Organic Geochemistry 42 (2011) 425430

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Identication of carotane breakdown products in the 1.64 billion year old

Barney Creek Formation, McArthur Basin, northern Australia
Carina Lee , Jochen J. Brocks
Research School of Earth Sciences, The Australian National University, Canberra, ACT 0200, Australia

a r t i c l e

i n f o

Article history:
Received 10 August 2010
Received in revised form 16 February 2011
Accepted 18 February 2011
Available online 23 February 2011

a b s t r a c t
Some of the oldest, indisputably indigenous, and thermally exceptionally well preserved biomarkers
occur in the uppermost sections of the 1.64 billion year old (Ga) Barney Creek Formation (BCF) of the
McArthur Basin in northern Australia. These rocks preserve more than 22 different C40 carotenoid derivatives, including the saturated hydrocarbons b-carotane, c-carotane and lycopane. However, in deeper
sections of the BCF, saturated carotenoid derivatives were not detected. To determine whether their
absence from the deeper sections is a primary biological phenomenon or the result of degradation, we
simulated the catagenesis of b-carotane in the laboratory by way of hydrous pyrolysis. Using breakdown
products as elution standards, we were able to conrm the presence of b- or c-carotane derivatives in the
deeper sections, where the C40 parent compounds had been degraded.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Carotenoids are widespread and abundant in the biosphere.
However, their fossil products appear to be comparatively rare in
the geological record. This could possibly be caused by their
tendency to break down into smaller units or undergo complex
aromatisation and rearrangement reactions (e.g. Koopmans et al.,
1997; Sinninghe Damst et al., 1997). The most frequently observed
fossil derivatives of carotenoids are derived from the aromatic pigments isorenieratene (I) and chlorobactene (II; see Appendix for
structures). These biomarkers are probably only common because
the aromatic head groups of the cleavage products yield strong
and easily identiable signals in selected ion chromatograms from
gas chromatographymass spectrometry (GCMS) analysis.
In contrast, fossil derivatives of carotenoids with the nonaromatic b- and c-carotane skeletons are less commonly reported.
This apparent scarcity is likely caused by the degradation of the C40
parent structures to smaller saturated hydrocarbon fragments that
are difcult to detect in complex hydrocarbon mixtures. The
generation of shorter carotane fragments may occur via thermal
degradation of b-carotane (III) or c-carotane (IV), or thermal
cleavage of carotenoid moieties bound to kerogen. However, because of the inherent reactivity of their polyunsaturated structure,
carotenoids are often already fragmented and altered during
diagenesis. Therefore, the absence of easily identied structures
Corresponding author. Present address: Department of Geological and Planetary
Sciences, California Institute of Technology, 1200 E California Blvd, Pasadena, CA
91125, USA. Tel.: +1 424 248 8232.
E-mail address: Carina.Lee@anu.edu.au (C. Lee).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.02.006

in the geological record does not necessarily indicate primary

absence from the depositional environment.
Known mechanisms of diagenetic alteration of carotenoids
include sulfurisation (e.g. Payzant et al., 1986; Schaeffer et al.,
1995), expulsion of xylene or toluene (e.g. Byers and Erdman,
1983), microbial fermentation and degradation (e.g. Repeta,
1989; Rontani et al., 1999; Hopmans et al., 2005), quenching of
carotenoids in macromolecular structures (e.g. Kohnen et al.,
1991; Adam et al., 1993) and biological or abiotic oxidation during
early diagenesis (e.g. Repeta, 1989; Rontani and Grossi, 1995;
Hopmans et al., 2005; Hebting et al., 2006). Under rare and specic
conditions, b-carotene may also form easily identiable aromatic
products, including di- and trimethyl aryl isoprenoids. These
aromatics have been detected in, for example, the Parachute Creek
Member (Mahogany Zone) of the middle Miocene Green River oil
shale (Utah) and in North Sea oil (Koopmans et al., 1997).
Saturated cleavage products of b- or c-carotane have been
reported to occur in oils and sediments (Anders and Robinson,
1971; Hall and Douglas, 1983; Jiang and Fowler, 1986). However,
the identication of these cleavage products was only tentative
on the basis of mass spectra. Payzant and colleagues have also
reported organic sulfur compounds such as bicyclic terpenoids that
could be related to b-carotane products (Payzant et al., 1986).
The oldest known carotenoid derivatives and other C40 isoprenoids come from 1.64 Ga dolomites of the Barney Creek Formation
(BCF) in the Glyde River region of the McArthur Basin, northern
Australia. The isoprenoids include (Brocks et al., 2005; Brocks
and Schaeffer, 2008) the unusual bacterial oligoprenyl-curcumanes
(Brocks et al., 2009) and more than 22 C40 carotenoid derivatives,
including the saturated hydrocarbons b-carotane (III), c-carotane

