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1 The Sea Journal of the Korean Society of Oceanography Vol. 12, No. 3, pp , August 2007 [Note] Membrane Inlet Mass Spectrometer (MIMS) ts } r š r } ld 1 * x 1 rs 1 qt 2 x 3 1 x ff, 2, 3 p x / mn Dissolved Methane Measurements in Seawater and Sediment Porewater Using Membrane Inlet Mass Spectrometer (MIMS) System SOONMO AN *, JINAM KWON, JEAHYUN LIM, YUNJUNG PARK 2 AND DONG-JIN KANG 3 1 Division of Earth Environmental System/Marine Science Major, Pusan National University, Busan , Korea 2 Department of microbiology, Pukyung National University, Busan Korea 3 School of Earth & Environmental Sciences/Research Institute of Oceanography, Seoul National University, Seoul , Korea MIMS edšp k~ e p ns d r r pn l m, l l m r l sq ns ˆ r n l. rp r p Žk o l, l k p ˆ l k~ e t mp p MIMS edšp r m. r p ns ~p q p m. rp t m p 0.13~0.9% r m. p edšp pn l k p p ns ˆ r, ns ˆp p rp n sn ppp k pl. MIMS systemp pn l, p ns ˆ p p l pl. e l MIMS edšp inlet p ˆ ˆ rq l r pl n s ˆp r pl. Membrane inlet mass spectrometer (MIMS) has been used to accurately quantify dissolved gases in liquid samples. In this study, the MIMS system was applied to measure dissolved methane in seawater and sediment porewater. To evaluate the accuracy of the measurement, liquid samples saturated with different methane partial pressure were prepared and the methane concentrations were quantified with the MIMS system. The measured values correspond well with the expected values calculated from solubility constants. The standard error of the measurements were 0.13~0.9% of the mean values. The distribution of dissolved methane concentration in seawater of the South Sea of Korea revealed that the physical parameters primarily control the methane concentration in sea water. The MIMS system was effective to resolve the small dissolved methane difference among water masses. The probe type inlet in MIMS system was proven to be effective to measure porewater methane concentration. Keywords: Methane, MIMS, Dissolved Gas, Porewater, Methane Hydrate, Probe o, ol r oo (IPCC) v m p p ˆ pp m. v m r e mp f, me ~ (CO 2, CH 4, N 2O, CFCs, O 3, v )p o, p, r p ~p ˆl l l ep kv p (Cicerone and Oremland, 1988; Middleburg et al., 2002; Bange, 2006). p tl ˆ *Corresponding author: sman@pusan.ac.kr d(ch 4) CO 2l kp rp, me p p CO 2 l l k 20 r pp, r~ me p 15% r k r p (Cicerone and Oremland, 1988;, 1995). t CH 4p p r v r 2003 l 1790 ppbp, l v pp 1990 p k 5 ppb r p (WMO, 2005). rv rp CH 4p p l 535 Tg(CH 4)l pt 70% porp op 30% ql rp opl p k r p (, 2002). kp ˆp o(source)p l v pp kp v k (5~50 Tg; Cicerone and Oremland, 1988; Middleburg et al., 244

