Res. Org Geochem. 20, 39-47 (2005)

有機地球化学会30周 年記念事業 地球・環境有機分子検索マニュアルNo.7〕〔

Occurrences of sesqui-, di-, and triterpenoid hydrocarbons
in the Tertiary oils and sediments from the Pacific side of Japan
Svetlana Yessalina* and Noriyuki Suzuki*(Reccived April 15,2005;Accepted October 3,2005)

1. Introduction
Sesqui-, di-, and triterpenoid hydrocarbons
are thought to be mainly derived from compounds present in higher plants (Simoneit,
1986 with references therein). Numerous studies have documented occurrence of thesecompounds in sedimentary organic matter, fossil resins, coals and petroleum (Moldowan
et al., 1994). They are essential biomarkers
for the assessment of origin of organic matter,
depositional environment, maturation, and forcorrelation studies (Peters et a1.,2005). Amongthese compounds particular attention has been
given to the investigation of pentacyclic triterpenoids, especially to those with oleanane typeskeleton. Structural affinity of these compounds to the naturally occurring triterpenoid
constituents of angiosperms allows to consider

them as molecular markers for angiosperms(Moldowan et al., 1994). Indeed, increased
abundance of pentacyclic triterpenoids in geolo-

gical samples does not start until the Tertiary,
the time of widespread occurrence of angios-

perms (Moldowan et al., 1994). Therefore,
these compounds are considered as age-specificbiomarkers. In the present study, we document
occurrence of higher plant terpenoids in thehydrocarbon fractions of Tertiary sediments,

coals, and petroleum, which can be useful forfurther studies to increase our understandingof terrestrial biomarker distributions.

2. Samples and Experimental
Twenty eight conventional core samples from
the MITI Sanriku-oki borehole (JNOC, 2000),
7 oil samples from the Yufutsu oil and gas

field and offshore wildcats, and 4 samples
from the Sagara oil field were analyzed in thisstudy. The sediment samples analyzed weremainly from depth interval t820-4250 m, ranging in geologic age from Late Cretaceous to
Middle Eocene. The major core lithologies
are mudstones, siltstones, sandstones and coals.

The total organic carbon contents of thesediments are in the range from 0.5 to 2.0%.
Maturity levels based on measurements of
vitrinite reflectance values are in the ransefrom 0.3 to 0.6 o/o, Ro.
The oils from the Yufutsu field and offshore
wildcats were obtained at depth intervals between 2,296-4,275m, which corresponds to the
Ishikari Group, Poronai, and Minami Naganuma Formations and fractured granitic rocks of
Cretaceous age (JNOC, 2000). The oils fromthe Sagara oil field were collected from theTokigaya Formation during Sagara Drilling
Program (SDP) (Hirano et a|.,2003).

*Division of Earth and Planctary Sciences, Graduate School of Science, Hokkaido University,
N10 W8, Kita-ku, Sapporo 060 0810, Japan
Corresponding author : Noriyuki Suzuki

Tel *8-11 706'2'730, Fax *81-11-746-0394
Email : suzu@ep.sci.hokudai.ac.jp―‑39‑―

Svetlana Yessalina and Noriyuki Suzuki

Soluble organic matter was extracted fromsediment samples (3 g) by ultrasonication for
15 minutes with dichloromethane/methanol (99 : 1).
Organic extracts and oil samples were fractionated into aliphatic hydrocarbons and threearomatic fractions by preparative high pressureliquid chromatography (HPLC; JASCO Gulliver series PU-986/UV-975), using a pressureresistant glass column (29 cm X 8 mm l.d.) withsilica gel (WAKOGEL LP 20). A mixture ofhexane,/dichloromethane (95/5) was used aseluent with constant flow rate at 2.0m1/min.
The cut points of fractionation were detectedby ultraviolet light detector at 254 nm using athen held at 300"C for 2}minutes. The instrument was operated in the electron impact
mode at 70 eV. The identification of compounds was accomplished using the mass spectra library data (NIST 98) together with data
available from the literatures.