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C. Lee, J.J. Brocks / Organic Geochemistry 42 (2011) 425430

ltered over silica gel (Silica Gel 60, 70230 mesh, ASTM, Scharlau)
and b-carotane recovered (yield 93%).

(IV) and lycopane (V). However, carotenoid derivatives were below

detection limits in the lower sections of the BCF; it is unknown
whether this is a result of the paucity of source organisms, a
change in diagenetic conditions, or increased maturation.
Here, we report the synthesis, mass spectral characteristics and
chromatographic behaviour of a full pseudohomologous series of
b-carotane cleavage products. We have applied this mixture as a
new elution standard to identify b-carotane derivatives in thermally mature sedimentary rocks from the BCF.

2.4. Preparation of b-carotane breakdown products via hydrous

pyrolysis
An aliquot of b-carotane (2.8 mg, 5.2  106 mol) was dried in a
0.5 cm3 quartz reactor (6 mm outer , 4 mm inner , 1 mm wall
thickness, Vycor silica glass tubing). Distilled water (200 ll) was
added and a ca. 1 cm solid quartz ller rod was placed into the
tube. Oxygen was removed by freezing and thawing under
vacuum. The quartz reactor was sealed by melting the tube walls
around the glass ller rod under vacuum.
The reaction vessel was placed in a cold-seal pressure vessel
(Ren 41 alloy) lled with water and a stainless steel ller rod. A
wateroil mixture was employed as the pressure medium; pressure was generated by an air-driven water pressure intensier.
Pressure vessels were heated in horizontally-orientated Kanthalwound tube furnaces, controlled by Eurotherm 91e temperature
controllers. Temperature was monitored using two Type K
(ChromelAlumel) thermocouples; one was positioned in a well
at the end of the bomb and the other on the bomb surface at the
estimated position of the end of the reactor. The conning pressure
was monitored so that it did not exceed ca. 35 MPa. Higher conning loads often resulted in reactor failure. The reactor was heated
to 360 C for 24 h. Under the prevailing P/T conditions, 78% of
the reactor volume was lled with liquid water.
After quenching and extraction from the cold-seal pressure
vessel, the reactor tube was cooled in liquid N2 to condense volatiles, opened and extracted (4) with 50 ll n-hexane. The combined extracts were dried over Na2SO4 (Univar, Ajax Finechem).

2. Geology and methods

2.1. BCF
The geology of the BCF has been summarised by Brocks and
Schaeffer (2008). Briey, the 1.64 (0.003) Ga formation (Page
and Sweet, 1998) is part of the Paleoproterozoic McArthur Group.
It was deposited in the Batten Fault Zone, a northsouth trending
intracratonic rift basin in the McArthur Basin of northern Australia.
The Glyde River sub-basin lies immediately west of the Emu Fault
Zone, a north-trending fault zone dening the eastern limit of the
Batten Trough within the McArthur Basin.
2.2. Samples
The 16 samples were from drill core GR-7, collected in the thermally well-preserved Glyde River sub-basin in the south of the
Batten Fault Zone. The samples are generally dolomitic mudstones
and shales (Brocks et al., 2005). For their lithological context, refer
to Fig. 2F.
2.3. Preparation of b-carotane

2.5. GCMS
The alkane was prepared from b-carotene (31 mg, 5.8 
105 mol; Fluka Analytical, Sigma Aldrich) via catalytic hydrogenation in a 60 ml vessel with 50 ml hexane (95% n-hexane; UltimAR,
Mallinckrodt Chemicals) in the absence of oxygen. H2 was delivered into the solution through a capillary column at 41 kPa. The
solution was saturated with H2 before 20 mg dry Pt/C (10% Pt; Alfa
Aesar) was added. After allowing the reaction to proceed for 7 days
with constant stirring at room temperature, the solution was

