Вы находитесь на странице: 1из 8

Pergamon

Org. Geochem. Vol. 26, No. 5/6, pp. 391-398, 1997


1997 Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PII: S0146-6380(97)00006-5 0146-6380/97 $17.00 + 0.00
Kinetics and mechanism of the thermal elimination of alkenes from
secondary stanyl and triterpenyl esters: implications for sedimentary
processes
ROBERT ALEXANDER, PAUL G. KRALERT, IMAM B. SOSROWIDJOJO and
ROBERT I. K A GI
Australian Petroleum CRC/Centre for Petroleum and Environmental Organic Geochemistry, School of
Applied Chemistry, Curtin University of Technology, GPO Box U1987, Perth, 6001, Western Australia
(Received 25 July 1994; returned to author for revision 21 October 1994; accepted 3 January 1997)
Abstract--The liquid phase thermal decompositions of a secondary stanyl ester and a secondary triter-
penyl ester have been investigated in the temperature range from 275 to 320C. First-order rate con-
stants have been measured and the activation energies and frequency factors for the processes
determined. The reactions of naturally occurring sedimentary esters were also investigated by heating
an oil shale at 295C in the presence of tetralin for various periods of time. Analysis of the reaction
products showed that A2-sterenes and da-sterenes were produced at a rate consistent with their for-
mation from secondary stanyl esters by a concerted reaction mechanism. The extent of reaction of sec-
ondary triterpenyl esters in a sedimentary sequence from the Gippsland Basin, Australia, was also
investigated. A correspondence was observed in the depth-calculated-for-reaction obtained using the
laboratory-derived kinetic parameters and the measured depletion of triterpenyl esters in the soluble or-
ganic matter in samples from the sequence. 1997 Elsevier Science Ltd
Key words--stanyl esters, triterpenyl esters, biomarker kinetics, Gippsland Basin, Australia, sterenes
INTRODUCTION
Carboxylic esters occur widely in natural products
that become incorporated into sediments. They are
sufficiently refractory to survive diagenesis and are
present in sedimentary rocks that enter the maturity
zone where thermally induced reactions of organic
compounds take place. Alkyl esters undergo a con-
certed elimination reaction to yield an alkene and a
carboxylic acid, and are an important target for
research for two reasons. Firstly, concerted reac-
tions are insensitive to catalytic effects from the
mineral or maceral matrix of the rock, and the kin-
etic parameters of these processes are therefore po-
tentially useful for inferring the possible thermal
histories of sedimentary sequences in basin model-
ling studies. Secondly, release of alkenes from car-
boxylic esters during the maturation process
provides a reactive species that can readily undergo
carbocation rearrangement reactions, the products
of which are common in hydrocarbons from mature
sedimentary rocks. A knowledge of the timing of
ester elimination might therefore shed light on the
mechanism of formation of these hydrocarbons
with carbon skeletons that are not of natural pro-
duct origin.
The kinetics and mechanism of the thermal de-
composition of esters with long-chain primary alkyl
groups have been reported (Alexander et al., 1992).
This paper compared the reactions of sedimentary
alkyl esters heated under both laboratory and natu-
ral conditions and suggested that the reactions were
similar in both systems. The data suggested that
such well-characterised reactions can be used for
reconstructing the thermal history of sediments (cf.
Alexander et al., 1991).
Carboxylic esters with secondary alkyl groups are
usually more thermally labile than the correspond-
ing primary alkyl esters (Richardson and O' Neal,
1972). They react by a concerted mechanism similar
to the primary alkyl esters (Taylor, 1979;
Richardson and O' Neal, 1972) as shown in
Reaction Scheme 1 and are, therefore, potentially
useful for providing information about the thermal
history of sediments. Due to their increased thermal
lability, they are especially useful in sediments that
have been subjected only to mild heating.
Secondary alkyl esters with the alkyl group in the
form of a six membered ring are of special interest
because such compounds occur widely in sediments.
Steryl esters, for example, have been reported in
Recent and contemporary sediments from marine
environments (de Leeuw et al., 1983; Wakeham et
al., 1984). Fatty acid esters of pentacyclic triter-
penoids and of steroids have also been found in
lacustrine sediments with a terrestrial input
(Cranwell, 1986; Cranwell and Volkman, 1981).
