0016-7037/85/$3 00 + .

oo
Georhrmrca o Cosmc-zhhrmrco
Acla Vol. 49. PP. 385-395
0 Pergamon Pra Ltd. 1985. Pnnted in U.S.A.

The effects of thermal maturity on distributions of dimethylnaphthalenes and

trimethylnaphthalenes in some Ancient sediments and petroleums
R. ALEXANDER, R. I. MAGI, S. J. ROwLANDt, P. N. SHEPPARDand T. V. CHIRILA
Petroleum Geochemistry Group, School of Applied Chemistry, Western Australian Institute of Technology,
Kent Street. Bentley, Western Australia 6102, Australia

(Received July IO, 1984; accepted in revised form October 29, 1984)

Abstract-The distributions of di- and trimethylnaphthalenes in two sedimentary sequencesfrom Western

Australia have been examined by capillary gas chromatography and combined gas chromatography-mass
spectrometry. A general decrease was observed in the relative proportions of aadimethylnaphthalenes
and aa&trimethylnaphthalenes with increasing thermal maturity. Similar trends were also observed for
six crude oils which have very different ratios of ethylcholestane epimers indicating very different thermal
histories. These results suggest that changes in the relative abundances of certain methyl substituted
naphthalena may be useful indicators of thermal maturity of sedimentary organic matter. and the use of
a number of isomer ratios is illustrated.

INTRODUCI’ION DOUGLAS, 1955; YEW and MAIR, 1966; DUSWALT

and MAYER, 1971) resulted in the identification of
ALKYLNAPHTHALENES are common constituents of
eleven TMN isomers in petroleums. Capillary gas
petroleums derived from various type of sediments
chromatography has proven to be a suitable method
(GAVAT and IRIMESCU, 1941, 1942; CARRUTHERS
for accurate analysis of the complex aromatic mix-
and DOUGLAS, 1955; ROSSINI, 1960; MAIR and
tures, (e.g. MAIR and MAYER, 1964; YEW and MAIR,
MAYER, 1964; YEW and MAIR, 1966; DUSWALTand
1966: DUSWALT and MAYER, 1970; TE~A~IK et al.,
MAYER, 1971; VANDENBROUCKE,1980: ALEXANDER
1978; MUTTON, 1979; WHITE and LEE, 1980; AL-
et al., 1983a). They have been reported to occur
EXANDER ef al.. 1983a) and recently, the relative
widely in Ancient sediments and coals (e.g. KARR ef
abundances of ten TMN isomers in an Australian
al., 1967; WOLLRAB and STREIBL, 1969; ALBRECHT
crude oil has been reported (ROWLANDef al., 1984).
et al., 1976; RADKE et al., 1982a,b) where they are
In this paper we present compositional data for
believed to be derived, at least in part, from degra-
DMN and TMN isomers in a number of sediment
dation of natural terpenoids (e.g. HANSON, 1959:
extracts from Northwest Western Australia, and in
BREGER, 1960; DOUGLAS and MAIR, 1965: ISHIWA-
some crude oils from China, Nigeria and Australia.
TARI and FUKUSHIMA, 1979; ISHIWATARI, 198 1a.b).
Samples were chosen to represent a range of thermal
Alkylnaphthalenes have also been reported to occur
histories, source types, geological ages and geographical
in Recent marine sediments (SMITH, 1954; MEIN-
locations so that the effects of these factors upon the
SCHEIN, 1959; JONES e[ al.. 1983), and the same
relative abundances of DMNs and TMNs could be
precursors were proposed (BYERS and ERDMAN.
evaluated.
1983).
Changes observed in the relative abundances of
EXPERIMENTAL
dimethylnaphthalenes (DMNs) have been used to
obtain information about the thermal maturity of Samples
sediments. RADKE efal.( 1982b) reported that changes The sediments studied comprised five samples of cores
in the abundance of the l,5-isomer relative to those obtained from the Cape Range-2 well in the Camarvon
of the 2,6- and 2,7-isomers correlated with increase Basin, and fourteen samples of well cuttings from the
in coal rank, and ALEXANDER et al. (1983~) showed Jupiter-l well located in the Exmouth Plateau; both wells
that the relative abundance of the l,8-isomer was are located in Northwest Western Australia (Fig. 1). The
main geological features and some of the geochemical
also a sensitive indicator of thermal maturity of properties of the sediment sample-sare given in Table I.
sediments. The effect of biodegradation on the distri- These sediment sequences were selected because they have
bution of dimethylnaphthalene isomers in crude oils been well characterized and have experienced quite different
has also been reported (VOLKMAN et al.. 1984). thermal regimes (Moo=, 1980; Coon and KANTSLER,
1980; MARTINand SAXBY,1980; BARBER,1982). The six
Trimethylnaphthalenes (TMNs) were first identified
crude oils examined were obtained from reservoirs ranging
in a Rumanian crude oil by GAV~T and IRIMESCU in age from Miocene to Jurassic in Nigeria, Australia and
(1942). Subsequent investigations (CARRUTHERSand China (see the description in Table 2). These oils were
selected for study because they cover a range of geological
ages and also because of existing published data on source
type and thermal history for similar oils (e.g. for some
t Present Address: Organic Geochemistry Unit, Depart- Nigerian oils see EKWEOZORet al.. 1979a,b; for some
ment of Geology, University of Newcastle, Drummond Chinese oils see SHI JI-YANGet al.. 1982; for Muderong
Building, Newcastle-upon-Tyne, NE I 7RU, United Kingdom and Barrow oils see VOLKMAN et al.. 1984). The differences

385
 R. Alexander et ai

r margin of Northwest Western Austraha. This area rncom-

passes the Camarvon Basin and the Exmouth Plateau which
are separated by a gentle downwarp across the central
I eastern part of the Plateau, the SSW/NNE trending Kangaroo
Trough (Fig. I: BARBER,1982). Jupiter-l lies to the North

1
I
FIG. 1. Map showing well locations in Northwest Western
Australia.
in thermal maturity and source type between the oils for
which little published information is available were inferred early Jurassic time. but did not reach full maturity (&,
by using sterane biological marker data (Table 2). This
approach has been widely advocated as useful for these
purposes (e.g. SEI~=ERT and MOLDOWAN,198 1: MACKENZIE geothermal gradient of 30°C km-’ (MOORS, 1980). Table I
et al., 1980, 1982, 1983).
Geologicalsating
The two sequences of sediments examined in the present
study were taken from wells drilled in the continental
West of the area on the Exmouth Plateau and close to the
continental slope. Cape Range-2 lies to the South in the
Camarvon Basin and near to the Pre-Cambrian shield (Fig.
I). The geology of the region has been described in detail
(PLAYFORDet al.. 1975). The sediments of the Exmouth
Plateau area comprise a thick sequence of Permo-Triassic
strata overlain by much thinner Jurassic, Cretaceous and
Cenozioc cover due to the fact that the Plateau was isostat-
ically positive and aerially exposed for much of the Mesozoic
and Cenozoic (BARBER,1982). Sediments in the Cape Range
area comprise a much greater thickness of Jurassic rocks
because, unlike the Plateau, the area was not isolated from
the major sources of sediment supply by extensional rifting
during Jurassic time and did not experience the major
erosional events of the Callovian Break-up (BARBER,1982).
The thickness of the strata in the study area generally
decreases to the East (i.e. the sediments thin against the Pre-
Cambrian Shield). The Exmouth plateau has a geothermal
gradient of 23°C km-’ measured for Jupiter-l (BARBER,
1982). It is therefore. broadly speaking, a region of low-
moderate heat flow compared to an estimated world average
range in sedimentary basins of 15-50°C km-’ or to other
proposed values (TISSOTand WELTE, 1978). BARBER( 1982)
has calculated that the bottom 800 m of the Mungaroo
formation had reached early maturity (I&, = 0.5-0.7) by
= 0.7-1.3) until the Upper Cretaceous. The Cape Range
area has a higher heat flow, with an average and measured
shows that values for vitrinite reflectance in the Cape Range-
7 well range from 0.37 at 1378 m. present temperature.
61 “C. through to 2.56 at 3911 m, present temperature.
133°C: the comparatively high value for & suggests that
palaeotemperatures and palaeotemperature gradients in the
sequence have been higher than at present. The difference