GCMS was carried out with a Micromass Autospec Premier as

described by Brocks and Schaeffer (2008). The chromatograph was
equipped with a 60 m DB-5 column (0.25 mm i.d., 0.25 lm lm
thickness) and He was used as the carrier gas (constant ow of
1 ml/min). Samples were injected in splitless mode into a Gerstel
PTV injector at 40 C (held 0.1 min) and heated at 285 C/min to
325 C. For full scan analysis, the GC oven was programmed from

31

m/z 125 123

29

C9

C11

C14

C16

C21

C15

C13

C24

C26

C29

C31

C10

C19

30

C18

C20

C22

C25

C27

C30
26

15

10

11

13

21

14

18
16

x4

15

20

25

30

24

35

27
19

40

45

25

22

20

50

55

60

65

70 min

Fig. 1. Partial ion chromatogram (m/z 123 subtracted from m/z 125) of hydrous pyrolysis products from b-carotane. The peaks are assigned by way of carbon number; black
and white triangles represent isomers of major fragments. The asterisks in the fragmentation diagram of b-carotane mark branching positions where the generation of
breakdown products is unlikely.

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C. Lee, J.J. Brocks / Organic Geochemistry 42 (2011) 425430

40 C (4 min) to 315 C at 4 C/min, with a total run time of

120 min.

3. Results and discussion

Fig. 1 shows the m/z 125123 chromatogram (i.e. m/z 123
subtracted from m/z 125) of the b-carotane cleavage products
generated under hydrous conditions at 360 C for 24 h. The
subtraction was carried out to show the isomer and homologue
distributions of the saturated compounds, without interference
from the minor unsaturated compounds generated. As expected,
products with 12, 17, 23 and 28 carbons were below detection limit because their generation requires the unlikely cleavage of two
carboncarbon bonds (asterisks in Fig. 1). Pseudohomologues with

2.6. Pseudo-Kovats indices (I0 ) values

I0 values were computed using a second order regression equation tted to the elution times of C8 to C34 n-alkanes as reference
compounds. The n-alkane standard was injected into the GC instrument via a PTV injector at 40 C (0.1 min) and ramped at 260 C/
min to 300 C with a purge time of 2 min. The GC oven was
programmed as above.

Table 1
Mass spectral data and pseudo-Kovats indices (I0 values) for b-carotane breakdown fragments.

a
b
c

Compounda

Mass fragments m/zb

I0 c

C9H18
C10H20
C11H22
C13H26
C14H28
C15H30
C16H32
C18H36
C19H38
C20H40
C21H42
C22H44
C24H48
C25H50
C26H52
C27H54
C29H58
C30H60
C31H62

111(100), 69 (83), 83(27), M+ = 126(10)

69(100), 125(45), 83(30), M+ = 140(18), 97(13), 111(12)
69(100), 83(43), M+ = 154(28), 111(14), 97(14), 139(13), 125(9)
69(100), 83(38), 97(30), M+ = 182(27), 112(20), 126(20), 111(17), 125(17), 167(10)
69(100), 83(40), 109(38), 126(31), 95(25), M+ = 196(24), 179(23), 125(23), 111(20), 181(6)
69(100), 83(48), 125(39), 111(25), 97(23), M+ = 210(23), 140(14), 195(7)
69(100), 83(44), 125(28), 97(26), 111(23), M+ = 224(19), 154(8), 209(5)
69(100), 83(44), 125(36), 126(32), 97(32), M+ = 252(25), 112(22), 182(6), 237(6)
69(100), 83(50), 125(27), 111(20), M+ = 266(10), 196(2), 251(1)
69(100), 125(51), 83(40), M+ = 280(26), 111(25), 140(22), 97(22), 196(6), 210(5), 265(4)
69(100), 83(43), 125(41), 111(32), 97(29), M+ = 294(22), 154(10), 197(5), 279(3), 224(3)
69(100), 126(62), 111(46), M+ = 308(46), 125(35), 140(20), 168(17), 196(13), 293(10), 238(6)
69(100), 111(50), 83(47), 126(43), 125(37), 97(32), M+ = 336(21), 196(11), 140(10), 266(4), 321(3)
69(100), 83(43), 125(38), 111(34), 126(33), 97(30), M+ = 350(19), 140(16), 196(6), 210(5), 335(3)
69(100), 83(49), 111(44), 125(43), 126(38), 97(35), M+ = 364(23), 196(7), 154(7), 224(5), 139(5), 349(3), 294(2)
69(100), 83(54), 111(43), 197(43), 125(43), 126(25), M+ = 378(12), 320(3), 238(3), 363(1)
69(100), 83(66), 125(64), 111(61), 197(54), 126(53), M+ = 406(36), 140(18), 196(17), 266(9), 391(4), 336(3)
69(100), 126(65), 111(62), 125(61), 83(58), M+ = 420(17), 196(12), 210(9), 280(5), 266(5), 350(4), 405(3)
69(100), 125(73), 83(69), 111(66), 126(56), 97(55), M+ = 434(39), 140(31), 196(13), 294(5), 419(3), 364(3), 350(2)