2 Membrane Inlet Mass Spectrometer (MIMS) edšp pn r ns ˆp r ). k tl lkvlp ˆ l tn p k v pp, q, vl e r l l n s p (Jones and Mullholland, 1998; Middleburg et al., 2002). v m l l ˆp t n k, l v qop ˆ (methane hydrate) p t p k r,, p m p l ~ ˆp r r p n r. ˆ p l v qop p tn k, v m rl kp p(positive feedback)p qn l, v m eˆ p qqrp o v vr m (Damm et al., 2005). v v m v l m kv, p p ˆp ˆp d ˆ tl o, v ˆl p me ƒr, v m p. v m rp ˆ qo ˆ kp ˆ l l l pl, ns ˆp ˆp r r n p kv p. p rp ns ˆp rp p lv, ~w ns ˆp ˆ d ~ ˆ m pp d r p. ns ˆp d l t d pd(headspace) pn, purge-trappingp pn, equilibrator pn p n l (Middleburg et al., 2002; Seifert et al., 1999). p ˆp flame ionization detector(fid) q d Š photo-acoustic infrared detector(middleburg et al., 2002)l r. tp ˆ n p pl, e p mm p r, r l n (detector)p p r p l, p rp r m rp p. d pd purge-trappingp n e p } l e p k, ns d l p r l lv (An and Joye, 1997). rl n e p k 50~600 ml p p r ƒ rp e p l npp (Middleburg et al., 2002). tp ns d r r o l v edšp Membrane inlet mass spectrometer (MIMS) l l kl pn p (Kana et al., 1994; An et al., 2001; Vrana, 2005; Sheppard et al., 2005; Tortell, 2005; Demeestere et al., 2007). MIMS system l e p pl v p l, k~e l kp ns d VOC (volatile organic carbon), quadrapole v (mass spectrometer) pn l r (Kana et al., 1994; An et al., 2001). k~e r e p e n l v ˆ ov l p k~ e ns d. d d r v l op l r l ns dp l p e p mm p o}rp, m l l d pp pp pn p f rp r p p p (Kana et al., 1994). MIMS system p rl n e p kp r, p e p l rp r ns d rl l qrp v p. l MIMS systemp l, tl q rp MIMS system(underwater membrane introduction/quadrupole mass filter system; Short et al., 2005)p lp, membrane inlet system p l, r p p ns d p (Sheppard et al., 2005; Hartnett and Seitzinger, 2003) l l MIMS systemp pn l, ns ˆ dp p kk m. l m m ˆp ks l eˆ t nkp mp, pp rp MIMS systemp pn ns ˆ rp r p k k k. er rp m lk l pl ns ˆ r l, p l ns ˆp k. pm ˆ (probe) ˆp inlet system p pn l r p ns ˆ r m. m MIMS system l l n MIMS systemp r e p s l 2 v ns ~ edš(membrane inlet)p n l (Fig. 1). k~ e p n v ˆl p, 0.75 mm( 0.15 mm) p 20 mmp e pn l ns d l (Fig. 1A). k~ e r pn l d p d (n : 0.75 mm, 0.5 mm)p op, d p d p v p p T-q ƒ kl e m pl v k~e e v e p n s ~. ns ~ k~e d p d p r v. T-q ƒ kl ns ~ r o k~v p, p r o quadrapole v op (Kana et al., 1994; An et al., 2001). w edšp r l p p ns ˆ r o n l. p edšl d p d l e q e p rl mp, rp e p kyp d p d m v edš l m (Fig. 1B). r~ v p 2 mm r mp, p r l vr p l, p ns ~ e l v p ov MIMS system l ˆp r m. ns d rl Pfeiffer vacuump gas analyzer(pfeiffer QMA 200) pn l. pm dp v : r (massto-charge ratio; m/z) t r d( ˆ m/z=15, m/z=32, k m/z=40) p v :r ˆ m. ˆ d(ch 4)p e (m/z=16)l pm (O m/z=16)l p (interference) p sq l, CH 3 +(m/z=15)p kp r m, ˆ CH 3 + sp p k r p (Benstead and Lloyd, 1994; Sheppard et al., 2005). ˆ e p k l t nk(20 o C, 0 pptm 20 o C, 30 ppt) ˆ l.

246 k Ë v Ëpq Ë orë v Fig. 1. Inlet diagram of MIMS system showing membrane inlet for liquid samples (A), and porewater sample (B). h o m ko ~o l m m s l nkp e t m (Table 1).

3 246 k Ë v Ëpq Ë orë v Fig. 1. Inlet diagram of MIMS system showing membrane inlet for liquid samples (A), and porewater sample (B). h o m ko ~o l m m s l nkp e t m (Table 1). m 0 ppt p nkp v 2 v m (20 o Cm 30 o C) ov m sl 48e p l, l p m (S 0T 20, S 0T 30). nk p m k e 30 ml o n l lr. v m p 0, p 35 ppt t l 48e p l e p p headspace lp n l }o. p r t pn l 10 mlp headspace l, 23 ppm p t ˆ(23 ppm CH 4, N 2 balanced) tp (S 0T 20C, S 0T 30C, S 35T 20C, S 35T 30C, S 35T 20CH, S 35T 30CH), (S 35T 20A, S 35T 30A) 30 C ov m o }o l. p k~ e 20 Cm o sl 48e l, headspace p ˆ p m. pm l k~ l p sq p ns dp kp tp o l, d k 20 (bubbling) eˆ pl om p } l, l p sq ns dp m k (S 35T 20CH, S 35T 30CH). m e, p 95% p p ns d l r lpp k d k k pl. r~ 10 v s p t e t lp, s p e 3 j l r l (Table 1). m ~o o ks ˆk s t (34~34.30 N, 128~129 E)p 6 s rr(station 1~6)l e ns ˆ rp p lr (Fig. 2). s rrp ep 30~80 m r Niskin-rosette } pn l 5~10 m p }, m k e 30 ml o n l p Table 1. Saturated water samples in various salinity and temperature for dissolved methane analysis. Sample ID Salinity (ppt) Temperature ( o C) Headspace (10 ml) Degassing with Helium S 0T none n S 0T none n S 0T 20C ppm CH 4 n S 0T 30C ppm CH 4 n S 35T 20C ppm CH 4 n S 35T 20CH ppm CH 4 y S 35T 20A Air n S 35T 30C ppm CH 4 n S 35T 30CH ppm CH 4 y S 35T 30A Air n Fig. 2. Study sites for vertical profiles of dissolved methane.