3. Results and Discussion
Investigation of the saturate and aromatic

analyzed by Gas Chromatography/Mass Spectrometry (GCIMS; HP6890/HP5973), equip-

fractions of the organic extracts from the
MITI Sanriku-oki borehole and oils from the
Yufutsu field and adjacent wildcats, and fromthe Sagara oil field revealed significant abundance of various biomarkers of higher plant origin. The distribution patterns of these compounds and their corresponding mass spectra
are given in the Figs. 1-6, respectively. Detected compounds belong to different groupsof biomarkers of both angiosperm and gym-

ped with the fused silica capillary column

nosperm origin : bicyclic sesquiterpenoids, diter-

DB-5 (30mX0.25mm l.d.). Helium was used
as a carrier gas with flow rate at 1.5 mllmin.
The temperature of oven was initially programmed to hold at 40'C for 2 minutes. subsequently programmed to 300"C at 4'C/min andpenoids, and triterpenoids.

mixture of standard aromatic hydrocarbons(tetracosane, toluene, dimethylnaphthalene, andphenanthrene). Isolated hydrocarbons were

Presence of bicyclic sesquiterpanes in thesediment and oil samples was revealed after

selective ion monitoring (SIM) of m/z I23(Fig. 1). All prominent peaks in the mass
Diterpanes

mlz 123
Bicyclic sesquiterpanes

15８

ヽ ＯＣＯ¨Ｃ一９´

17Time (minlFig. 1. Reprcsentative mass chromatogram at m/z 123, showing the distribution of bicyclic sesquiterpancs and diterpanes in Paleogene oil from the adjacent to the Yufutsu oil and gas field
offshore wildcats (sample H-063), Hokkaido. Identification of compounds is shown in Table l.

-40-

Occurrencesof sesqui-, di-, and triterpenoid hydrocarbons in the Tertiary oils and sediments from the Pacific side of Japan

chromatogram at mlz 123 eluting in the region

between n-Crr and n-Cro-alkanes (peaks 1-13)
exhibit mass spectra similar to those identified
as bicyclic sesquiterpanes by Anders and Robinson (1971), Bendoraitis (1974), and Richardson
and Miller (1982) (Fig. 3). Mass spectra withintense peaks at m/z 179 and molecular ion at
m/z 194 were reported for Cra-bicycloalkanes

Noble et al. (1986) (Fig 3). Detected compounds include tri- and tetracyclic diterpanes,
such as norpimarane, norisopimarane, norabietane (fichtelite), phyllocladanes and abietane.

Norpimarane, norisopimarane, norabietane, andabietane are tricyclics in structure, while phyllocladanes are tetracyclics. Both tri- and tet-(Anders and Robinson, 197I ; Bendoraitis, 1974).

racyclic diterpanes generally exhibit a major
fragment at m/z 123, which forms as a result

Crs-bicycloalkanes have been described to showof cleavage of the B-ring. Tetracyclic diter-

mass spectra with intense peaks at m/z 193

panes are distinct from their tricyclic counter-a;ad 123, and molecular ion at m/z 208 (Richard-parts by diagnostic ions at m/z 231., 245 and274 (Noble et al., 1985). The difference be-son and Miller, 1982). Base peaks at m/z
I79 and 193 have been interpreted to correspond to cleavage of one methyl group.
Identification of diterpanes in the oils fromthe Yufutsu field and ajacent wilcats, and in
the sediment samples from the MITI Sanrikuoki by use of SIM at m/ z 1,23 (peaks 14-19,
Fig 1) was confirmed by comparison with mass
spectra published in Barrick and Hedges(1981), Noble et a/. (1985), Philp (1985), andtween mass spectra characteristics of phyllocladanes and the other common tetracyclic diterpanes, such as kauranes, can be seen in agreater intensity of mlz 231, comparatively to
mlz 259, especially for 16p(H)-phyllocladane(Noble et al., 1985).

Dicyclic and tricyclic terpenoids of higher
plant origin were also detected in the aromatic
fraction of analyzed sediment samples and oils
Aromatic Fraction 2

Saturate Fraction

40

T'me(min)Fig.2.