More recently steryl chlorin esters have been idento
391
392
R e a c t i o n S c h e m e I
Robert Alexander et al.
R , , ,
, [ L H
I O " ~ R
H
h e a t
R = H o r a l k y l
e s t e r
v
ified in surface sediments (King and Repeta, 1991;
Eckardt et al., 1992) and Miocene shale/mudstone
samples (Prowse and Maxwell, 1991; Eckardt et al.,
1992).
A preliminary report on the kinetics of the stanyl
ester used in this study has been made (Alexander
et al., 1993). In this paper we report in detail on the
elimination reaction of this stanyl ester and of a tri-
terpenyl ester.
EXPERI MENTAL
Preparation of st anyl and triterpenyl esters
Cholestan-3/?-yl nonanoat e (I) was prepared by
hydrogenat i on of the corresponding cholest-5-en-
3/%yl ester (East man-Kodak) in 70:30 v/v glacial
acetic acid:cyclohexane (275kPa hydrogen, 40C)
R'~,,,C j R ' " H ~ O
I I , I
R,~C~H o~C~R
a l k e n e a c i d
using Adam' s catalyst (cf. Nace, 1951; Augustine,
1965).
3//-Acetoxy-17/%carboxymethyl-lupane (II) was
synthesized from betulic acid (3/~-hydroxy-17/~-car-
boxyl-lup-20(29)-ene), isolated from the bark of the
tree Melaleuca rhaphiophylla, located on the banks
of the Swan River, Perth, Western Australia, by
ether extraction and recrystallization from ethanol
courtesy of Dr S. G. Errington, School of Applied
Chemistry, Curtin University of Technology, WA.
Treatment of the acid with ethereal diazomethane
gave the methylated derivative 3/~-hydroxy-17/~-car-
boxymethyl-lup-20(29)-ene, which was subsequently
converted to the 3/%acetoxy-compound by heating
under reflux with acetic anhydride/pyridine.
Hydrogenat i on of the product after workup (etha-
nol; 330 kPa hydrogen, ambient) using 5% palla-
dium on carbon as catalyst yielded 3/~-acetoxy-17/~-
carboxymethyl-lupane (II).
C6H17 "~O ~ O It,,..
I
J & ,,.
A | ~ ' ~ ~ O'CH3
C H , ~ O ~ L-" v o
I I
I I I
IV
~
O~cH 3
V
Thermal elimination of alkenes from esters 393
Heating experiments
Heat i ng experi ment s were per f or med in two sep-
ar at e studies. One i nvol ved the st anyl est er (I) and
the t ri t erpenyl ester (II); the ot her an oil shal e from
Jul i a Creek, Aust r al i a (Pat t erson et al., 1986).
Kinetic studies using single compounds
Fo r ki net i c measurement s, react i ons were carri ed
out in evacuat ed and sealed 8 0 mmx 2 mm i.d.
glass ampoul es previ ousl y deact i vat ed accordi ng t o
the pr ocedur e of Al exander et al. (1988). In a t ypi -
cal experi ment , ampoul es were charged with the
ester (30/~g) and a sufficient quant i t y of Dexsil
300GC (ca. 400 #g, Al l t ech Associ at es) to afford
an i nert medi um at el evat ed t emperat ures.
Dot r i acont ane (30 #g) was added as an i nt ernal
st andar d. Batches of sampl e t ubes were heat ed at
const ant t emper at ur e (__.0.5C) over the range 275-
320C in a modi fi ed Var i an 2700 gas chr omat o-
gr aph ( Kagi et al., 1990) and removed at appr opr i -
at e t i me intervals. Af t er r api d cool i ng, t he cont ent s
were ext ract ed with di chl or omet hane (3 200 #1).