872
953
1031
1189
1257
1366
1456
1660
1717
1834
1924
2020
2222
2282
2391
2472
2654
2708
2810

For structures see Fig. 1.

Intensity (%) relative to base ion (100%).
Pseudo-Kovats index.

A
0

200

400

600

Depth (m)

HI (mg HC/g Corg)

800 0
0

TOC (%)
2

435
0

100

100

100

200

200

200

300

300

300

400

400

400

500

500

500

600

600

600

700

700

800

800

800

900

900

900

1000

1000

1000

2,3,6-trimethylisoprenoids

-carotane fragments

C40 aromatic carotenoids,

including
chlorobactane, okenane,
renieratane, renieratane,
renierapurpurane

440

445

450

isoand

455

+
+
+
+
+
+
+
+
+

110.56 m B03252
*
142.73 m B03174
**
209.60 m B03073
*
287.67 m B03183

+
+---

426.70 m B03075

- +

601.50 m GA2911

- -

**

683.54 m B03200

700

2,3,4-trimethylisoprenoids
-carotane

Tmax (C)

- - -

*
**

SANDSTONE

CARBONACEOUS
DOLOMITIC SHALE

DOLOMITIC SHALE
+SILTSTONE

PYRITIC BLACK SHALE

GRADED DOLOMITIC
BRECCIA

SHEARED LAYERING

BRECCIATED
LAYERING

Fig. 2. Rock Eval data, distribution of carotenoid derivatives, sample depth and general lithology for drill core GR-7. (A) Hydrogen index (HI), (B) total organic carbon (TOC)
and (C) Tmax (data from Powell et al., 1987). Dashed lines depth of signicant change in carotenoid derivative assemblage. (D) Position of samples (). Samples mentioned in
the text are identied by name and depth. (E) Bar diagrams showing depth distribution of C40 aromatic carotenoids, trimethylaryl isoprenoids, b-carotane and b-carotane
fragments. Shaded bars indicate areas where compounds were only tentatively assigned; +, compounds detected and , compounds not detected. (F) Dominant lithology of
core.

428

C. Lee, J.J. Brocks / Organic Geochemistry 42 (2011) 425430

To test how well the hydrous pyrolysis conditions simulated

the degradation of b-carotane under geological conditions, we
searched for the cleavage products in thermally well-preserved
sections of the BCF in samples from drill core GR-7. The signals
were most readily detected with a combination of m/z 125123
and M+ chromatograms. In two samples that contained intact
b-carotane (B03162, 45.35 m; B03174, 142.73 m), we were able
to detect the full pseudohomologous series of C9C31 b-carotane
breakdown products, including the isomers generated from
hydrous pyrolysis of b-carotane. Their identity was conrmed by
comparison of the mass spectra with those of carotane breakdown

1031 carbons are represented by two chromatographic signals

(black and white triangles in Fig. 1) or broadened peaks, corresponding to two or more isomers. MS characteristics and I0 values
of the earlier eluting isomers (black triangles) are summarised in
Table 1.
In the pyrolysate, we also identied structures with one unsaturation in the trimethylcyclohexyl ring and one unsaturation in the
isoprenoid chain, as well as possible hydroxy derivatives generated
in low concentration (not shown), perhaps by the quenching of
hydrocarbon radicals. As these byproducts do not occur in mature
bitumen, they are not discussed further.

