The distribution of phenylalkanes in the modern sediment associated with gas hydrate from the Gulf o

Acta Oceanologica Sinica 2008, Vol 27, No 6, p 71-82http://www.oceanpress.com.cnE-mail,hyxbe@263.netThe distribution of phenylalkanes in the modern sediment associatedwith gas hydrate from the gulf of MexicoWANG Cuiping, SUN Hongwen, SoNG Zhiguang, ZHANG Tao1. College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China2. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guang-zhou 510640. ChinaReceived 31 July 2007; accepted 2 November 2007AbstractPhenylalkanes with carbon numbers between 16 and 19, characterized by the main carbon-18, have been identified in the modern sediments collected from gas hydrate area from the Gulf of Mexico. The structure of pheny alkanes with four isomers for ever-y carbon number was determined by means of their mass spectra and previous studies. The distribution of the series character-ized by a low molecular mass was similar to the distribution of n-alkane, alkylcyclohexanes and alkylbenzenes in each sampleThere were differences in the distribution of the pheny alkane series between the s-1, s-4,s-7,s-9 samples and the s8, S-10 and S-1l samples. The phenylalkanes might be derived from Archaea associated with anaerobic oxidation of methane(AOM)processes in S-1, S-4,S-7 and S-9 samples according to their distribution resembled with the distribution of theextract from a type of Archaea. The distribution of alkylcyclohexanes and alkylbenzenes in S-1, S-4,S-7 and S-9 samplewas found to be similar to each other. The odd-over-even predominance of alkylcyclohexanes was seen as the input of some bacKey words: phenylalkane, gas hydrate, Gulf of Mexico1 IntroductionHartmann et al., 2000: Chalaux et al. 1995Takada et al. 1994: bouloubassi and saliotPhenylalkanes have been identified in sam- 1993; Chalaux et al., 1992; Taada et aples from natural sources, they have been usually 1992; Valls et al., 1989; Eganhouse and Kapregarded as indictors of contamination because of lan, 1988; Albaiges et al., 1987; Murray ettheir presence in surfactant formulations and thekada and Hiwatari, 1987; Egan-lack of credible precursor natural products for this中国煤化工=83: Ishiwatari et alclass. Detection and distribution of alkylbenzenes 198CNMHtilized as molecularwere reported in many coastal zones in the world markers of sewage inputs to the coastal waters overFoundation item. The Chinese academy of science under contract Nos KZCX3-SW-224 and KGCX2-SW-309Correspond数据-mal:wepphs@sohu.comWANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p. 71-8220 a( Takada and Eganhouse, 1998). In some tra and the previous reports( Eganhouse, Blumfieldcases, from geochemical samples, naturally-deet al., 1983; Ishiwatari et al., 1983 ). We tried torived phenylalkane was also identified in crude oil provide some information for the investigation of gasand sediments( Ellis et al., 1996: Ellis et al1995) and in the saturated fraction of the LowerPaleozonic and Pre-Cambrian rock( Bao and 2 Samples and experimentWang, 1996). They have been reported as indigenous components of sedimentary organic matte2. 1 Sample collectionHowever, only a very few reports have beenavailable on the detection of naturally-derived phenyduring dives of the "Johnson Sea-Linkalkane in marine sediment. Moreover, the occur-("JSL") research submarine to the Gulf of Mexicorence of phenylalkane in marine sediment associated on 18--27 May 2002, a total of nine samples werewith gas hydrate has received much less attention collected. The" Johnson Sea-Link"("JSL")re-than the archaea lipids biomarkers suchsearch submersible was used to recover sedimentane,2,6, 10, 15, 19-pentamethylicosane( PMI) from the Green Canyon ( GC) 238, 527 andIs well as the glycerol ether lipid archaeol. So, their Ew1001 site in the Gulf of Mexico where gas ven-distribution in the samples collected from gas hydrate ting and gas hydrates are in abundance. Samplingarea has not been reportedlocations were far from sewage outfalls or urban rivHedrilling leto report the phenylalkits of six sedications. Samples