4 Membrane Inlet Mass Spectrometer (MIMS) edšp pn r ns ˆp r 247 ZnCl 2(vol/vol 50%, 0.1 ml)p l p p rve m. e e e rm MIMS systemp pn l r m. ˆn ko ~o o ˆ (probe) ˆ lv membrane inlet system p pn l r ns ˆp rp p lr (Fig. 1B). p l v 10 cm, p 25 cmp r l } e e rm q m l, rp p lr (Fig. 1B). r p ˆ e p t nk(20 o C, 0 pptm 20 o C, 30 ppt) ˆ l. ko ~o 10 v s p ns e p ˆ 2~3.4 nmp o m (Table 2). tl eˆ 4 v e t ˆ 1.9 ppm r(bange et al., 1994) m m r n (Bunsen solubility coefficient; Yamamoto et al., 1976) f ~ p p m (Fig. 3). v k tl eˆ S 0T 20, S 0T 30 p m p m (Fig. 3). ˆl tpeˆ, r e (S 35T 20A, S 35T 30A)l r p l p ˆ, p e headspacep k p k kr p. rl t m 0.004~0.027 nm e p CH 4 p 0.13~0.9% n r rp m (Table 2). e l 23 ppm t ˆ ~ eˆ nkl l eˆ nkl ns ˆ kk o l, e p ˆ e k e m ˆ l (Fig. 4). p m 20 Cm o 30 o C, kl nk (S 0T 20, S 0T 30) tp k e l l l p p l ˆ e (excess methane signal) v p v m (Fig. 4). Headspace }n e (S 35T 20A, S 35T 30A)p Fig. 3. Measured and calculated methane concentrations in saturated water samples of various temperature and salinity conditions. See Table 1. for the saturation conditions. n pl ˆp llp, CH 4:Arp pp S 0T 20, S 0T 30m p p m. 23 ppm t ˆ ~ headspacel tp e p n n p k m. n t ~l ˆ v d sq v tn d p k~ e headspace lp p. t ~ tp e l k 82%, 92% m. n rp d l ns d r pl, t ˆ d tp e (S 35T 20CH)l v k t ˆ d tp e m p o k, m, p 23 ppm t ˆ dl k sq v kk, p mpp k pl. k m ˆp p l k - ˆ ep pl ˆp 2.4~3.3 nml p. e l 23 ppm p v t d p Table 2. Methane and argon signal (mbar) and concentration (nm) in saturated water samples of various salinity and temperature. See Table 1. for the saturation conditions. Sample ID Methane Signal (mbar) Argon Signal Methane Concentration (nm) Excess Methane Average SE (mbar) mean 1 SE Signal (mbar) S 0T S 0T S 0T 20C S 0T 30C S 35T 20C S 35T 20CH S 35T 20A S 35T 30C S 35T 30CH S 35T 30A