TABLE 1: Oeoohemioaldata for sadimnt samples.

QeOlOgiOal Depth Tsrqature* Rob T_'

Ul* Looation m Lithology cm) ( C)

Cap*Itallge-2 C8lYlWVO~
Bnsin
cot-a 18 JUIWSSiC Siltstone 1378 61 0.37 416
core 19 JlllV,SSiC Siltstone 2256 61 0.95 no data
core41 Jurassic Siltatone 1850 94 1.62 443
Core 56 JUlXBaiC si1tl)tone 321s 101 2.03 no data
core 78 JWXSSiC Siltstone 3911 133 2.56 459

Jupiter1 BZploUth
Plateau
TPlpsSiO sand and clay 1400 71 0.38d 425
TPiADSiC sand and 01ay 2555 74.5 no data 432
TPtiaIIiC sand and ClPY 2700 7a 0.38 434
TriMSiC sand and clay 2910 82.5 0.49' 433
Tri4SaiC sand ami o1ay 3150 88 0.57 429
TriMsi sala and 01ay 3450 95 no data 436
TriMal sand md 01ay 3600 98.5 0.63 429
Tl.irsBiC saod ux3 clay 3770 102.1 no data 437
Tl-iuaiC sand and OlW 3900 105.5 o.a3 436
TFiMSiC %nd and clay 4050 109 no data 441
TriMal sand and 018Y 4220 112.5 0.77 440
Tt‘iM8if sand and 01ay 4100 119 0.86 433
TI%USiC Smld and clay 4672 123 no data 437
TPiMSiC sand and clay 4815 126.5 1.36 453

Data mum for Cap. RambZ maples: artin aal Suby, 1980. Data sQI1'0afor Jupiter-1Slolple,s:
Earbar. 1982: otb.r ".lues in tbia a0ri.s: 0.76s at 4399m and 1.3&at 4946E.
' TIw valuu mre d&WaUmd loaordingto the l tf~dmtiRook-Hal pIWO6We (qpittiidti U..1977).
otb*r va1u.a w: for cq tuga-2 aeri*s:485 C at 192C (Core IS1 .ad 440 C at 254h (Corn 34);
ror .Jup1tm-1"rim: 441 c at 43ssm ati 459 c at 4946m.
d Suple depth: 22500.
' Smpla depth: 3OOOm.
 Methylnaphthalenes in sediments 38-l

TASLE 2: Coochemical data fo&%P~ai ‘6x1s.

Field or A@ ot API
Yell Ram Loaat1on Rs~rsolr Gravity 2WZORa

Shangli China cretaoews n.a. 0.7

North Apol Ni@ria niocene 42.2 0.8

Lubert Rankin Platform. TrtiSiC n.a l.Ob

Northusst Western
Australia

Parrow 199DmC Barrow Field, Naooooian 36.ld l.Od

Northwest Western
Australia

Barrow 2010mc Barrow Field. Upper Jurassic 39.6d l.ld

Nortbwsat Western
Australia

Parrow Condensate Barrow Field, JlWaSSiC 40.5 1.1

(Top Zone) Northwest Vestem
Australia

a Ratio 2OS-So~H~,14a~H~,17o~A~-etbylcholestcme / 20R-Sa(H).lla(H).17o(H)-

b ethylohol~stanc.
Philp & &. ,
1912.
4 Dln(yo Clayatone Formation (see Yolkman .& &..1993).
” vo1kman &pI.*l9(3.
n.a.: data ape not available.

in heat flow between the two areas appears to be caused by
the thickness of the sedimentary column-where the sequence
is thinnest, the sediments more rapidly reach thermal equi-
librium with the basement heat source. Migration of hot
fluids along fault lines in the Cape Range Fault Zone may
also be a factor in this region. incomplete dissipation of
deformational energy from fault reactivation in the Miocene
may add to this (Mm, 1980). The Jupiter-l well sediments
are probably cooled further by deep (>looO m) circulating
waters (BARBER, 1982).
The sediments examined in this study comprised fluvio-
deltaic elastic deposits of the Triassic Mungaroo Formation
(Jupiter-l) obtained from depths of 2400-4946 m, and
siltstones of the Jurassic Dingo Claystone Formation (Cape
Range-2) obtained from 1378-3911 m depths. The source
material type for each sequence has been shown to be Type
II-II1 organic matter using 01 and HI measurement by
Rock-Eva1 pyrolysis (Jupiter-l) and by kerogen-typing using
C, H, 0 elemental compositional data (Cape Range-2)
(BARBER, 1982).
Organic extracts and crude oils separations
Air-dried cuttings and core samples (IO-50 g) were crushed
to ca. I50 pm in an N. V. Tema grinder at room temperature.
The crushed samples were extmcted with redistilled dichlo-
romethane (320-350 ml) using a kinematic high speed
blender (IO minutes). The extracted material was separated
from the sediment by filtration with a Buchner system and
was then recovered by removing the solvent in two steps,
first by a fractional distillation through a I5 cm column
packed with Raschig rings, followed by a careful evaporation
to a volume of 1 ml or less using a Kudema-Danish
apparatus.
These organic extracts were subjected to a column chro-
matography separation on silicic acid which had been acti-
vated at 250°C for 24 hours. A stream of dry nitrogen was
used to assist the passage of the eluting solvents through the
column. The saturated hydrocarbon fraction was eluted with
n-pentane, then a crude aromatic fraction was obtained by
eluting with n-pet&me: ether (95:5). Excess solvent was
removed in a Kudema-Danish apparatus, leaving a volume
of 100-200 cl. An aromatic fraction was isolated from the
crude oil samples in a similar manner.
The crude aromatic fractions were subjected to a thin
layer chromatography separation on alumina plates (Merck
Alumina G; 0.6 mm, activated at 120-14O’C for at least 12
h). The plates were developed with n-hexane, and the
required band (Rr = 0.3-0.7). comprising di- and trinuclear
aromatics, was located using short wavelength UV light.
The alumina bands were extracted with dichloromethane
(20 ml) and the solutions were concentrated to l-l.5 ml in
a Kudema-Danish apparatus. In several trial experiments,
aromatic fractions isolated Born crude oils directly by TLC
gave identical results to fractions which had been subjected
to the prior silicic acid fractionation. Accordingly, we now
recommend the use of direct TLC for isolation of DMN,
TMN, and phenanthrene fractions.
GC and CC-MS anai.vses
Gas chromatogmphy was performed using Hewlett-Packard
(HP) chromatographs, either HP 5880 or HP 589OA. fitted
with 50 m WCOT columns (0.2 mm i.d.) coated with either
OV-I, OV-1701, 5% crosslinked phenylmethyl silicone or
crosslinked methyl silicone as described elsewhere (ALEX-
ANDER et al.. 1983a; ROWLAND et al.. 1984). In a typical
analysis, using HP 589OA and 5% cross-linked phenylmethyl
silicone. hydrogen was used as carrier gas at a linear velocity
of 30 cm XC-‘, detector (RD) and injector temperatures
were 300°C and 280°C respectively, and the oven was
temperature programmed from 45°C to 155°C at 1°C
min-‘, then from I55’C to 2 I5’C at 2°C mitt-’ and finally
to 300°C at 15°C mitt-‘. Peak areas were automatically
integrated using an HP integrator. Mass spectra were recorded
using an HP 5985B GC-MS system fitted with one of the
above mentioned WCOT columns. Typical mass spectrom-
eter operating conditions were: ion source temperature,
250°C; electron voltage, 70 eV; mass range, 50-450 amu in
1.3 second cycles; and EM voltage of 2600 V. Methylnaph-
thalenes were assigned by mass fragmentography of the
molecular ions (m/z 142, 156, 170) and by comparison of
retention times with those of authentic isomers (ALEXANDER
ef al., 1983a; ROWLAND et al., 1984). 1,8Dimethylna-
phthalene occurred at very low concentrations in sediments
and oils. It was therefore necessary to perform selected ion
monitoring GC-MS techniques to identify and quantify this
compound. The level of I.8-DMN was related to those of
 3xx R. Alexander ef ai