41■me(min)

Representativc total ion chromatograms of saturatc and aromatic fractions of organic matter
isolatcd from thc Middlc Eoccnc scdimcnt(1840m)frOm thc MITI Sanriku‐ oki borcholc
ldcntiflcation of compounds is shown in Tablcs l, and 2‑41‑

Svetlana Yessalina and Noriyuki Suzuki

Fomula MWｍ

ComDound name

Pcak

ｃ
ｓ
螂
ａ
Ｂ

Table 1. Identification of saturate higher plant biomarkers detected in sediments from the MITI
Sanriku-oki borehole and in the oils from the Yufutsu field and adiacent wildcats. andfrom the Saeara field.
LI* LI**

Reference

1,2 bicyclic scsquitcrpancs
clJ126 194 179 YO,SO,MS(1,2)Andcs and RoЫ nson(1971),BcndOrJis(1974)2(2) 1
3 7 bicydた scsqutclpancs c千 ,H28 208 193 YO,SO,MS(1,2)Rに hardson and Millcr(1982)
2(2) 18 13 bicydた scsqu■ cpancs

14 norpimarancc16Hm 222 123 YO,SO,MS(1,2)Richardson and Millcr(1982)

cl,H. 262

15 4'(H)19 nO● sopimaranc cl,H,4 262

cl,H. 262

PhIP(1985)

233 YO,MS(1,2,4,5)Noblc̀′ α′(1986)

BarHck and Hcdgcs(1981)
Noblc′ ′′′(1985)
18 abictanc
c20H% 276 163 YO
Phlp(1985)
19 10(H)― phメ 10dadancc20H34 ν 4 123 YO,MS(15) Noblc
α ″ (1985)
20 dcs A― tritcrPanC
C24H42 330 191 YO,SO,MS(1,2)wOOlhousc
α ′(1992)
̀′
21 dcs A■ upanec2.lL2 330 123 SO,MS(1,2,4,5)schmittcr′ ′α′(1981)16●chtcitc

233 YO

17 1o3(H)― phyl10Cladanc

22 olcan 13(18)― cnc

23 olcan 12 cnc

Z olcan 18 cnc
25 1路 (H)‑OICan‑12 cnc

cmH■

274

109 YO

123 YO,MS(1,2)

C3。 H, 410 205 SO,MS(1,2,4,5)Ph‖ P(1985)/1ibrary(84255)
cmHm 410 218 SO,MS(15) Philp(1985)/1ibrary(126853)
cmHヵ 410 204 SO,MS(2,4) Philp(1985)/1ibrary(84088)cЮ Hm 410 218 MS(2)Runtttcr

2(2) 12(2) 2(2)2(2) 42(2) 42(2) 32(2) 2(2)2(2) 3
1(2) 12(2) 3

ι ′(1994)/hbra7(87272)̀′2(1/2)2(2)2(1/2)2(2)2(1/2)2(2)2(1)* 2(2)MW, molccular 、vcight; LI*, lcvcl of idcntincation in thc prcscnt papcr, LI**, lcvcl of idcntiflcation in thc rcfcrcncc papcr:
YO,oils from thc Yufutsu flcld and adiaccnt Widcats;SO,ols from thc Sagara flcld i MS,scdimcnts flom thc MITI
Sanriku― oki borcholc: 1, carly Latc Palcoccnc― carly Middlc Eoccnc (3321hl; 04%, Ro); 2, carly Latc Palcoccnc― carly Mid―dlc Eoccnc(3120m;035%,Ro),3,Middlc Eoccnc(231Xlm;035%,Ro);MS4,Middlc Eoccne(1900m;03%,Ro);

MS5,Middlc Eoccnc(1840m103%,Ro) StruCtural assigmcnt was bascd on l l,intcrprcta■ on of mass spcctra data;2(1),coincidcncc in mass spcctral data from library(NIST 98);2(2),coinCidCncc in mass spcctral data with that in a rcfcrcncc
or litcraturc: 3, coincidcncc in mass spcctrum and GC data rctcntion tirnc with that of rcfcrcncc compound i 4, coincidencc
in mass spcctrum and GC rctcntion timc with that of authcntic standard; 5, conflHnation of lcvc1 4 idcntiflcation by othcr
mcthods ネ, assigmcnt Of compound was conirlncd by matching of its rclativc rctcntion timc data with that rcportcd in thc
litcraturc(Rullkttter ι′α′,1994)

Table 2. Identification of aromatic higher plant biomarkers detected in the sediments from the MITI

Sanriku-oki borehole and in the oils from the Yufutsu field and adiacent wildcats, andfrom the Saeara field.