Conversi on of the pr oduct aci d t o the t ri met hyl si l yl
ester deri vat i ve by t r eat ment with N, O-bi s(t ri -
met hyl si l yl ) t r i f l uor oacet ami de (Supelco, Inc.) facili-
t at ed anal ysi s of the mi xt ure by gas
chr omat ogr aphy (GC). Concent r at i ons of r eact ant
and pr oduct s were det ermi ned by compar i son of
chr omat ogr am peak areas wi t h t hat of the i nt ernal
st andar d and appl yi ng t he appr opr i at e det ect or re-
sponse correct i on factors. I n all experi ment s t he
t ot al mass of unreact ed ester and pr oduct s consti-
t ut ed 90- 100% of t he initial amount of react ant .
Pl ot s of r eact ant concent r at i on (expressed as a log-
ar i t hm) versus time at vari ous t emper at ur es T were
const ruct ed to det ermi ne fi rst -order rat e const ant s
f r om the comput ed line of best fit accordi ng to the
rel at i onshi p bel ow (equat i on 1), where Co is t he in-
itial concent r at i on of react ant , C the concent r at i on
at t i me t, and k t he rat e const ant .
In(C/Co) = - k t (1)
These results were then used t o pr epar e a pl ot of
In k agai nst l I T f r om which t he act i vat i on energy
(E) and t he frequency f act or (Z) for the react i on
were cal cul at ed from t he gr adi ent and i nt ercept re-
spectively using t he Ar r heni us equat i on (equat i on 2),
where R is t he gas const ant .
k = Ze -E/Rr (2)
Experiments with oil shale
Pyrol ysi s experi ment s were conduct ed on a pre-
ext ract ed cal careous oil shal e from the Jul i a Creek
deposi t (Tool ebue For mat i on) pr ovi ded by Dr C.
Boreham, AGSO, Canber r a. A sampl e (20 g) of t he
shal e was gr ound in a disc mill t o pass t hr ough a
100/~m sieve and ext ract ed by ul t rasoni cat i on with
di chl or omet hane (150ml ) for 2 h. Fl ot at i on of the
less dense mat eri al using aqueous zinc br omi de sol-
ut i on (densi t y 2.1 g cm -3) pr ovi ded an organi c
enriched fraction. Dri ed subsampl es (100mg) of
this organi c rich mat er i al were placed i nt o deacti-
vat ed 80 mm x 7 mm i.d. glass t ubes t oget her with
squal ane (12.5/~g, i nt ernal st andar d) and redistilled
t et ral i n (200 #1). Tet ral i n was added as a radi cal
scavenger to i nhi bi t al kene f or mat i on from free rad-
icals. Ampoul es were t hen evacuat ed and sealed,
and pl aced in a const ant t emper at ur e oven at 295C
for 0. 5-72 h.
When quenched, the liquid pyr ol ysat e was recov-
ered by fi l t rat i on and combi ned with the residue
washings (3 x 2 ml di chl oromet hane). Fol l owi ng
evapor at i on of the vol at i l e solvent on a sand bat h,
the sol ut i on was furt her concent rat ed to small
vol ume (ca. 25/ d) by careful l y removi ng the bul k of
the t et ral i n under a st ream of ni t rogen at 75C.
Pyrol ysat es were subsequent l y separ at ed by thin-
l ayer chr omat ogr aphy (TLC) i nt o al i phat i c
(Rf>0. 75), ar omat i c (By 0.05-0.65) and pol ar
( Rf < 0.05) fract i ons on act i vat ed al umi na (60
GF254 neut ral , t ype E, Merck; 0.6 mm), devel opi ng
with n-hexane (t et ral i n band Rf 0.65-0.75). The ali-
phat i c fract i on was furt her subjected to liquid chro-
mat ogr aphy ( Li Chr opr ep Si 60, 40-63/~m, Merck;
n-hexane el uant ) pr i or to GC analysis in or der to
remove traces of tetralin.
GC analysis
Product s were dissolved in n-hexane and anal ysed
using a Hewl et t Packar d 5890A gas chr omat ogr aph
fitted with a 60 m x 0.25 mm i.d. WCOT fused-silica
bonded met hyl si l i cone phase col umn (DB-1, J & W
Scientific) and a flame i oni zat i on detector.