the other isomers using their ratios to the level of acenaph-

thene, knowing that the latter eiutes approximately 30
seconds after I,%DMN (cfVASSLAROS PI nl.. 1982). using ~._~.._~___.. ~____
the procedure described in ALEXANDER er al (1983a).
Dimsthyinaphtbalensa (C)=
Sanp1e ----II~-_ __ .I.^_._
depth
RESULTS AND DI!YXXJSSION (oetrss) I.2 1.3r1.7 2,3+1.4 1,s 1,6 2.6 :1 7
-_--_-- _.-,-.-
The proportions of DMN and TMN isomers in 2400 5.9 32.6 22.4 IO.2 14.7 6.6 ?.6
zsss 6.8 29.6 lV.V 9.3 18.1 9.4 lx.9
sediment extracts are given in Tables 3, 4, 5 and 6 2700 7.6 29.8 21.5 7.3 17.8 7.2 8.3
2910 2.4 31.8 22.3 9.6 18.9 6.7 8.3
as a percentage of total isomers of each group. The 3150 9.6 29.3 20.V 7.9 17.8 6.8 :.,
values reported are the average of at least two anaiyses. 3450
3600
8.7
8.6
30.4
30.4
17.6
16.2
7.0
6.8
18.3 8.8
13.9
9.2
18.9 5.2
Since the Cape Range-2 samples were analyzed using 3770 9.7 17.7 17.4 7.1 19.9 10.5 ?.7
3900 7.9 29.8 15.9 6.2 19.4 15.0 5.8
two different GC columns, values for all DMN 4050 9.1 17.6 13.8 6.J 23.2 12.3 7.5
4220 7.7 29.9 15.0 6.2 20.4 11.7 0.1
isomers were obtained. The Jupiter-l samples, how- 4500 17.3 21.1 28.4 5.1 15.0 7.4 5.7
ever. were analysed using only one type of column 4672 6.7 28.5 12.6 6.0 22.8 14.4 9.0
4815 4.9 29.2 17.? 5.0 22.8 9.1 10.6
(phenylmethyl silicone). and because co-eiution of --
a Does not include 1.8~DIU.
the 1,3-. I,7-DMN and X3-, 1,CDMN isomer pairs
occurred, individual abundance of each isomer could
not be measured. The results of similar analyses that most parameters exhibit good correlations with
carried out on the six crude oils using two different depth (r > 0.85).
GC columns are presented in Tables 7 and X. The rate of increase of these parameters with
It is apparent from these results that the n@ and increasing depth (tern~~tu~) is generalfy greater
&3 DMN isomers (1,3-. 1,6-. l-7-. and 2.6. 2,7- within the Cape Range-2 sequence than within the
DMN) are present in all samples at greater concen- Jupiter- I sequence. This observation is consistent
trations than are the a(~ isomers (I,CDMN. 1,5- with the higher palaeotemperature gradient and greater
DMN. and especially, I,&DMN). Further. in the thermal maturity range of the Cape Range-2 sediments
sediment samples one observes that the IA-DMN compared with those from the Jupiter-i sequence
and the I,5-DMN concentrations decrease shghtly (MWRS, 1980;BARBER,1982). Theseresults show
with increasing depth. and the I.&DMN concentra- that the thermal maturity range of the Jupiter-i
tion decreases dramatically with increasing depth. samples cover a range beginning with that usually
The major TMN isomers are 1.3.6 and 1.3.7- associated with the onset of petroleum formation
TMN (a&3). The lowest concentration IS exhibited (Re, 0.5; MPI- I, 0.29) through to maturities associated
by 1,2,4-TMN (on@): however. the various isomers with peak petroleum formation (Re, I .2; MPI-1,
possible with l.8-substitution were not present in 0.81) (BARBER, 1982). The range is extended within
detectable amounts. Compared with those for the the Cape Range-2 sequence to include sampies from
DMNs, relative abundances of the TMN isomers maturity zones usually associated with condensates
exhibit a more irregular vanation (see Tables 5. 6 and wet gas through to dry gas zones (& > 2, MPI-
and 8). however a tendency of the 1.2.6-. i.2.7- and 1 r I).
1,6,7-TMN to maintain a fair)? constant level is
noticeable.
Two widely-accepted maturity parameters. vitrinite
reflectance (R,) and Rock-Eva1 7.,,,, (see TISSOTand Figure 3 shows a plot of some selected ratios of
WELTE, 1978). and also a recently proposed one. the methylnaphthalenes for these sedimentary sequences.
methylphenanthrene index MPI (RAKL (‘1 al., The ratios involving dimethylnaphthalene isomers,
i982a,b; 1983) have been plotted against sediment DNR-I and DNR-2, and the ratio of trimethylnaph-
depth for Jupiter-l and Cape Range-2 samples (Fig. thalene isomers TNR-1 (Tabie 9) a11 change in a
2, A-D). Each parameter increases with depth of regular manner with increasing depth and matu~ty
sediment burial at both locations. The correlation of the sediments. They show similar trends to those
coefficients for the linear regression analysis show of the established maturity parameters in that similar
linear correlations with depth occur and a greater
range of values was obtained for the Cape Range-2
TABLE3 sequence than for the Jupiter-f sequence. The DNR-
I parameter was first proposed by RADKE el al.
( 1982b) who reported that it correlated with increased
coal rank and vitrinite reflectance. He suggested that
with increasing thermal maturity the %a-substituted
isomer (1,5-DMN) might rearrange to yield the W
substituted isomers (2,6- and 2,7-DMN). The DNR-
2 ratio shown here is similar in that it too incorporates
both a,a- and ~,~-su~titut~ compounds, and results
in a relative decrease in the abundance of the a,(~-
 Methylnaphthalenes in sediments 389