were collected by use of Van Veenments and carbonate sample(s-4)and compareab. Samples descriptions, location, water temtheir distributions with those obtained from the previ- peratures, and depth are listed in Table 1. In thisous studies Bao and Wang, 1996; Ellstudy, seven samples were chosen for the analysis of1996)in order to forecast the origin of these com- sedimentary organic matter. All samplespounds in sediments collected from the gas hydrate at -20 C immediately upon recovery at the sea sur-area from the Gulf of Mexico, as well as to identify face and kept frozen until analysisphenylalkane and guess their structure by mass specTable 1. Characteristics of samples in the Gulf of MexicoDescription of samplesLatitude and longitudeT℃black mud sediments onbacteria mats27°4.4453N,91°03.0470′Wwhere have smell of h sblack mud sediments on the bacteria mats mud no detail5.41901.01volcano with gas ventingblack mud sediments on the bacteria mats中国煤化工7.86517.6EW1001 S-9plack mud sediments on the bacteria mats mud 27HCNMHG 7.8olcano with gas ventingblack mud sediments on the bacteria mats27°57.937lN.90°23.7770W7.84521.6black mud sediments on the bacteria mats27°58.01l4′N23.5835′W7.84529.39WANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p. 71-82mode(70 eV). The temperature of ms detector was2. 2 Experimental procedures180C and the mass scanning ranged from m/z 50 toThe sediment samples from the Gulf of MeexIcom/z 550. Helium was the carrier gas at a 1.2 mvere air-dried in a desiccator and stirred to homoge- min flow rate. The oven temperature was initiallynize. Forty-five grams of the hoiheld at 80 C for 5 min, and then programmed at awere subjected to Soxhlet extraction for 72 h using a heating rate of 3 C/min to 290C and maintained9: 1 mixture of dichloromethane/methanol. Activated for 10mncopper turnings were used for the removal of elemental sulphur during extraction. The total extracts were 3 Results and discussiondried with anhydrous Na, so, before filtration to remove insoluble particles and copperirwinSix sediments and one carbonate sample fromfiltrate was then concentrated by rotary evaporation three different stations in gas hydrate area were ana(<30C)to a small volume of about 3 mL. Subse- lyzed for biomarkers. S-l sample was black mudquently, the total extracts were dissolved in hexane sediment, while s-4 sample is a piece of carbonateto precipitate asphaltene. The maltene fraction was associated with S-1 sediments. In the aliphaticseparated into aliphatic fraction, aromatic fraction fraction of the samples, we detected the series of al-and polar fraction by using column chromatography. kylcyclohexanes with characteristic fragment of m/zThe total extract, aliphatic, aromatic and polar frac- 83 and branched alkylbenzenes with characteristicified byfrof m/z 91 and 92. The detailsric method( Song et al., 2005). In the entire laboratory procedures, glasswares were washed first with3.1 alkylcyclohexanesdecontamination washing powder, and washed withiquid potassium dichromate by ultrasonic cleaningTheir distribution of light mass of n-alkylcyclo-then with dichloromethane by ultrasonic cleaninghexanes was different from these samples. Their dis-The aliphatic hydrocarbon fraction and aromatic tribution types about light mass had two kinds: nohydrocarbon fraction were analyzed using a Tcarbon predominance and odd carbon predominanceFinnigan trace ultra gas chromatography that was (see Fig. 1)equipped with a flame ionization detector( FID). AIn S-1 sample, the range of n-alkylcyclohexDB-5 fused silica capillary column 30 m x anes distribution was Ci4-C2 with CI as the domi0. 25 mm (i d)x0. 