26 cadalene
C,,H,, 198
27 dehydroabietane
C.Hn, 2'/0
28 6-isopropyl2-methyl-1{4-methylpentyl) naphthalene Ce,Hzr 268
29 simonellite
C,,H:. 252
30 retene
C,*H,. 234
31 2-methylretene
C,rHru 248
32 des-A-triterpenoid
Cr.Ho, 306
33 3,3,71rimethyF1,2,3,4-tetrahydrochrysene C,,H., 274
34 24,25-dinor-ursa-1,3,5(10),12-tetraene C,sFI{, 376
35,37 2,2,4a,9-tetramethly-1,2,3,.1,4a,5,6,14b-octahydropicer€

CznH:o 342

36 1,2,4a,g1etramethyl-1,2,3,4,4a,5,6,14b-octahydropicenc C,6H.0 342
38 8,14-seco-oleanoid
C:rHr. 356
39 l-isopropylpropano-7-methylchrysene C,,H.. 324
40 1,2,9-trimethyl-1,2,3,4-tetrahydropicene C,,H,, 324
47 2,2,9trimethyl-1,2,3,4tetrahydropicene C,,H,, 324ｍ

Formulaｃｓａ螂ＢCompound name

Ｗ
Ｍ

Pcak

Rcferencc

LI* LI*オ

183 YO,SO,MS(15) Bcndoraitis(1974)
2(2) 4
255 YO,MS(15)Philp(1985)
2(2) 2(2)197 YO,MS(1,2,3,5) Ellis̀′ α′(1996)
2(2)3
237 YO,SO,MS(15) Simoncit(1977)
2(2)3
219 YO,SO,MS(15) Simoneit(1977)
2(2)2(1)233 YO,MS(1,5)
Bastow ι′α′(2001)
2(2)3
187 YO,SO,MS(15) Stout(1992)
2(2) 1
218 YO,SO,MS(15) Spyckcrcllc ι α′(1977)
2(2) 3̀
145 so,Ms(3‑5)
Wolff̀′ α′(1989)
2(2)3
257 YO,MS(15)Wakcham ι′α′(1980) 2(2)2(2)342 YO,MS(15)Wakcham̀′ α′(1980) 2(2)2(2)
169 YO,MS(14)Chaffcc and Fookcs(1988)2(2)5
281 YO,MS(15)Chaffcc and Fookcs(1988)2(2)5309 YO,MS(15)Chaffcc and Fookcs(1988)2(2)5
268 YO,MS(1‑5)

Chaffec and Fookcs(1988)2(2)5

MW, molecular weight; Ll*, level of identification in the present paper; LI**, Ievel of identification in the reference paper;YO, oils from the Yufutsu field and adjacent wildcats ; SO, oils from the Sagara field ; MS, sediments from the MITI

Sanriku-oki borehole: 1, early Late Paleocene-early Middle Eocene (3320m; O.4Vo, Ro\;2, early Late Paleocene-early Middle Eocene (3120m; 0.35%, Ro); 3, Middle Eocene (2300m1'0.357o, Ro); MS4, Middle Eocene (1900m; O.3Va, R.o);MS5, Middle Eocenc (1840m ; 0.37o, Ro). Structural assigment was based on: 1, interpretation of mass spcctra data; 2(1),coincidence in mass spectral data from library (NIST 98);2(2), coincidence in mass spectral data with that in a reference orliterature ; 3, coincidence in mass spectrum and GC data retention time with that of reference compound; 4, coincidence inmass spectrum and GC retention time with that of authentic standard; 5, confirmation of level 4 identification by othcr
methods.