C22

C22

m/z 308

C21

C21

m/z 294
C20

C20

m/z 280
C19

C19

m/z 266
C18

C18

m/z 252
C16

C16

m/z 224
C15

C15

m/z 210
C14

C14

m/z 196
C13

x2

m/z 182

C13
x2

C11

m/z 154
x2

m/z 140

C10

x8

L
126-434

x2
x4

20

25

30

35

40

45

50

55

min

M
Fig. 3. (A)(K) Partial M+ chromatograms from full scan experiments with carotane cleavage products in B03183 (GR-7, 287.67 m). (L) Summed M+ chromatograms for m/z
126 to 434 from b-carotane hydrous pyrolysis product standard mixture. Black and white triangles represent isomers of the breakdown product series. (M) Bar diagram
highlights elution position of each pseudohomologue.

C. Lee, J.J. Brocks / Organic Geochemistry 42 (2011) 425430

products formed from the hydrous pyrolysis of carotane. We also

detected C32 to C37 pseudohomologues in B03162 and B03174,
albeit in very low abundance. These fragments were probably
generated by the cleavage of c-carotane, which contains a trimethylcyclohexyl ring at one terminus but is acyclic at the other.
In conclusion, the C9 to C31 fragments in the BCF are derived from
b- as well as c-carotane, but with a lower contribution from the
latter.
Fig. 2 juxtaposes lithology, maturity and occurrence of carotenoid derivatives in drill core GR-7. Intact aromatic C40 carotenoid
derivatives were detected to 209.6 m, while 2,3,4- and 2,3,
6-trimethyl arylisoprenoids persisted to 426.7 m and 601.5 m,
respectively (Brocks et al., 2005). In contrast, intact b-carotane
was observed to 142.73 m, while carotane breakdown fragments
up to C22 were detected to 287.67 m. Generally, the average molecular weight of the carotane fragments declined with depth down

429

record. We predict that carotane cleavage products may be more

common in the geological record than suggested by the scarcity
of their C40 parent precursors.
Acknowledgements
We thank J. Hope, J. Wykes, J. Mavrogenes and J. Cowley for
technical advice and support, A.J.M. Jarrett for proof reading and
editing, and M.D. Lewan and T. Ruble for expert advice on pyrolysis
techniques. We thank the two anonymous reviewers for generous
feedback. The work was supported by the Australian Research
Council (DP0557499).

Appendix

II

III

IV

V
l

the core. As the Rock Eval parameters, HI and Tmax indicated a clear
and gradual increase in thermal maturity with depth (Fig. 2A and
C), the disappearance of C40 carotenoid derivatives, followed by
carotenoid cleavage products, may largely be caused by thermal
degradation. However, the disappearance of C40 b-carotane at
110.56 m and reappearance at 142.73 m indicate that maturity is
not the sole cause of carotenoid degradation. Diagenetic mechanisms, as outlined in the introduction, presumably also played a
role. Diagenetic products of sulfurisation, rearrangement and aromatisation products were, however, not detected.
We also searched for b-carotane degradation residues in more
mature sections below 287.67 m of GR-7 (Fig. 3). At 426.7 m
(B03075) and 683.54 m (B03200), we tentatively assigned carotane
breakdown products with 1018 carbons, although each assignment is ambiguous because of low signal/noise ratio. Thus, the observed fragments at 287.67 m represent the oldest evidence for
non-aromatic carotenoid derivatives in the geological record. The
results conrm that the disappearance of intact C40 carotanes with
increasing depth in GR-7 is a result of diagenetic and thermal degradation and not necessarily an indicator of shifting biological
facies.
4. Conclusions
The alkane b-carotane was pyrolysed under hydrous conditions
to create a standard mixture for the identication of thermal
breakdown products in geological samples.
Using the standard mixture, we identied a full series of
carotane breakdown products in sedimentary rocks from the
1.64 Ga BCF where intact b- and c-carotanes had been observed
previously. However, a partial series of carotane cleavage products
was also found in older samples, where the primary signal of carotanes had been degraded. These components represent the oldest
published evidence for non-aromatic carotenoids in the geological