TABLE 5: Distributions of ~%W8l@tWbtW.W..iS~~ in Cm i*ape-2

samples aa percent&w or the total trimthyln*phthaleneb

Triathylnaphtbalenes W
?,El@e
depth
(meres) 1.3.1 1.3.6 1.4,6+1.3.5 2.3.6 1.2.1 1.6.1 1.2.6 1.2.4 1.2.5

1378 13.5 36.9 19.9 4.2 O.Ua 1.9 2.5 5.6b 14.7
2256 1.8 14.2 16.4 13.4 3.5 15.8 8.9 2.2 17.8
2850 10.8 17.4 19.8 12.1 3.1 13.1 8.5 2.0 13.2
3215 15.4 23.8 13.7 18.6 5.1 9.6 8.2 0.4 5.2
3911 1.9 20.4 7.6 31.3 3.4 6.2 11.6 1.4 10.2

; Approximatevalue.
Unidentified co-aluting COmPOUnd.

isomer with increasing thermal maturity of the sedi-
ments. Again the TNR-1 parameter incorporates a
ratio of compounds with different substitution pat-
terns. In this case the presumably more stable &/3.@-
substituted isomer (2,3,6-TMN) increases relative to
the a,a,&substituted isomers (1,4,6- and 1,3,5-TMN)
with increasing thermal maturity, suggesting that the
DMN and TMN isomers with the greatest degree of
a-substitution and which are presumably less stable
are also the most susceptible to change with increased
thermal maturity. Further supporting evidence is
provided by the absence of the highly reactive a,a,a-
substituted TMN isomers even in the comparatively
immature sediments.
The greater reactivity of the a-substituted isomers
can be rational&d in terms of steric strain. Substit-
uents located at these ring positions have strong peri
interactions either with hydrogen or other methyl
substituents (MILLIGANeIal., 1956; PACKER el al.,
1958; BALASUBRAMANIYAN, 1966). This steric strain,
which will clearly be greatest for compounds with
two methyl groups with peri relationships such as
1,I-DMN, promotes chemical reaction, particularly
when the reaction intermediate involves relief of this
strain.
Reactions which may be favoured by a-substituted
naphthalenes therefore would include isomerisations
via 1,2-methyl shifts, disproportionation via transal-
kylation processes and degradations such as reduction
or dealkylation. The extent to which the latter pro-
cesses occur in sediments is largely unknown. Dis-
proportionation reactions in which a moderately sub
stituted aromatic is converted by transalkylation pro-
cesses into one component with a higher degree of
substitution and another with lesser substitution than
the reactant are apparently of minor importance in
sediments. This conclusion is based upon the obser-
vation that no major change in the distribution of
aromatics towards unsubstituted and highly substi-
tuted aromatics is observed with increasing thermal
maturity of the sediments. Such reactions, which are
bimolecular in character, will be less favoured than
unimolecular reactions when the reactants are dis-
persed in sediments. The unimolecular isomer&ion
process is therefore likely to be a favourable process
to occur in sediments. Such processes have been
extensively studied for methyl substituted aromatic
hydrocarbons under laboratory conditions (MAYER
and SCHIFFNER,1934, CULLINANEand CHARD, 1948;
MCCAULAY and LIEN, 1952; BROWN and JUNGK,
1955; DEWAR, 1959, 1963; SULD and STUART, 1964;
SHINE, 1967: OKU and YUZEN, 1975; LAMMERTSMA,
I98I ) where it has been established that: acid catalysts
are required: ring isomerisation occurs by 1,2-methyl

TABLE 6: Distributionsof trlmethylnaphthalene lsmera in Jupiter1

samples as p%rceatqes of the total triathylnaphthalenes

Trimethylnaphthalenes
W
SWlC
depth
(meres) 1.3.1 1.3.6 1.4.6+1.3.5 2.3.6 1.2.7 1.6.7 1.2.6 1.2.4 1.2.5

2400 12.8 21.0 21.1 9.3 3.7 10.1 4.1 2.1 15.8=
2555 11.8 17.2 19.9 8.5 6.0 11.1 3.5 0.5 21.8'
2700 13.6 17.7 17.2 10.9 4.6 15.0 5.2 1.0 14.8
2910 6.8 18.7 19.7 9.0 3.7 13.4 6.1 0.9 21.1
3150 11.2 21.0 18.8 9.3 4.3 12.2 7.0 0.5 15.7
3450 13.5 21.2 18.9 9.9 5.1 12.0 7.0 1.0 11.4
3600 12.1 19.9 17.1 9.7 5.6 10.8 6.6 0.7 17.5a
3170 11.3 19.4 15.7 10.5 6.1 12.4 9.1 0.6 14.9
3900 10.6 19.5 15.6 11.4 6.6 12.2 10.9 0.5 12.7
4050 10.9 17.0 15.3 10.7 5.1 12.7 9.4 0.6 18.3a
4220 12.3 18.5 16.2 12.1 5.1 12.7 9.1 0.6 12.8
4500 8.0 10.3 11.4 12.8 5.9 12.0 8.6 0.2 30.8'
4672 15.2 19.4 16.0 10.4 5.4 10.0 6.3 2.0 15.3
4815 14.3 15.3 11.2 13.0 2.9 9.1 5.1 1.5 27.6'

a Unidentifiedco-alutingcoaparnd.
 K. Alexander
etal

TABLE 7: Distributionsof di~thylaPphtha.leneisaoers in crude oils

aa perasntsges of the total dimthylnaphthalenes

Sample
1.2 1.3 1.4 1,5 1.6 1.7 1.8 2.3 2.6 2,'