―‑42‑―

Svetlana Yessalina and Noriyuki Suzuki(Fig. 2). These are cadalene, dehydroabietane,

coincidence with mass spectra from the libraryisohexyl alkylnaphthalene, simonellite, retene,and 2-methylretene. Their presence was re-and literatures (Schmitter et al., 1981. ; Philp,
1985; Woolhouse et al., 1992) (Frg.q. Oleanenes
have diagnostic ions at m/z 218 and molecularions at m/z 410. Assigment of 18a(H)-oleanL2-ene was based on comparison with mass
spectra from the library and retention time described in the literature (Rullkotter et al., 1994).
Des-A-triterpanes have mass spectra with molecular ion at m/z 330. The mass spectra ofdes-A-lupane reported by Schmitter et al.
(1981) is characterized by diagnostic ion at
m/z 287, which corresponds to the loss of anvealed by comparison with mass spectra published in Bendoraitis (1974), Simoneit (1977),

Philp (1985), Ellis et al. (1996) and Bastow
et al. (200I) (Fig. 5). All of these compounds,
except isohexyl alkylnaphthalene, exhibit prominent ion peaks, corresponding to the loss of
one methyl group. The prominent peak ofisohexyl alkylnaphthalene, which is at m/z
197, is due to loss of Cs-alkyl moiety.
Occurrence of higher plant triterpanes, suchas unsaturate oleanenes and des-A-triterpanes(peaks 20-25, Fig.2) in the sediments and oils
was detected by SIM of the m/z l9l andBrcyclic sesquiterpane (1,2)

isopropyl sidechain.

Aromatized triterpenoids such as des-Atriterpenoid, trimethyltetrahydrochrysene, dinor-

NoDimarane (14)100

Bbyclic sesquiterpane (3-7)

41] (H)-1 g-Norisoprmarane (15)

Abietane ('18)

100

16a (HlPhyllocladane (19)

Bioyclic sesquiterpane (&1 3)

123

123

300

Fig.3. Representative mass spectra of bicyclic sesquiterpanes and diterpanes detected in the saturate
fractions of organic matter isolated from the early Late Paleocene-Middle Eocene sedimentsfrom the MITI Sanriku-oki borehole and the oils from the Yufutsu field and adjacentoffshore wildcats, and from the Sagara field.

-43-

Occurrences of sesqui-, di-, and triterpenoid hydrocarbons in the Tertiary oils and sediments from the Pacific side of Japanursatetraene, tetramethyloctahydropicenes, 8,14-

based on comparison with mass spectra fromseco-oleanoid, isopropylpropanomethylchrysene,

the literatures (Spyckerelle et al., 1977 ; Wakeham et al., 1980; Chaffee and Fookes, 1988;

and trimethyltetrahydropicenes were assigned

Olean-18€ne (24)Olean-13(18)-ene (22)Des-A-trtterpane (20)
191

︒
薇
︲
︲
︲
︲
︲
︲
︱
︲
﹇
´
櫛
４
ユ
︲
鋼
︲
︲
︲
＾
＾

一∞

簗／岬︲凛
′︲

300

100

400

18 c (H)-olean-12-ene (25)

4&

400

flz

rdz

Fig.4. Representative mass spectra of saturate and unsaturated triterpanes of higher plant origin detected in the saturate fractions of organic matter isolated from the early Late PaleoceneMiddle Eocene sediments from the MITI Sanriku-oki borehole and the oils from the Yufutsu
field and adjacent offshore wildcats, and from the Sagara field.
Cadalene (26)lsohexyl alkylnaphthalene (28)Retene (30)

to7

2A

０確

Fig.S. Representative mass spectra of sesqui- and diterpenoids of higher plant origin detected in thearomatic fractions of organic matter isolated from the early Late Paleocene-Middle Eocene
sediments from the MITI Sanriku-oki borehole and the oils from the Yufutsu field and adjacent offshore wildcats, and from the Sagara field.