Associate EditorP. Schaeffer

References
Adam, P., Schmid, J.C., Mycke, B., Strazielle, C., Connan, J., Huc, A., Riva, A., Albrecht,
P., 1993. Structural investigation of nonpolar sulfur cross-linked
macromolecules in petroleum. Geochimica et Cosmochimica Acta 57, 3395
3419.
Anders, D.E., Robinson, W.E., 1971. Cycloalkane constituents of the bitumen from
the Green River Shale. Geochimica et Cosmochimica Acta 35, 661678.
Brocks, J.J., Love, G.D., Summons, R.E., Knoll, A.H., Logan, G.A., Bowden, S.A., 2005.
Biomarker evidence for green and purple sulfur bacteria in a stratied
Palaeoproterozoic sea. Nature 437, 866870.
Brocks, J.J., Schaeffer, P., 2008. Okenane, a biomarker for purple sulfur bacteria
(Chromatiaceae), and other new carotenoid derivatives from the 1640 Ma
Barney Creek Formation. Geochimica et Cosmochimica Acta 72, 13961414.
Brocks, J.J., Bosak, T., Pearson, A., 2009. Oligoprenyl-curcumanes and other new
aromatic isoprenoids from the 1.64 billion year old Barney Creek Formation.
Organic Geochemistry 40, 795801.
Byers, J.D., Erdman, J.G., 1983. Low temperature degradation of carotenoids as a
model for early diagenesis in recent sediments. In: Bjory, M. et al. (Eds.),
Advances in Organic Geochemistry 1981. John Wiley & Sons Limited,
Chichester, pp. 725732.
Hall, P.B., Douglas, A.G., 1983. The distribution of cyclic alkanes in two lacustrine
deposits. In: Bjory, M. et al. (Eds.), Advances in Organic Geochemistry 1981.
John Wiley & Sons Limited, Chichester, pp. 576587.
Hebting, Y., Schaeffer, P., Behrens, A., Adam, P., Schmitt, G., Schneckenburger, P.,
Bernasconi, S., Albrecht, P., 2006. Biomarker evidence for a key preservation
pathway of organic carbon. Science 312, 16271631.
Hopmans, E.C., Schouten, S., Rijpstra, W.I.C., 2005. Identication of carotenals in
sediments. Organic Geochemistry 36, 485495.
Jiang, Z.S., Fowler, M.G., 1986. Carotenoid-derived alkanes in oil from northwestern
China. Organic Geochemistry 10, 831839.
Kohnen, M.E.L., Sinninghe Damst, J.S., de Leeuw, J.W., 1991. Biases from natural
sulfurisation in paleoenvironmental reconstruction based on hydrocarbon
biomarker distribution. Nature 349, 775778.
Koopmans, M.P., de Leeuw, J.W., Sinninghe Damst, J.S., 1997. Novel cyclised and
aromatised diagenetic products of b-carotene in the Green River Shale. Organic
Geochemistry 26, 451466.
Page, R.W., Sweet, I.R., 1998. Geochronology of basin phases in the western Mt Isa
inlier, and correlation with the McArthur Basin. Australian Journal of Earth
Sciences 45, 219232.

430

C. Lee, J.J. Brocks / Organic Geochemistry 42 (2011) 425430

Payzant, J.D., Montgomery, D.S., Strausz, O.P., 1986. Suldes in petroleum. Organic
Geochemistry 9, 357369.
Powell, T.G., Jackson, M.J., Sweet, I.P., Crick, I.H., Boreham, C.J., Summons, R.E., 1987.
Petroleum Geology and Geochemistry, Middle Proterozoic McArthur Basin.
Bureau of Mineral Resources Record 1987/48, 286pp.
Repeta, D.J., 1989. Carotenoid diagenesis in recent marine sediments: II.
Degradation of fucoxanthin to loliolide. Geochimica et Cosmochimica Acta 53,
699707.
Rontani, J.F., Grossi, V., 1995. Abiotic degradation of intact and photooxidised
chlorophyll phytyl chain under simulated geological conditions. Organic
Geochemistry 23, 355366.

Rontani, J.F., Bonin, P.C., Volkman, J.K., 1999. Biodegradation of free phytol by
bacterial communities isolated from marine sediments under anaerobic and
denitrifying conditions. Applied and Environmental Microbiology 65, 5484
5492.
Schaeffer, P., Reiss, C., Albrecht, P., 1995. Geochemical study of macromolecular
organic matter from sulfur-rich sediments of evaporitic origin (Messinian of
Sicily) by chemical degradations. Organic Geochemistry 23, 567581.
Sinninghe Damst, J.S., Baas, M., Koopmans, M.P., Geenevasen, J.A.J., 1997.
Cyclisation, aromatisation, and expulsion reactions of b-carotene during
sediment diagenesis. Tetrahedron Letters 38, 23472350.