Shsagli 6.9 12.4 4.7 5.8 26.3 13.9 0.22 8.4 10.9 10.6
North &aoi 3.0 15.7 3.9 3.4 22.6 14.8 0.045 1.3 13.S 14.8
Lasbort' 3.0 17.3 3.2 4.1 21.1 13.0 0.02 1.1 16.8 14.3
Barrow 189Om 4.0 15.7 3.0 4.0 21.1 IS.5 0.015 6.1 IS.7 14.3
Barrow 201om 3.7 15.4 3.0 3.9 21.2 lS.6 0.012 6.1 16.0 14.5
Barrow Condensate 2.4 16.2 2.3 3.5 20.7 14.8 0.0043 6.0 18.4 15.6
--.l

shifts via o-complexes as intermediate species; the
reaction obeys first order kinetics; migrational barriers
exist between adjacent aromatic rings and between
adjacent ,~3positions; disproportionation reactions
proceed to a negligible extent.
The demonstrated acidic properties of clays (e.g.
BROOKS, i 948, t 952; FRIPIAT and ~RUZ~MP~I~,
1974; JOHNS, 1979; SIEWND et al., 1979; SHAW,
1980) and some petroleum source rocks (e.g. GOLD
STEIN, 1983) suggest that suitable acidic sites are
available to catalyze such reactions in sediments.
TUCHIHASHI and HANZAWA ( 1942) reported the
isomerization of 1,6-DMN (&I) into 2.6~DMN (p/3)
in the presence of a “Japanese acid clay”. Mortiand
and coworkers have detected charge-transfer com-
plexes formed from aromatic hydrocarbons, as ad-
sorbed species, and cations in lattice positions of
clays (DONER and MORTLAND. 1969: MORTLAND
and P~NNAVIA, 1971: PINNAVIA and MORTLAND,
1971). It is known (DEWAR, 1959, 1963; SHINE,
1967) that ring isomerisation reactions can proceed
by similar charge-transfer complexes. Our previous
studies of aromatic hydr~en-exchange reactions of
naphthalene on the day surfaces (ALEXANDER ~'f al..
1982, 1983b) have suggested that these reactions
could occur in sedimentary environments due to the
acidic properties of clays. If, as is presumed, proton-
exchange occurs via a protonated intermediate. these
intermediates might be expected to undergo 1.2-
methyl shifts. The observed greater reactivity of the
more highly a-substituted isomers compared with the
&substituted counterparts in sediments is therefore
compatible with a ring isomerization process involving
1,tmethyi shifts.
Figure 4 shows a plot of four dime~ylnap~th~ene
ratios (DNR-2 . . . DNR-5) against depth in Cape
Range-2 sequence. These ratios were chosen to rep
resent compounds with different substitution patterns
(see Table 9) and hence different s~~b~h~ towards
chemical reactions in the sediments. These ratios are
based upon I,8-DMN which is the most reactive
DMN isomer. They exhibit a much greater sensitivity
to changes in thermal matu~ty compared with DNR-
1 which is based on 1,5-DMN; values for the latter
ratio range from 4 to I 1 (Fig. 3) whereas the DNR-
2 . . DNR-5 ratios have values ranging from 50 to
240. Clearly this effect is consistent with the lower
stability and hence greater reactivity of 1,8-DMN
@eri-methyl-methyl interaction) compared with IS-
DMN @&methyl-hydrogen interaction).
Methylnaphthalene ratios in crude oils
In order to further assess the generality of DMN
and TMN isomer ratios as indicators of thermal
maturity, we have measured these ratios for a suite
of crude oils which were selected to represent oils
from sources of different maturity. An independent
assessment of thermal maturity was made on the
basis of the C-20 epimer ratios of ethylcholestane.
The concentration of 20R-5a( H), 14a(H), 17a(H)-
ethyicholestane decreases relative to that of the cor-
responding 20s epimer with increasing thermal ma-
turity. The epimer ratio 20S/20R increases with

TABLE 8: Distributionsof'trimsthylnaphthaleneismw's in crude oils

as psrcsntegasof the total triwthylnaphthtalenes

Trlmthylnaphthalensa (W

sample
1.3.7 1.3.6 1,4,6+1,3,S 2.3,6 1.2.7 X,6,7 1.2.6 1.2.4 3.2,s

Shsn&li 24.1 20.6 19.3 9.8 2.9 S.l 5.9 -= 11.7b

North A~01 17.3 27.1 17.0 10.1 4.4 7.0 8.2 1.1 7.8
Lambert 21.7 30.7 19.9 11.9 -a 7.1 2.6 0.9 3.2
&lrrow 1890s 16.7 22.8 17.5 14.6 3.0 10.8 S.0 4.8 S.6
Barrow ?.Ololp 21.0 28.2 18.6 13.6 2.1 7.7 4.7 - 4.1
Barrov Condensate 20.2 23.2 15.7 16.0 2.2 9.0 6.2 4.2 3.3

; Not detected.
Unidentifiedco-elutiw ComPound.
 Methylnaphthalenes in sediments 391

. MPI-2

5_ : g
123 3 0.5 0.9 1.3 1.7 2.1
%
FIG. 2. Geochemical maturation parameters for Jupiter-l (0) and Cane Range-2 (0) sequences: A.
Mean maximum vitrinitc reflectance; B. Rock-Eva1 T,,,,,; C and D: Methylphenanthrene indices MPI-I
and MPI-2 respectively (see Table 9).

maturity up to the equilibrium value of around 1.1
(MACKENZIE et al., 1980, 1982, 1983; SEIFERT and
MOLDOWAN, 198 1; VAN GRAAS et al.. 1982). Table
2 shows the value for this ratio obtained for six crude
oils from China, Nigeria and Austraha together with
some geochemical data for each sample. Figure 5
shows a plot of these vahres for each sample against
the parameters DNR-2 and DNR-5. It is apparent
that the DNR values increase with increasing 2OS/
20R values, indicating that both DNR ratios are
sensitive to change in thermal maturity. It is interesting
to note that the Barrow Condensate sample, which
has a 20!3/20R value indicative of equilibration, has
DNR ratios considerably greater than that of the
other samples. This suggests that it separated from
source beds which were appreciably more mature
than were those from which the other samples were
derived. It also shows that the DNR parameters have

TNR- 1

FIG. 3. Dimethylnaphtbalene and trimethylnaphthalene isomer ratios plotted against depth for
Jupiter-l (0) and Cape Range-2 (0) sequences. For definitions refer to Table 9.
 R. Alexander el ai

Substitution
NO. Abbreviation Definition= Pattern RefelW”W

1 WI-1 Radke 81 a.,

1982a.b:1983

2 “PI-2 Radke at &.

1982a,b;1983

3 DNR-1 Radke fi a..

1982b

4 DNR-2
This York

5 DNR-3 This work

6 DNR-4 This K)rk

1 DNR-5 This work

8 TNR-1 t2.3.6-Ml em This work

tl,4,6-ll4Nl+~l,3.S-TWll acle + oell

= P-phenantbrmc
HP-methylphemnthrene

a greater dynamic range than does the parameter
based on epimer ratios. Figure 6 shows a similar plot
using the TNR-1 parameter. Again a correlation is
observed between the two variables indicating that it
too is reflecting changes in the thermal maturity of
the source beds at the time when the crude oils
separated, and migrated into reservoirs where thermal
alteration apparently proceeded at a lower rate.
The use of dimethylnaphthalene and trimethyl-
naphthalene relative abundances as oil maturation
indicators has some advantages and some disadvan-
tages over those based on biological marker com-
pounds. The DMNs and TMNs are abundant in
most crude oils and are usually present in higher
concentrations than are the steranes and triterpanes
particularly in light crudes and condensates. Their
high relative abundance means that the use of alkyl-
ated naphthalenes as maturity indicators is less sus-
ceptible to interference. For instance, in circumstances
where multiple generation and accumulation episodes
have occurred, one oil which is only a minor com-
ponent of the total accumulation may provide erro-

3.8,

4.8, DNR-4

400 1200 2000

DNA

FIG. 4. Variation with depth of dimethylnaphthalene ratios based on 1.8dimethylnaphthalene in Cape