5 248 k Ë v Ëpq Ë orë v Fig. 4. Argon versus methane signal of MIMS measurement in saturated water samples. See Table 1. for the saturation conditions. n mp, v t ˆ d pn l op e p ee, s r rp p. ~o o p lp ns ˆ 2~3 nmp o m. s p o lk p ns ˆ o(4~150 nm; Middleburg et al., 2002)l p p. v l ˆp p p p (Jones and Mullholland, 1998), s vlp lkp p m p vr rp vlp k r rp p p mp p, ovl n rr l rr p p m. e ns ˆp, l p p p 40~60 m v pr p p mk el 60 m p l kv p m. p p r rp lt rp rrp rr 5p el ns ˆp m, m Fig. 5l ˆ l. p rrl el m m p v e k 50~60 m l o mk p tep (Fig. 5). ns ˆp p p r p q m l, l r pr p p, mk k l Fig. 5. Depth profile of dissolved methane concentration in station 5. Water temperature and salinity were also shown together. kv p ˆ. p rp p ns ~p n op r op l n rp np rp npl p sr. rp npp ~p n r m m p n rp qn l p ~l n r. t ~p n m m p p ~p n. p t ml p m p m l p m ˆ. n s ˆp nl mp 1 p m 1 ppt l k 4 r n l m p t. m n s ˆ p (Fig. 6), r rp l ltl p vlp ns ˆp rp npl p p rp sr p p p r pp, MIMS systemp pn ns ˆ rp n p l qp p p rp n p. ˆn ko r m, k r p k 1cml kp mbar p, kp 1%l p l, p l (Fig. 7). r o 1 cml ˆ k 5 nmpl r - l 8 nm r v m, p r pl

6 Membrane Inlet Mass Spectrometer (MIMS) edšp pn r ns ˆp r 249 Fig. 6. Relation between water temperature and dissolved methane concentration measured by MIMS. Fig. 7. Dissolved methane concentration (nm) and oxygen signal strength (mbar) during MIMS probe measurement of sediment porewater. Negative depth denotes water above the sediment surface. v l 1 cm p l 12 nm n ˆ. r p 3.5 cml perp v m pm l ns ˆp 9 nm r mp 5 cm v p ov l. 3.5 cm pl v ˆp opp q p lp, r p p sq l p p lp p p (Aller 1980). MIMS probe pn ˆp rp ~ ( ) k Šk l l r l (Sheppard et al., 2005), q l 1500~2500 nm n p p ˆ l. e } r l r q lp, p ˆp t n o(source)p l v pl(kelly et al., 1995; Middelburg et al., 2002) r pl p mp, l 2~3 p l ~. p rp p ˆ p r(methanogenesis)p kp t rp r p m o r prp, m o r j p pl pl k r p (Capone and Kiene, 1988). s l r r pl ˆp l p l, tl lp p p. ˆ ˆp MIMS systemp pn l, r ns ˆp rp e mp, r Žk p rl m p t r npp Žk pp p. p ns ˆ r s p p p ˆv r o r p f p rp pp p. r ns ˆp p ˆ lk l ˆp l p p rp ˆp k(flux)l l m p v, tn r r p (Frans- Jaco et al. 1998). kh MIMS systemp rl n e p kp r, pe p l rp ns d rl l qrp v pl, l l kl pn p. l l l m m m s ˆp ks l eˆ t nkp mp, p p rp MIMS systemp p n ns ˆ rp sd p pl. p m l, lk, r p ˆ r m. k m, m, ˆ dp k s l eˆ ns e rl ns ˆ s l n f m q p p m. rl t m 0.004~0.027 nm k~ e p ns ˆ p 0.13~0.9 % sd n r r rp m o p lp ns ˆ 2~3 nmp o m. e ns ˆp, l p p p 40~60 m v pr p p 60 m p l kv p m. p rp n p l q p p p MIMS systemp rp n pp k pl. r l p ns ˆ d p, r o 1 cm l ˆ k 5 nmpl r - l 8 nm r v m, p r pl v l 1 cm p l 12 nm n p ˆ. r p ns ˆp r p f r l tp