Hydr ogen was used as carri er gas at a l i near flow
velocity of 30 cm s - l . Samples were injected on-col -
umn at 45C and the oven was t emper at ur e pr o-
gr ammed to 280C at 4C min - l . Dat a acqui si t i on
and processi ng were managed using a PC-based
DAPA software package ( DAPA Scientific
Software).
Pyrolytic methylation-gas chromatography
On-line pyrol yt i c met hyl at i on- gas chr omat og-
r aphy was carri ed out on the asphal t enes ext ract ed
from sediments from the offshore region of the
Gi ppsl and Basin, Aust r al i a (for sampl e details see
Al exander et al., 1991), with a Pyr oj ect or mi crofur-
nace ( SGE Scientific) i nt erfaced via the capi l l ary
inlet system to a Hewl et t Packar d 5890A gas chro-
mat ogr aph fitted with a 25 m x 0.2 mm i.d. WCOT
fused-silica cross-l i nked methylsilicone phase col-
umn (HP-1, film thickness 0.33/am, Hewl et t
Packard). In an adapt at i on of a met hod described
by Chal l i nor (1989), samples (ca. 3 mg) were pre-
par ed as sol i d pellets moi st ened with 25% w/w aqu-
394 Robert Alexander et al.
eous t et r amet hyl ammoni um hydr oxi de sol ut i on
(2.0/A) and i nt r oduced di rect l y i nt o the pyrol yser,
which was mai nt ai ned at 400C. Hel i um was used
as bot h pyrol ysi s and carri er gas (linear velocity
3 0 c ms - l ) , and injections were splitless ( l mi n
hold). The oven was pr ogr ammed from 10C
( 2mi n) to 215C at 4 Cmi n -1 and t hereaft er at
2C min - t to 280C (15 min). El ut i ng compounds
were moni t or ed by a Hewl et t Packar d 5970B mass
selective det ect or in the full dat a acqui si t i on mode,
scanni ng from 40 to 540 amu in 1.3 s cycles. Typi cal
mass spect romet er oper at i ng condi t i ons were: elec-
t ron mul t i pl i er vol t age 1750V; emission current
220/~A; el ect ron energy 70 eV; source t emper at ur e
2200C. Pyrol ysi s pr oduct s were identified from t hei r
mass spectra.
C o m p u t e r mo d e l l i n g
A commerci al l y avai l abl e model l i ng package
( PDI / PC from IES, Julich, Ger many) was used to
obt ai n buri al histories and to pr oduce the vari ous
heat flow-time rel at i onshi ps t hat best describe the
present t emper at ur es in t he sedi ment column.
RESULTS AND DI SCUSSI ON
K i n e t i c s
Cholestan-3/~-yl nonanoat e (I) and 3/~-acetoxy-
17~-carboxymet hyl -l upane (II) were selected as
exampl es of esters with secondary al kyl groups and
with sufficiently low vol at i l i t i es t o enabl e measure-
ment s t o be made on liquid phase processes. The
sampl es were heat ed for vari ous peri ods of time at
precisely regul at ed t emperat ures, and the react i on
mi xt ure was anal ysed using capi l l ary GC techniques
t o det ermi ne the extent of reactions. In all exper-
iments used for kinetic measurement s, chr omat o-
grams of t he react i on mi xt ures showed no
significant peaks from ext raneous compounds and
conversi on of the esters t o carboxyl i c acids and
alkenes was essentially quant i t at i ve. Rat e const ant s
for the t her mal decomposi t i on of the stanyl ester
were det ermi ned over the t emper at ur e range 275 -
320C. In all cases t he react i on pr oduct s were the
A2-sterene (III) and the A3-sterene (IV) which
formed in a 2:1 rat i o. Fi gur e l a shows a pl ot of the
results obt ai ned from one set of experiments: the
l i near rel at i onshi p exhi bi t ed by the vari abl es in this
pl ot was t ypi cal of the kinetic dat a obt ai ned at all
t emperat ures, and showed t hat t he process can be
adequat el y descri bed by a fi rst -order kinetic t reat -
ment. In the case of the t ri t erpenyl ester (II), a
single react i on pr oduct , compound V, was obt ai ned
in all experiments. Rat e const ant s for the t hermal
decomposi t i on of this ester were obt ai ned from rat e
pl ot s of similar qual i t y t o t hat shown for the stanyl
ester (Fig. l a). Fi gur e l b shows the Ar r heni us pl ot s
for the stanyl and t ri t erpenyl esters. The act i vat i on
energies (E) and frequency fact ors (Z) for the reac-
t i ons were cal cul at ed using the slopes and inter-
cepts. The det er mi nat i on of E and Z has been
carri ed out with similar preci si on to our previ ous
kinetic studies (Kagi e t al . , 1990; Al exander e t al . ,
1992) and are suitable for meani ngful i nt er pr et at i on
when used in geological systems. The kinetic par-
amet ers for the two subst rat es are shown in Fig. l b.