Range sequence. For definition of DNR-2 (0). DNR-3 (*), DNR-4 (A) and DNR-5 (0) refer to Table 9.
 Methylnaphthalenes in sediments 393

Secondly, DMNs and TMNs abundances are affected

DNR-2
by microbial degradation at an earlier stage than are
1.1. . -.. . 1
&jR_5 steranes
(VOLKMAN et al., 1984). Finally, as RADKE
. .. . et al. (1982a) have pointed out, the volatility of the
dinuclear aromatics makes them more susceptible to
evaporation losses during separation and analysis
. .
than are the trinuclear aromatics. They are also more
0.0 IT
0.1.P.
volatile than steranes. However, we have shown (AL-
EXANDER et41.. 1983a) that this is not a problem in
@al 1000 3ooo
‘200 DNR the present context. The use of ratios of isomers with
FIG. 5. A plot of C-20 epimer ratios of ethylcholestane very similar physical properties does not result in
versus DNR-2 (0) and DNRJ (A) ratios. distorted values even when some evaporation has
occurred from the sample: apparently equal propor-
tions of the compounds involved are removed, and
neous biomarker maturity results if it is enriched in
evaporative losses are minim&d by using very volatile
biological marker compounds due, for example, to
solvents during separations (ALEXANDER et al.,
biodegradation (cf VOLKMAN et al.. 1984).
1983a).
DNR-2 and DNR-5 ratios have values ranging
from 50-100 for immature samples to values in
CONCLUSIONS
excess of 1000 for mature petroleum (Fig. 5). By
contrast, epimetization at chiral centres in biological ( 1) In two sedimentary sequences from Northwest
markers usually produces ratios which vary between Western Australia the proportions of certain di- and
0.2 and 1. I (e.g.MACKENZIE ef al.. 1982). DNR-2 trimethylnaphthalenes changed in a regular fashion
and DNR-5 (as well as other ratios based upon 1.8- with increasing sediment maturity as determined by
DMN relative abundance) are therefore more sensitive vitrinite reflectance, Rock-Eva1 T,,,,, and methyl-
indicators of thermal maturity differences than the phenanthrene index. Similar behaviour was observed
sterane ratios. The sterane ratio also has a restricted when the same proportions were compared with C-
range of application in that epimerization reaches 20 epimer ratios of ethylcholestane in some crude
equilibrium either before or at about the stage of oils from China, Nigeria and Australia.
maximum oil generation in sediments. DNR and (2) Ratios of compounds which involve the isomers
TNR measurements have an advantage here in that with a high degree of a-substitution to the others
they appear to undergo a regular change through the with a high degree of &substitution are the most
region of the oil window (as defined by vitrinite sensitive to changes in thermal maturity.
reflectance) and have a useful range which extends (3) The methylnaphthalene isomer ratios provide
into the wet gas zone. a useful additional technique for assessment of petro-
The use of methylnaphthalene ratios also has certain leum maturity.
disadvantages for assessing oils maturity when com-
pared with the biological markers ratios. Firstly. the A~,knou,led~ements-We are grateful to G. Chidlow and R.
low concentrations 1.8-DMN are more difficult to Noble for help with GC-MS analyses, to P. Lester for
measure accurately than are those of sterane epimers. obtaining Rock-Eva1 data and to Dr E. Horstmann for
helpful discussions pertaining to the geological aspects. We
thank Phillips Australia Oil Company and West Australian
Petroleum Ltd. for providing samples. This project was
[2os carried out as part of the National Energy Research Devel-

I
opment and Demonstration Programme, administered by
[20R 3 the Department of National Development.