25 um( film thickness nant peak. In addition, a group of 2,6, 10, 15was used. The temperatures of injector and Fid de- 19-pentamethylicosenes( PMIA )containingtector are 290 and 300C, respectively. The oven unsaturated double bonds has been identified in thetemperature was initially held at 60 C for 5 min, seafloor sediments from the sample S-l in the Gulfand then programmed at a heating rate of 3 C/min of Mexico( see Fig. 1). These PMIA compoundsto 290C and maintained for 30 min. High purity N2 are n中国煤化工 and no24 on the masswas used as a carrier gas at a flow rate of 1.0 mHCN MH Gion. Their 8 C valuesmin. The aliphatic hydrocarbon fraction and aromat- are very much depleted in carbon-13 and in theic fraction were further analyzed using a HP 6890 se- range of -86.7 x to -115 5 x 10-3.Theries Il gas chromatography interfaced with a HP sampling site of S-1 is likely associated with meth5972 mass sleeve detector using electron impact ane venting( Song and Wang, 2006)WANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p 71-82S-1-A100m/z 99250030.0035.0040.00450050005500600065.0070007500Time/minm/z 83PMI0250030.0035.0040.00450050.00565.0070.0075.00Time/minm/z 8Pr Phz99中国煤化工CNMHG2500300035.00400045.0050.0055.006U0065.0U1U.007500Time/minFig. 1. Partial mass chromatograms(m/z 91)showing the distribution of phenylalkane in Ss-4 and s-10 samples from the Gulf of Mexico.WANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p. 71-82The distribution of n-alkylcyclohexanes in S-4 even carbon-number predominance ranging from Csample ranged between CI and Cs, but they pos- C2s. However the distribution of alkylcyclohexanes insessed unconspicuous odd carbon predominance in the S-8, S-10 andightlythe range. In S-7 and S-9 samples, the distribu- odd-over-even carbon-number predominance rangingtion of n-alkylcyclohexanes resembled that in S-4 from Cl to C21. These supported a substantial algalsample. In S-8,S-10 and S-ll samples, thcontribution to organic matter in all samplesdistribution of n-alkylcyclohexanes ranged in carbonThe distributions of n-alkylcyclohexanes inchain length from Ci to Cz and showed a slightly odd S-4, S-7 and S-9 samples were similar, whichto even carbon number predominanceindicated the similar mechanism of the n-alkylcyclo-From Fig. 1, the distribution of n-alkylcyclo- hexanes formation. However, the distributions of nhexanes was allied to the distribution of n-alkane in alkyleyclohexanes in the samples s-8, S-10 andcorresponding sample, which was hiher relatives-11 were different from those in other samples dueabundance of low molecular mass of n-alkylcyclohex- to severe biodegradation or petroleum contaminationanes and n-alkanes than that of heavy molecular through oil seepage in S-8, S-10 and S-11 sammass of n-alkylcyclohexanes and n-alkanes in these ples( Wang and Song, 2007)samples, respectively. In all samples, the distribuon of n-alkylcyclohexanes was almost unimodal3. 2 Identifications and distribution of penylalkaneswith a maximum peak at CI. The characteristic ofFigure 2 showed partial mass chromatographyalkylcyclohexanes distribution in the sediment sam- z91)of the aliphatic fraction of S-8 and S-1l sediples from the Gulf of Mexico was different from the ments and S-4 carbonate sample. The distribution ofcharacteristic of that with C2 main peak Connan et the penylalkanes in S-1, S-7 and s-9 samples wasal. (1986) found in oil. And the retain time of n-al- not listed, because their distribution was considerekylcyclohexanes is longer than that of the same car- similar with that in S-4 sample. Figure 3 indicatebon number of n-alkanethe mass spectra of these compounds that were characThe distribution characteristic of odd, even or no terized by a commonly existing m/z 91 base peak. Ac-Eills et al., 1996; egannism of origin. The alkylcyclohexanes can be formed house, 1986), these compounds are identified as aby decarboxylation of cyclic fatty acids of algalgroup of penylalkanes. The chromatogram suggestecbacterial origin( Schulze and Michaelis, 1990; Rubi- that phenylalkanes carbon numbers ranged from 16 tonstein and Strausz, 1979). The algal cyclic fatty 19 in the aliphatic fraction from this sampleacids have an even number of carbon atoms and theThe distribution of these phenylalkanes in thebacterial cyclic fatty acids have an odd number of caS-8, s-10 and s-1l samples was not coincidentalbon atom( mainly thermoacidophilic bacteria, Fowler with the distribution in S-1, s-4, S-7 and S-9et al., 1986). Therefore, decarboxylation of cyclic samples. In the S-8, S-10 and