The react i vi t y of the t ri t erpenyl ester compar ed
with the steryl ester is l ower at all t emperat ures
used in this st udy (Fig. l b) . Because the act i vat i on
energies for the two subst rat es are similar, the
difference is due t o the frequency fact ors (entropies)
of the processes. The ent r opy difference between the
two react i ons is pr obabl y rel at ed to the number of
hydrogen at oms on the car bon adj acent t o the ester
funct i onal gr oup t hat can par t i ci pat e in the reac-
tion. I n the case of the st anyl ester, four fl-hydro-
- 0 . 5
r .
- - - 1 . 0
- 1 . 5
0
o . o , .
stanyl ester a
Time (h)
_=
- 9
- 1 0
- 11
- 1 2
- 1 3
b
stanyl ester
~'~,.\ ~ E= 195kj moll
\ ' . . . , ~ ~ 2"48 x 101s s'I
t r i t er panyl e ~ " \
E = 195kj tool -1 "",.,.,,. ~ .
Z = 1"92 x 1m2sl ~ " ~
i i I i , ~ I , i
1 , 7 0 1 . 7 4 1. 8 1 . 8 2
(1/1") x 10 s (K "1)
Fig. 1. Plots showing (a) typical kinetic data used for determining the first-order rate constants and (b)
Arrhenius plots for the stanyl and triterpenyl e s t e r s .
Thermal elimination of alkenes from esters 395
gens are available, whereas in the case of the triter- 0.0
penyl ester the presence of the gem dimethyl group
at C-4 reduces the number of adjacent hydrogens to
two. -o.s
The values obtained in this study for the acti-
vation energies and frequency factors for the reac-
tions of secondary esters are within the range of A
values reported in the literature for gas phase reac- ~ -1.0
tions of secondary alkyl esters. For example, acti- =
vation energies and frequency factors for the
decomposition of secondary alkyl acetates in the
gas phase are in the range 181-203 kJmol -] and -1.5
4 . 0 1 0 1 2 - 8 . 5 1 0 ]3 S - 1 respectively (Richardson
and O' Neal, 1972; Scheer et al., 1963), while
O' Connor and Nace (1953) have reported kinetic
parameters of 184.6 kJ mol -l and 5.1 x 1012 s -I for
the elimination reaction of cholesteryl acetate to
give 3,5-cholestadiene over the temperature range
281-329C.
React i on of secondary al kyl esters in kerogen
In order to measure the sterenes released via a
concerted reaction process during pyrolysis of oil
shale esters the experiment was carried out in the
presence of tetralin. Under these conditions free
radicals formed by other reaction pathways during
the pyrolysis experiment are quenched by hydrogen
donation from tetralin and consequently appear as
saturated products; only the reaction products that
arise via concerted reactions should therefore
appear as alkenes. Figure 2 shows a rate plot for
the formation of A2-cholestene from oil shale or-
ganic matter heated at 295C in the presence of tet-
rails. The value for the initial concentration (Co) of
A2-cholestene was obtained from a plot of In C ver-
sus time (equation 1) by extrapolation to zero time
and placing a greater weighting on the earlier data
points in order to minimise the effects of secondary
reactions of cholestene. The expected rate of for-
mation of the sterene calculated using the kinetic
parameters derived from measurements on chole-
stan-3fl-yl nonanoate is shown as a broken line in
Fig. 2. Clearly, the measured rate of formation of
sterene from the oil shale is similar to the calculated
rate. It is apparent from these data that when
heated under laboratory conditions the stanyl esters
which occur naturally in the oil shale react at a
similar rate to the single synthetic ester used for
kinetic measurements. The result is consistent with
previous reports (cf. Alexander et al., 1992) that
changes in the nature of the alkyl moiety of the car-
boxyl component within one class of ester (i.e.
whether an ester of a primary or secondary alcohol)
have only a minor effect on the kinetic parameters.