7 250 k Ë v Ëpq Ë orë v ˆ kl m p l npp p l. m p p qo r l (2 )l p l l p. s p p te p e oo. y, kvlp tep ˆp qt r l. v v, 23(3): , me ~p v m p., 13(4): Aller, RC., Relationships of Tube-dwelling Benthos with sediment and overlying water chemistry. In Marine Benthic Dynamics, Tenore, K.R. and Coull, B.C. (eds.) Univ. S. Carolina Press An, S. and Joye, S.B., An improved gas chromatographic method for measuring nitrogen, oxygen, argon and methane in gas or liquid samples. Marine Chemistry, 59(1-2): An, S., Gardner, W.S. and Kana, T.M., Simultaneous measurement of denitrification and nitrogen fixation using isotope pairing with membrane inlet mass spectrometer (MIMS) analysis. App. Env. Micro., 67(3): Bange, H.W., Nitrous oxide and methane in European coastal waters. Estuarine Coastal and Shelf Science, 70(3): Bange, H.W., Bartell UH, Rapsomanikis S. & Andreae MO Methane in the Baltic and North Seas and a reassessment of the marine emissions of methane. Global Biogeoch. Cycles 8: Benstead, J.,Lloyd D., Direct mass spectrometric measurement of gases in peat cores. FEMS Microbiology Ecology 13(3): Capone, D.G. and Kiene, R.P., Comparison of microbial dynamics in marine and freshwater sediments: Contrast in anaerobic carbon metabolism. Limnol. Oceanogr., 33: Cicerone, R.J., Oremland, R.S., Biogeochemical aspects of atmosphere methane. Global Biogeoch. Cyclces, 2: Damm, A. Mackensen, Budéus, G., Faber, E. and Hanfland, C., Pathways of methane in seawater: plume spreading in an Arctic shelf environment (SW-Spitsbergen). Continental Shelf Research, 25: Demeestere, K., J. Dewulf, B.D. Witte and H.V. Langenhove, Sample preparation for the analysis of volatile organic compounds in air and water matrices. Journal of Chromatography, 1153(1-2): Frans-Jaco WA, van der Nat, J. Middelburg Seasonal variation in methane oxidation by the rhizosphere of Phragmites australis and Scirpus lacustris Aquatic Botany, 61(2): Hartnett, H.E., Seitzinger, S.P., High-resolution nitrogen gas profiles in sediment porewaters using a new membrane probe for membrane-inlet mass spectrometry. Marine Chemistry, 83: Jones and Mullholland, Influence of drainage basin topography and elevation on carbon dioxide and methane supersaturation of stream water. Biogeochemistry, 40: Kana, T.M., Darkangelo, C., Hunt M.D., Oldham, J.B., Bennett, G.E., Cornwell, J.C., Membrane inlet mass spectrometer for rapid high-precision determination of N 2, O 2, and Ar in environmental water samples. Anal. Chem., 66(23): Kelley, C.A., Martens, C.S. and Ussler, III W., Methane dynamics across a tidally flooded riverbank margin. Limnology and Oceanography, 40: Middelburg, J., Nieuwenhuize, Iversen, N., Høgh, N., H. De Wilde, Helder, W., Seifert, R. and Christof, O., Methane distribution in European tidal estuaries. Biogeochemistry, 59: Seifert, R., Delling, N., Richnow, H.H., Kempe, S., Hefter, J., Michaelis, W., Ethylene and methane in the upper water column of the subtropical Atlantic. Biogeochemistry, 44(1): Sheppard, S.K., Gray, N., Head, I.M., Lloyd, D., The impact of sludge amendment on gas dynamics in an upland soil: monitored by membrane inlet mass spectrometry. Bioresource Technology, 96: Short, R.T., Fries, D.P., Kerr, M.L., Lembke, C.E., Underwater Mass Spectrometers for in situ chemical analysis of the hydrosphere. J. Am. Soc. Mass Spectrom., 12: Tortell, P.D., Dissolved gas measurements in oceanic waters made by membrane inlet mass spectrometry. Limnol. Oceanogr.: Methods, 3: Vrana, B., Mills, G.A., Allan, I.J., Dominiak, E., Svensson, K., Knutsson, J., Morrison, G., Greenwood, R., Passive sampling techniques for monitoring pollutants in water. Trends in Analytical Chemistry, 24(10): WMO(World Meteorological Organization), WMO WDCGG data summary. WDCGG No.29, WMO, 85pp. Yamamoto S., Alcauskas, JB, Crozier, TE., 1976, Solubility of Methane in distilled Water and Seawater. Journal of Chemical Engineering Data. 21(1): o 16p o r o 20p r }ˆ voo:

44(3)-16.fm

44(3)-16.fm Korean Chem. Eng. Res., Vol. 44, No. 3, June, 2006, pp. 270-276 지능형헬스케어욕조시스템개발을위한온수온도변화 r ~r l o l l e l 561-756 r rte v v 1 664-14 (2006 3o 9p r, 2006 6o 20p }ˆ) Change of the Warm Water emperature for