Edirorral handling: C. Barker

0.a REFERENCES
ALBRECHT P.. VANDENBROUCKE M. and MANDENGU~ M.
(1976) Geochemical studies on the organic matter from
the Douala Basin (Cameroon)-I. Evolution of the ex-
tractable organic matter and the formation of petroleum.
0. 7 &whim. Cosmochim. AcIa 40, 79 1-799.
ALEXANDER R., KAGI R. 1. and LARCHER A. V. (1982)
Clay catalysis of aromatic hydrogen-exchange reactions.
4 Geochim. Cosmochim. AM 46, 2 19-222.
0 nr
_.- 0.8
TNR- 1 ALEXANDER R.. KAGI R. 1. and SHEPPARD P. N. (1983a)
Relative abundance of dimethylnaphthalene isomers in
FIG. 6. A plot of C-20 epimer ratios of ethylcholestane crude oils. J. Chromamgr. 267, 367-372.
versus a trimethylnaphthalene isomer ratio for six crude ALEXANDER R., KAGI R. I., LARCHER A. V. and WOOD-
oils. For definition of TNR-I refer to Table 9. HOUSE G. W. (1983b) Aromatic hydrogen exchange in
394 R. Alexan der n ui
petroleum source rocks. In Advance.r rn Or~unir (;eo-
chetnistr_r 1981, pp. 69-7 I. Wiley.
ALEXANDERR., KAGI R. and SHEPPARD P. ( 1984) 1.8
Dime~hyinaphthalene as an indicator of petroleum ma-
turity. Nature 308, 442-443.
BALASUBRAMANIYAN V. ( 1966) per&Interaction in naphtha-
lene derivatives. Chem Rev, 66, 567-64 I,
BARBERP. M. ( 1982) Palaeotectonic evolution and hydro-
carbon genesis of the Central Exmouth Plateau. APE,4 J.
22(l), 131-144.
BREGERI. A. (1960) Diagenesis of metabolites and a dis-
cussion of the origin of petroleum hydrocarbons. Geochim.
Cosmochim. Acla 19, 297-308.
BRWKS B. T. (1948) Active-surface catalysts in formation
of petroleum. Amer. Assoc. Pewol Geol. Bull. 32, 2269-
2286.
BROOKSB. T. (1952) Evidence of catalytic action in petro-
leum fo~ation. Ind. Eng. Chem. 44,2570-2577.
BROWNH. C. and JUNGK H. (1955) The isomerization of
o and pxylenes and some reiated alkylbenzenes under
the influence of hydrogen bromide and aluminium bro-
mide: the relative isomerimtion aptitudes of alkyl groups.
J. Amer. Chem. Sac. 71, 5579-5584.
BYERSJ. D. and ERDMANJ. G. (1983) Low temperature
degradation of carotenoids as a mode1 for early diagenesis
in Recent sediments. In Advartws in &gunk Ge~hemis~~
1981, pp. 725-732. Wiley.
CARRUTHERSW. and DOUGLASA. G. (1955) The constit-
uents of high-boiling petroleum distillates Part II. Tri-
methylnaphthalenes in a Trinidad oil. J. C’hem. Sac.:
1847-1850.
COOK A. C. and KANTSLERA. J. ( 1980) The maturation
history of the epicontinen~l basins of Western Australia.
1%’ ESC4P. CCOP/SOPAC Tech. Bull. 3, 17I-195.
CULLINANEN. M. and CHARD S. 3. (1948) Mechanism of
substitution in the naphthalene nucleus. Narurr 161,690.
DEWARM. J. S. (1959) Aromatic rearrangements. In Theo-
retical Organic Chemistry (Kekuli Symposium. London,
1958). pp. 179-208. Buttenvorths.
DEWAR M. J. S. (1963) Aromatic rearrangements. In MO-
iecular Reawange~~enf.~fed. P. DE MAYO). pp. 295-344.
Interscience.
INNER H. E. and MORTLAND M. M. (1969) Benzene
complexes with copper (II) montmorillonite. Science 146,
I406- 1407.
DOUGLAS A. G. and MAIR B. J. (1965) Sulphur: role in
genesis of petroleum. Science 147, 499-501.
DUSWALTJ. M. and MAYER T. J. (1970) Separation and
characterization of methylnaphthalene isomers by chro-
matographic and spectrometric methods. Ana/. Chem. 42,
1789- 1794.
DUSWALTJ. M. and MAYER T. J. (1971) Characterization
of the dinuclear aromatics in the 275 to 295’C fraction
of catalytic gas oil. Preprims. Div. Petrol. Chem.. ACS 16,
A i7-A36.
EKWEOZORC. M.. OKOGUN J. 1.. EKONG D. E. U. and
MAXWELLI. R. (1979a) Preliminary organic geochemical
studies of samples from the Niger Delta (Nigeria). I.
Analyses of crude oils for triterpanes. C’hmr. G& 27,
I l-28.
EKW~EOZOR C. M.. OKOGUN J. I., EKONG D. E. U. and
MAXWELLJ. R. (1979b) Preliminary organic geochemical
studies of samples from the Niger Delta (Nigeria). II.
Analyses of shale for triterpenoid derivatives. Chem. Geoi.
27,29-37.
ESPITALI~J., LAPORTEJ. L., MADEC M., MARQUIS F.,
LEPLATP., PAULETJ. and BOUTEFEUA. (I 977) Methode
rapide de caracterisation des roches meres, de leur potentiel
p&rolier et de leur degrk d’bolution. Rev. Insl. Fr. Pet.
32,23-42.
FR~PIATJ. J. and CRUZ-CUMPLI~ M. I. (1974) Clays as
catalysts for natural processes. Ann. Rev. Earth Planet.
Sk 2, 239-256.
CjAVAT I. and fRIMEsCU 1. i 194I) Aromatische Kohtenwas-
serstoffe aus ~m~ni~hern Erdiil, I. Mitteil.: lsolierung
von Dimethyl-napbth~inen aus Gasiil (Aromatic hydra
carbons from Rumanian petroleum. Part I: Isoiatron of
dimethylnaphthalenes from gas oil). Ber. Drsch C&W;
Ges. B. 74, 1812-1817.
GAVAT I. and IRIMESC~~ I. ( 1942) Aromattsche Kohlenwas-
serstoffe aus rumlnischem Erdol, II. Mitteil.: Isolierung
von T~methyl-naphthalinen und Phenanthmn. (Aromatic
hyphens from Rumanian petroleum. Part II: Isolation
of t~me~ylnaphth~en~ and of phenanthrene). ttcrr Ifis&
Chem. Ges. B 75, 820-826.
GOLDSTEINT. P. ( 1983) Geocatalytic reactions in formanon
and maturation of petroleum. Amer. .As.wc. Pe/roi Geol.
Bull. 67, l52- 159.
VANGRAASG.. BAASJ. M. A.. VANDE GRAAF B. and IX
LEEUW1. W. (1982) Theoretical organic geochemistry I.
The the~~ynamic stability of several chotestane isomers
calculated by molecular mechanics. Geachim. Cosmnchim.
Acta 46, 2399-2402.
HANSONW. E. (19.59) Some chemical aspects of petroleum
genesis. In Resmrchcs in Geochemistgs (ed. P. H. ABEL.-
SON), pp. 104-l 17. Wiley.
ISHIWATARIM. (198la) Thermal reaction of &carotene.
Part I. J. Anat A&. Prro1rsr.r 2, 153-167.
ISHIWATARIM. (I981 b) Thermal reaction of &carotene.
Part 2. Pyrolysis in the presence of Kaofinite. .f .lna/.
AppI Pyrolysis 2, 339-35 I.
ISHIWATARIR. and FUKUSHIMAK. (1979) Generation of
unsaturated and aromatic hydrocarbons by thermal alter-
ation of young kerogen. Gtwhim. Cosmochim. .&IO 43,
1343-1349.
JOHNS W. D. (1979) Clay mtneral catalysis and petroleum
generation. Ann. Rev. Earth Planer. Set. 7, 183-198.
JONES D. M., DOUGLAS A. G., PARKE.SR. J., TAYLORJ..
GIGER W. and SCHAFFNERC. (1983) The recognition of
biodegraded petroleum-derived aromatic hydrocarbons in
Recent marine sediments. Mar. foliur. Bull. 14, 103-108.
KARR C.. ESTEP P. A.. TA-CHUANGLo CHANG and COM-
BERIATIJ. R. (1967) Identification of distillable paraffins.
olefms, aromatic hydrocarbons and neutral heterocycfics
from a low temperature bituminous coal tar. t’.S. Bureau
Mines ff u/i. 637, 198 pp.
LAMMERTSMAK. (198 I) Protonation of polymethylnaph-
thalenes and hexahydropyrene. Formation of stable na-
phthalenium ions and observation of isomerizations based
on ‘H and i3C nuclear magnetic resonance studies. J