We suggest therefore that the kinetic parameters
measured in the laboratory for the stanyl nonanoate
are similar to those of the naturally occurring stanyl
esters in the oil shale.
" . " . . . .
\
" \
".,%
-..~.
"' . . . . . .
. 2 . C 0 t f ~ a , , J
4 8 1 2 1 6
T i m e ( h )
Fig. 2. Plots showing the similarity in the rate of release of
20R cholest-2-ene from Julia Creek oil shale (data points)
and the rate of reaction of the reference stanyl ester
(dashed line).
Reactions o f esters heat ed under geological conditions
in sediments
Using the laboratory determined kinetic data, the
depth interval in a sedimentary sequence over
which reaction occurs can be calculated using basin
modelling software. The result of such a calculation
for sediments heated under conditions typical of
natural heating due to increased subsidence is
shown in Fig. 3. The calculations used a uniform
heating rate (1.7C Ma -l ) and geothermal gradient
(35Ckm -l ) and a surface temperature of 14C.
The results show that reaction of the secondary sta-
nyl ester occurs more readily in sediments than
does reaction of the secondary triterpenyl ester
which, in turn, occurs much more readily than the
corresponding reaction of primary alkyl esters
(Alexander et al., 1992) or the processes of oil for-
mation. Also shown in Fig. 3 is the calculated
extent of reaction for steroid aromatisation using
the kinetic data of Mackenzie and McKenzie
(1983). Clearly the reaction of the stanyl ester and
the aromatisation process both occur at similar
depths (temperatures) in the sediment column. The
apparent coincidence of the two processes in the
depth profiles may be linked: the possibility that the
rate of formation of triaromatic steroids in sedi-
ments is determined by the rate of formation of
unsaturated steroids from esters needs further inves-
tigation; however since neither alkenes nor A-ring
monoaromatics are stable in mature sediments, the
triaromatic steroids might form from the reactions
of C-ring monoaromatic steroids that still contain
an ester functionality at C-3.
Depletion of the esters of olean-3-ol with increase
in depth in a sedimentary sequence from the
Gippsland Basin, Australia, is consistent with
the laboratory determined kinetic parameters for
396 Robert Alexander e t a l .
I I
E
v
P
CI
1000
2000
3000
4000
Age of oldest sediments = 83 Ma
Sur f ace t emper at ur e = 14 C
Heat i ng rat e = 1.7 C Ma "1
Geot her mal gr adi ent = 35 C km "1
" . o . " -
- - - , - . , . . . , . . . , . - - , . - . . . . . . . . . .
""" """'~"T-...,.....,.,,.
5 0 ~ I i i j
0 0. 2 0. 4 0. 6 0.8
Fraction of reaction
1.0
- - - - - pr i mar y al kyl est er s
. . . . . . . . . secondar y st anyl est er s
. . . . secondar y t r i t er penyl est er s
steroid aromatization
labile kerogen (oil formation)
Fig. 3. A plot showing the calculated progress of various reactions with depth for a sedimentary
sequence heated under conditions of a natural system. Kinetic parameters for each reaction type and
their sources were: stanyl and triterpenyl esters, Fig. l(b); primary alkyl esters (Alexander e t a l . , 1991);
steroid aromatisation (Mackenzie and McKenzie, 1983); labile kerogen (Quigley e t a l . , 1987).
ester elimination from a secondary triterpenyl
ester. Figure 4(a) shows the calculated depth profile
for the elimination reaction of the triterpenyl ester
to form the A2-triterpene for the Volador-1 well.
This calculation was done using the same heat flow
history that was previously reported to account for
the reaction of primary alkyl esters in this well
(Alexander e t a l . , 1991) and shows that alkenes
from reaction of secondary alkyl esters in the A-
ring of a triterpenoid begin to form just before
3000m and this process is near completion by
about 3500 m.