s-ll samples, the中国煤化工 as irregular due to thecyclohexanes with an odd to even predominance, reHCN M H Gth other peaks owing tospectively. The distribution of alkylcyclohexanes in severe biodegradation or petroleum contaminationthe S-1 sample only showed a clear odd carbothrough oil seepage in S-8, S-10 and S-1l sam-number predominance in the C1-C2, and that in ples. Figure 2 showed that the aliphatic hydrocarbonthe S-4 yi gnd S-9 samples showed odd-over- composition and distribution in S-10 and S-1176WANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p 71-82samples were clearly similar to those of mature crude carbon number range with clearly signature of severeoil and also showed high content of UCM in the higher biodegradation( Wang and Song, 2007)Cm/z 9I人人A31.0033.0035.0037.0039.0041.0043.0045.00Time/minS-8-Ali100m/z9127.00290031.0033.0035.0037.00390041.0043.004500Time/minm/z 91中国煤化工CNMHG27,0033.00350037Time/minFig. 2. The chart of distribution of alkylcyclohexanes(m/z 83)and n-akane(m/z 99)note: PMI-2, 6, 10, 15, 19-pentamethylicosaneWANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p. 71-82In S-1, S-4, S-7 and S-9 samples, long- molecular mass alkylbenzenes, with Cis the dominantchain alkylbenzenes were identified using m/z 92 peak, which was similar to the distribution n-alkanesFig. 3). Their base peaks were m/z 92, 119. In and n-alkylcyclohexanes. In addition, long-chain al-Fig. 3, the representative mass fragmentograms at kolbem/z 85, 83, 91 and 92 corresponding to the n-al- cording to the distribution of alkylbenzenes, the ori-n-alkylcyclohelong-chain alkyl- gin of long chain alkylbenzenes may be thought tobenzenes and phenylalkanes, respectively, dominaoriginate from bacterial in s-1.. s-7 andted by shorter chain homologs. The distribution of S-9 samples associated with gas hydrate from thehe long-chain alkylbenzenes was dominated by low Gulf of MexicoS-4-Ali以人从人人L这这100m/z92250030.00350040.0045.0050005500600065.0070.007500Fig 3. Mass fragmentograms of m/z 83(n-alkylcyclohexanes), m/z 99(n-alkanes)m/z 91 and m/z 92( branched alkylbenzenes)from Sample 4. Number above the peakk numl3. 3 Sources and signification of penylalkanesFirstly, sampling locations were far from sewage outfallrs. and were neBecause the phenylalkanes widespread occur in for中国煤化工 he occurrence and ththe environment Takada and Ishiwatari, 1990; relatCNMHGstronEganhouse, 1986), whether the phenylalkanes are theare not sindigenous to these samples collected from the gas such as cleaning our equipment using synthetic de-片为数e excluded gradually contaminationtergents containing linear alkylbenzene sulfonatesWANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p 71-82( LAS) as surfactants, but are indigenous to the sed- high abundance in S-1, s-4, S-7 and S-9 sam-iments. In further affirmation to eliminate the issue ples are likely to be related to Archaea. Whether theyof outside contamination and inappropriately cleaning could be used as an indictor associated with the oc-our equipment, we carry on these experiments at the currence of gas hydrates or gas venting system, the concorresponding period, which phenylalkane had not clusion confirmed need to carry on a further studybeen found in organic matter road dusts and gully3. 4 Structure of penylalkanessediments from Guangzhou and Hong Kong, Chinaand rainwater from Guangzhou, ChinaFigure 2 showed the distribution of the penylal-alkane analyzed in the samples indeednot rekanes, which was a series with five peaks for everysult from contamination and is indigenous to the sam- cluster. The carbon numbers of phenylalkane rangeples collected from gas hydrate area from the Gulf of from 16 to 19 with the main peak 18 in S-1,S-4MeS-7 and s-9 samples. But, the distribution of pe-In addition, the distribution of penylalkanes in nylalkanes was irregular in S-8, s-10 and S-llour samples ranged from C, to C1g, whichmaximumsamples because these series coeluted with othercarbon is CI(see Fig. 1). The distribution of penye mass spectraalkanes is significantly different from that of penylalIn representative of CI series