- 44-

Svetlana Yessalina and Noriyuki Suzuki

Wolff er al., 1989; Stout, L992). Monoaromatic (A-ring) triterpenoids include des-A-triterpenoid
and dinorursatetraene (Fig.6). Identification of
des-A-triterpenoid by Stout (1992) was basedon mass spectra interpretation. The base peakof this compound (m/z 187) is suggested tocorrespond to C-ring cleavage, at position of aC': double bond. Monoaromatic compoundsof similar type, like dinorursatetraene, are distinguished by characteristic ions at m/z 145
and 158, which have been interpreted to originate from A- and B-ring mono- and dimethyltetrahydronaphthalene fragments. Trimethyltet-

inent ion fragments at m/z 21,8 and 274. The

former one is due to rupture of the E-ring,
while the latter one represents the molecularion. C-ring cleaved structural configuration of
8,14-seco-oleanoid has been suggested basedon the presence of base peak at m/z 169(Chaffee and Fookes, 1988). Tetramethyloctahydropicenes have prominent molecular ionsat m/z 342. Intense ion at m/z 257 in mass
spectra of 2,2,4a,9-tetramethyl- 1. ,2 ,3 ,4 ,4a,5 ,6,14b-

is due to rupture of the E-ring.
Tetraaromatic triterpenoids such as I,2,9octahydropicene

trimethyl 1,2,3,4-tetrahydropicene

and 2,2,9'

rahydrochrysene, 8,14-seco-oleanoid, and tet-

trimethyl-1,2,3,4-tetrahydropicene

ramethyloctahydropicenes are triaromatic compounds. Trimethytetrahydrochrysene has prom-

inent molecular ions, which are at m/z 324.
The next most intense ions. in these com-

Des A■ rnerpen。 ld(32)also have prom-

Tetramethソ ∝tahydrolcene(35,371

(39)

187

2391 1279309
・,一

100

―一 〜― ^本 」Jb椰ヽユ
200

300

一

Fig. 6. Representative mass spectra of triterpenoids of higher plant origin detected in the aromatic

fractions of organic matter isolated from the early Late Paleocene-Middle Eocene sedimentsfrom the MITI Sanriku-oki borehole and the oils from the Yufutsu field and adiacentoffshore wildcats, and from the Saeara field.
―‑45‑―

Occurrenccs of sesqui-, di-, and triterpcnoid hydrocarbons in the Tertiary oils and sediments from the Pacific side of Japan

pounds are at m/z 309 and 268, representing
loss of methyl group and the rupture of the

E-ring, respectively.
Acknowledgments

We thank Japan Petroleum Exploration Co
Ltd (JAPEX) and Japan Oil, Gas and Metals
National Corporation (JOGMEC) for providing
the oil and sediment samples and permission
to publish this paper. Special thanks to Mr. H.
Saito for his sampling of oils in Sagara oilfield. Thanks are also due to Drs. K Sawada
and N. Ratnayake for their constructive suggestion and help in preparatory work. We
are grateful to Professor Shuichi Yamamoto of
Soka University and one anonymous reviewer
for their comments, which substantially improved the manuscript.

Org. Geochem. 12, 261-271.
Ellis, L., Singh, R. K., Alexander, R. and Kagi,
R. I. (1996) Formation of isohexyl alkylaromatic hydrocarbons from aromatizationrearrangement of terpenoids in the sedimentary

environment :A new class of biomarker.

Geochim. Cosmochim. Acta 60, 4747-4763.

Hirano, S., Araki, Y., Wada, H. and Sagara
Drilling Program Scientific Party (2003)
Lithology and physical properties of coresamples obtained from the Sagara oil field,
central Japan : Preliminary results of the
Sagara Drilling Program (SDP). In: IFREE
Report for 2001-2002, Frontier Research on
Earth Evolution, YoI.I, pp.253-257.
Japan National Oil Corporation (JNOC) (2000)
Report on the MITI Sanriku-oki drilling. (inJapanese), pp.48.

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32Appendix. Chemical structures in the text.
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