The abundance of oleanyl esters in the asphaltene
isolates of samples from the Volador-1 well was
determined by derivatisation- pyrolysis gas chroma-
tography (Challinor, 1989; Kralert e t a l . , 1995). As
is clear from Fig. 4(b), the abundance of the oleanyl
ester in these samples decreases with increasing
depth. Unfortunately, suitable samples were not
available from shallower sections which could be
used to establish the onset of this reaction; however,
the available data does suggest that depletion of the
oleanyl esters in the soluble organic matter (SOM)
Thermal elimination of alkenes from esters 397
3OOO
A
E
e-
K
E 3 4 0 0 0
b
19, 217-227.
Kagi, R. I., Alexander, R. and Toh, E. (1990) Kinetics
and mechanism of the cyclisation reaction of ortho-
methylbiphenyls. In Advances in Organic Geochemistry
1989, eds B. Dur and and F. B6har. Organic
Geochemistry 16, 161-166.
King, L. L. and Repeta, D. J. (1991) Novel pyropheo-
phorbi de steryl esters in Black Sea sediments.
Geochimica et Cosmochimica Acta 55, 2067-2074.
Kralert, P. G., Alexander, R. and Kagi, R. I. (1995) An
investigation of pol ar constituents of kerogen and coal
using pyrolysis-gas chromat ography-mass spectrometry
with in situ methylation. Organic Geochemistry 23, 627-
639.
de Leeuw, J. W., Rijpstra, W. I. C., Schenck, P. A. and
Volkman, J. K. (1983) Free, esterified and residual
bound sterols in Black Sea Uni t 1 sediments.
Geochimica et Cosmochimica Acta 47, 455-465.
Act i vat i on energies and frequency fact ors for the
el i mi nat i on of alkenes from cholestan-3fl-yl nonano-
at e and 3fl -acet oxy-17fl -carboxymet hyl -l upane have
been det ermi ned accurat el y under l abor at or y heat -
i ng condi t i ons. Sedi ment ary secondary st anyl esters
react when heat ed under l abor at or y condi t i ons in a
manner consi st ent wi t h these kinetic paramet ers.
Sedi ment ar y t ri t erpenyl esters, when heat ed under
nat ur al condi t i ons in sediments, are depl et ed in sol-
ubl e organi c mat t er (SOM) in a manner consi st ent
with t he l abor at or y deri ved kinetic paramet ers.
Associate Editor - - B. Si monei t
Alexander, R., Fisher, S. J. and Kagi, R. I. (1988) 2,3-
Dimethylbiphenyl: kinetics of its cyclisation reaction
and effects of mat ur at i on upon its relative concent rat i on
in sediments. In Advances in Organic Geochemistry 1987,
eds. L. Mattavelli and L. Novelli. Organic Geochemistry
13, 833-837.
Alexander, R., Kagi, R. I. and Kralert, P. G. (1993)
Kinetics of the t hermal elimination of sterenes from
5=(H)-stanyl esters: implications for geochemical pro-
cesses in sediments. In Organic Geochemistry: Poster
Sessions from the 16th International Meeting on Organic
Geochemistry, Stavanger 1993, ed K. Oygard, pp. 186-
189. Fai t h Hurtigtrykk, Oslo.
Alexander, R., Kralert, P. G., Marzi, R. and Kagi, R.
I. (1991) A geochemical met hod for assessment of t he
t h e r ma l histories of sediments: a two-well case study
from the Gi ppsl and Basin, Australia. APEA J. 31, 325-
332.
has occurred in the zone predi ct ed usi ng t he l abor a-
t or y kinetic dat a.
5 0 0 0 I I I I ~ I , , , f ,
0 . 0 0 . 2 0 . 4 0 . 6 0 . 8 1 . 0 0 1 0 2 0 3 0
T r i t e r p a n y l e s t e r O l e a n a n - 3 - o l (esterified)
Calculated fraction o f reaction ( n g g-1 S O M )
Fig. 4. Plots showing (a) calculated extent of the triterpenyl ester reaction and (b) measured change in
oleanyl ester concent rat i on in the soluble organic mat t er (SOM) for the Volador-1 well.