in S-4 sample,kanes from the detergent, but similar to that of peny- we analyzed the structure of the special series in salkanes from the extract of Thermoplasma bacteria 1, s-4,s-7 and s-9 samples. TEwith maximum CI&( Ellis et al., 1996), which sug- ular mass peak of C1 penylalkanes was all m/z 232gest that penylalkanes in the samples are likely de- for the front four peaks, which indicated that the fourrived from bacteria. Bao and Wang(1996)had found compounds were four isomers of the same carbonpenylalkanes with six isomers for every carbon num- number of phenylalkane. The mass spectra of penyber in maturate sediment of early Paleozoic era in Xi- lalkanes were presented in Fig. 4yangzi area, and their carbon range was between CI5The characteristic fragments of peaks 1-4 wereand Co with a maximum Cu. Thus, the phenylalkane respectively m/z 91, 105, 161; m/z 91, 105, 147series could been used as an indicator of the phot175;m/z91,105,133,189;m/z91,105,119plankton input( Bao and Wang, 1996). So, accord- 203. Each peak had base peak of m/z 91 and 10.5ing to the distribution characteristic compared with which should be the characteristic fragment of Bprevious study, a conclusion is drawn that phenylal- elimination-benzene in the position of alkyl sidekanes in our samples are assigned to a microbial chain. So the phenyl of the compounds should be insource associated with Thermoplasma bacteria. Ther- the middle of alkyl side chain. Namely, the strucmoplasma bacteria are named no-cell-wall Archaea ture of the series is diverse from that of straight chainbacteria. Fuhrman et al.( 1992)and DeLong et al. alkylbenzenes. The characteristic fragments of the(1992)suggest that Archaea are genetically related to fifth peak were m/z 92, 133 and 218, m/z 218Thermophiles. As well known, Archaea and sulfate re- the「YHE单the fifth peakduction (SR play an important role in the anaerobicound was concludedoxidation of methane( AOM) processes associated from mass spectral characteristics of this fifth peakith gas hydrate. At the same time, Archaea bicIt is noticeable that peaks 1-5 had the characker such as PMIA compounds was found in S-l and teristic fragment m/z 161/161, m/z 147/175, m/zS-4 samples. therefore, penylalkanes of the relative 133/189, m/z 119/203, the data that the sum ofANG Cuiping et al. Acta Oceanologica Sinica 2008, VoL. 27, No 6, p 71-82100CCsC5075100125150175200225250275C0751001251501752002252502755075100125150175200225250275中国煤化工CNMHG075100125150175200225250275Fig. 4. Mass chromatograms of m/z 91 and configuration of phenylalkane isomerNumber in the mass chromatograms denotes peak numberWANG Cuiping et al. Acta Oceanologica Sinica 2008, Vol 27, No 6, p 71-82these two characteristic fragment subtracted 90there were differences of distribution of alkylcyclo-rresponding com- hexanes and phenylalkane between S-1,S-4pound(m/z 232). According to these characteris- S-7, s-9 samples and S-8,S-10, S-1l santic fragments, phenyl is in the different substitution ples. The distribution of n-alkylcyclohexanes repre-position of alkyl side chain. We conclude the struc- sented biomarkers for some bacterialture of compounds of each peak (see Fig 4).Phenyl respectively located the position of C-6, C- Acknowledgements5, C-4, C-3 in each series. The fifth peakshould be c -l-decane. We conclude that the isoWe are grateful to Dr. Chen Duofu for provimers wIith the phenyl substituent located near the ding the samples from the gulf of Mexico. Thankscenter of the alkyl chain have lower retention times are also given to Mr. Xiang Tongshou and Dr. Ithan compounds with the phenyl substituent near the Jinzhong for their technical assistance in the gCend of the chain. In the case of compounds with 16 MS and GC-iRMS analyses and to these anonymousand 17 carbon atoms all isomers could not be rereviewers and editors for their useful comments andolved. However, higher members with the phenyl correctionssubstituent located near the center of the chain wereReferences4 ConclusionsAlbaiges J, Farran A, Soler M, et al. 1987. 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