Amer. Chem. Sac. 103, 2062-2069.
MACKENZIE A. S., PATIENCE R. L.. MAXWELL J. R.,
VANDENBROUCKE M. and DURAND B. C1980) Molecular
parameters of maturation in the Toarcian Shales. Paris
Basin, France-l. Changes in the configurations of acyclic
isoprenoid alkanes, steranes and triterpanes. Geochrm
Cosmtxhim. .&~a 44, 1709- I72 I.
MACKENZIEA. S., BRASSELLS. C‘., EGLINTON G. and
MAXWELLJ. R. (1982) Chemical Fossils: The geological
fate of steroids. Science 2 17, 49 t-504.
MACKENZIEA. S., MAXWELLJ. R., CC)LEMANM. 1. and
DEEGAN C. E. (1983) Biological marker and isotope
studies of North Sea crude oils and sediments. E/~Yw/I
iiiwid Petrol. Congress Prcpr. PD 114). I?. pp.
MAIR B. 1. and MAYER T. J. (1964) Composition of the
dinuclear aromatics, Cit to C,,, in the light gas oil fraction
of petroleum. Anal. Chum. 36, 35 l-362.
MARTIN A. R. and SAXBY 1. D. (1980) Source rock data
on samples from the Perth, Carnarvon. Canning. Browse
and Bonaparte Gulf Basins. CSIRO (Australia). InsI.
Earth Resources, Fuel Geoscience Unrl, Investigalion Re-
pan H.5. I5 pp.
MAYER F. and SCHIFFNERR. (1934) Umlagerung van o-
Na~th~in-~~vaten in ~-Naph~~in-~~vate unter dem
Einfluss von katalysatoren. (Rearrangement of a-naphtha-
lene derivatives into A-naphthalene derivatives under the
 Methyinaphthalen~
influence of catalysts). Ber. Dfsch. Chem. Ges. &‘%?; 63-
69.
MCCAULAY D. A. and LIEN A. P. (1952) Isomer&ion of
methylbenzenes. J. Amer. Chem. Sot. T&6246-6250.
MEINSCHEINW. G. (1959) Or&i of petroleum. Amer.
Assoc. Petrol. Geot. Buh. 43, 925-943.
MILL~GAND. E.. BECKERE. D. and PITZER K. S. (1956)
Thermodynamic functions of alkylnaphthalenes from 298
to lSO@K. J. Amer. Chem. Sot. 78.2707-271 I.
MOORSH. T. (1980) A formation temperature study of the
Camarvon Basin. Geol. Surv. Western Ausf. 1979 Ann.
Report, pp. 45-51.
MORTLANDM. M. and PINNAVIAT. J. (1971) Formation
of copper (I&amne complexes on the inter~mel~ suiikces
of montmo~llonite. Nature Phys. Sci. 229, 75-77.
MUTTONI. M. (1979) Capillary gas chromatography of the
isomeric dimethylnaphthalenes and of some additional
aromatic compounds. J. Chromatogr. 172, 438-440.
OKU A. and YUZENY. (1975) Acid-catalyzed rearrangements
of polymethylnaphthalenes. J. Org. Chem. 40, 3850-
3857.
PACKERJ., VAUGHANJ. and WONG E. ( 1958) Steric strains
in methylnaphthalenes. J. Amer. Chem. Sot 80, 905-
907.
PHILP R. P., GILBERT T. D. and FRIEDRICH J. (1982)
Geochemical correlation of Australian crude oils. APEA
J. 22(I), 188-199.
PINNAVIAT. J. and MORTLANDM. M. (1971) lnterlamellar
metal complexes on layer silicates. 1. Copper (II)-arene
complexes on montmo~llonite. J. Phys. Chem. 75, 3957-
3962.
PLAYFORDP. E., COPE R. N., COCKBAINA. E., Low G. H.
and LOWRY D. C. (1975) Phanerozoic. In The Geology
of Western Australia. Western Australia Geol. Survey
Mem. 2, pp. 223-433.
RADKE M., WELTE D. H. and WILLXH H. (1982a) Geo-
chemical study on a well in the Western Canada Basin:
relation of the aromatic distribution pattern to maturity
of organic matter. Geochem. Cosmochim. Acta 46, I-IO.
RADKE M., WILLSCH H., LEYTHAEUSERD. and TEICH-
MULLERM. ( 1982b) Aromatic components of coal: relation
of distribution pattern to rank, Geochim. Cosmochim.
Acta 46, 183 1- 1848.
RADKEM. and WELTED. H. (1983) The m~hylpheMnt~ne
index (MPH a maturity narameter based on aromatic
hydroc&ons. In Advances bz Organic Geochemistry 1981.
pp. 504-5 12. Wiley.
RO~SINIF. D. (1960) Hydrocarbons in petroleum. J. Chcm.
Educ. 37, 554-561.
ROWLANDS. J., ALEXANDERR. and KAGI R. 1. ( 1984)
Analysis of ~rn~ylMphth~n~ in petroleum by capillary
gas chmmat~phy. J. Chromatogr. 294. 407-4 I2.
SEIFERTW. K. and MOLDOWANJ. M. ( 198 1) Paleorecon-
struction by biological markers. Geochim. Cusmochim.
Acta. 45, 783-794.
SHAW H. F. (1980) Clay minerals in sediments and sedi-
mentary rocks. In Developments in Petroleum Geology-?
in sediments 395
(ed. G. D. HCIBSON).pp. 53-85. Applied Science Publish-
SH:?-YANC MACKENZIEA S ALEXANDERR EGLINTON
G., GOW~R A. P., WOLFF ‘G. A. and MAXWELLJ. R.
(1982).A biological marker investigation of petroleums
and shales from the Shengli oilfield, the People’s Republic
of China. Chem. Geoi. 35, l-3 I.
SHINE H. J. (1967) Aromatic Rearrangements, pp. 2-7.
Elsevier.
SIESKIND0.. JOLY G. and ALBRECHTP. (1979) Simulation
of the geochemical transformations of sterols: superacid
effect of clay minerals. Geochim. Cosmochim. Acta. 43,
1675-1679.
SMITH JR. P. V. (1954) Studies on origin of petroleum:
occurrence of hydrocarbons in Recent sediments. Amer.
Assoc. Petrol. Geol. Butt. 38, 377-404.
SULDG. and STUARTA. P. (1964) Isomerization of dimeth-
ylnaphthalenes. J. Org. Chem. 29, 2939-2946.
TE~ARIKK.. FRY&A J. and GHYCZYS. (1978) Gas chro-
matographic separation of naphthalene and biphenyl ho-
mologues on capillary columns. J. Chromatogr. M&223-
228.
TI~SOT8. P. and WELTED. H. (1978) Petroleum Formation
and Occurrenceq Springer-Verlag. 538 pp.
TUCHIHASHIR. and HANZAWAT. (1942) Sulfite terpentine
oil. Il. Pyrolysis of tetrahydrocadalene and the rearrange-
ment of dimethylnaphthalenes. J. Sot. Chem. Ind. Japan
45,273-279. In Chem. Abstr. (1949) 43, 5590.
VANDENBROUC~EM. (1980) Structure of kerogens as seen
by investigations on soluble extracts. In Kerogen: Insoluble
Organic Matter From Sedimentary Rocks (ed. B. DUR-
AND), pp. 41.5-443. Technip.
VASSILAROSD. L.. KONG R. C., LATER D. W. and LEE
M. L. ( 1982) Linear retention index system for polycyclic
aromatic compounds. J. Chromatogr. 252, l-20.
VOLKMANJ. K., ALEXANDERR., KAGI R. I., NO~LE R. A.
and W~DHOUSE G. W. (1983) A geological ~on~m~on
of oil generation in the Barrow SubBasin of Western
Australia. Geochim. Cosmochim. Acfa. 47, 2091-2 105.
VOLKMANJ. K., ALEXANDERR., KAGI R. I., ROWLAND
S. J. and SHEPPARD P. N. (1984) Biodegradation of
aromatic hydrocarbons in crude oils from the Barrow
Sub-Basin of Western Australia. In Advances in Organic
Ge(~hernjstr~, 1983. Wiley. (in press}.
WHITE C. M. and LEE M. L. (1980) Identification and
geochemical significance of some aromatic components
of coal. Geochim. Cosmochim. Acfa 44, 1825-l 832.
WOLLRAB V. and STREIBLM. (1969) Earth waxes, peat,
montan wax and other organic brown coal constituents.
In Organic Geochemistry. Methods and Results (eds. G.
EGLINTONand M. T. J. MURPHY), pp. 576-598. Long-
man.
YEWF. F. and MAIR B. J. (1966) Isolation and identification
of Cl3 to Cl7 alkylnaphthalenes, alkylbiphenyls, and al-
kyldibenzofurans from the 275’ to 305°C dinuclear aro-
matic fraction of petroleum. Anal. Chem. 38, 231-237.