Alexander, R., Kralert, P. G. and Kagi, R. I. (1992)
Kinetics and mechanism of the thermal decomposition
of esters in sediments. In Advances in Organic
Geochemistry 1991, eds C. B. Eckardt, J. R. Maxwell, S.
R. Lart er and D. A. C. Manning. Organic Geochemistry
CONCLUSIONS 19, 133-140.
Augustine, R. L. (1965) Catalytic Hydrogenation, p. 63.
Arnold, London.
Challinor, J. M. (1989) A pyrolysis-derivatisation-gas
chromat ography technique for the structural elucidation
of some synthetic polymers. Journal of Analytical and
Applied Pyrolysis 16, 323-333.
Cranwell, P. A. (1986) Esters of acyclic and polycyclic iso-
prenoi d alcohols: biochemical markers in lacustrine sedi-
ments. In Advances in Organic Geochemistry 1985, eds
D. Leythaeuser and J. Rullkotter, pp. 891-896.
Pergamon Press, Oxford.
Cranwell, P. A. and Volkman, J. K. (1981) Alkyl and
steryl esters in a recent lacustrine sediment. Chemical
Geology 32, 29--43.
Eckardt, C. B., Pearce, G. E. S., Keely, B. J.,
Kowalewska, G., Jaff6, R. and Maxwell, J. R. (1992) A
widespread chlorophyll t ransformat i on pathway in the
aquatic environment. In Advances in Organic
REFERENCES Geochemistry 1991, eds C. B. Eckardt, J. R. Maxwell, S.
R. Lart er and D. A. C. Manning. Organic Geochemistry
398 Robert Alexander et al.
Mackenzie, A. S. and McKenzie, D. P. (1983)
Aromat i zat i on and isomerization of hydrocarbons in
sedimentary basins formed by extension. Geological
Magazine 120, 417-470.
Nace, H. R. (1951) An improved hydrogenat i on of choles-
terol to cholestanol. Journal of the American Chemical
Society 73, 2379.
O' Connor, G. L. and Nace, H. R. (1953) Furt her studies
on the Chugaev reaction and related reactions. Journal
of the American Chemical Society 75, 2118-2123.
Patterson, J. H, Ramsden, A. R., Dale, L. S. and Fardy,
J. J. (1986) Geochemistry and mineralogical residences
of trace elements in oil shales from Julia Creek,
Queensland, Australia. Chemical Geology 55, 1-16.
Prowse, W. G. and Maxwell, J. R. (1991) High molecular
chlorins in a lacustrine shale. Organic Geochemistry 17,
877-886.
Quigley, T. M., Mackenzie, A. S. and Gray, J. R. (1987)
Kinetic theory of petroleum generation. In Migration of
Hydrocarbons in Sedimentary Basins, Collection
Colloques Seminaire, ed B. Doligez, Vol. 45, pp. 649-
665. Editions Technip, Paris.
Richardson, W, H. and O' Neal, H. E. (1972) The unimole-
cular decomposition and isomerization of oxygenated
organic compounds (other t han aldehydes and ketones).
In Comprehensive Chemical Kinetics, eds C. H. Bamford
and C. F. H. Tipper, Vol. 5, pp. 381--446. Elsevier, New
York.
Scheer, J. C., Kooyman, E. C. and Sixma, F. L. J. (1963)
Gas phase pyrolysis of alkyl acetates. Recl. Trav. Chim.
Pays-Bas 82, 1123-1154.
Taylor, R. (1979) Pyrolysis of acids and their derivatives.
In The Chemistry of Functional Groups, Supplement B,
ed S. Patai, Pt. 2, pp. 860-914. Wiley, New York.
Wakeham, S. G., Farri ngt on, J. W. and Gagosian, R. B.
(1984) Variability in lipid flux and composition of par-
ticulate mat t er in the Peru upwelling region. In
Advances in Organic Geochemistry 1983, eds P. A.
Schenck, J. W. de Leeuw and G. W. M. Lijmbach, pp.
203-216. Pergamon, Oxford.