bottle of water (80 ml=min carrier Observed concentration (CH4 in nmol=kg) and carbon isotopic Ž13 gas ¯ow), a CO2-trapping port with alkaline so- composition ( C in ½ PDB) of methane together with depth (D), water temperature (T), salinity (S) and oxygen concentration lution, a gas dryer (Na®on tubing), a liquid N2 (O ) temperature trap (150-mm-long column packed with 2 13 Porapak-Q), and a liquid N2 temperature cryofocus- D (m) T (ëC) S (PSU) O2 (ml=l) CH4 Ž C ing (5-mm-long column packed Porapak-Q) [13,19].