Magoon, L. B, and W. G. Dow, eds.

, 1994, The petroleum

system-from source to trap: AAPG Memoir 60.

Chapter 10

Diagenesis, Catagenesis, and

Metagenesis of Organic Matter
Brian Horsfield Jiirgen Rullkotter
Forschungszcntrum [iiticl: Unioersitiit OldL'll/1urg
[uiich, Germanu OldL'IlIJllI"g, GL'rl11lllllj

ABSTRACT
Upon burial, organic matter in sedimentary rock undergoes numerous compositional changes
that are dictated initially by microbial agencies and later mainly by thermal stress. This continuum
of processes is tenned thermal maturation and is divided into three consecutive stages: diagenesis <Ro
< 0.5%), catagenesis (0.5% < Ro < 2.0%), and metagenesis (2.0% < Ro < 4.0%). Kerogen, the major
global precursor of petroleum, consists of selectively preserved, resistant, cellular organic materials
(algal, pollen, spores, and leaf cuticle) and the degraded residues of less resistant biological organic
matter (amorphous material) in variable proportions. Kerogen formation is complete by the end of
diagenesis. The mode of kerogen formation exerts a strong influence on its structure and bulk
composition. and hence on oil- and gas-generating characteristics, during catagenesis. Sulfur-rich
type II kerogen, occurring in carbonate-evaporite source rocks, can generate oil at low levels of
thermal stress. Low sulfur type II kerogen requires more thermal energy to generate oil, and type I
and type ill kerogens still more. High-wax oils appear to be generated from both wax ester and
biopolymeric precursors, the first of which generates at an early stage of catagenesis and the other
throughout catagenesis. The base of the oil window (occurring at Ro < 1.3%) appears to be
controlled by the depletion of long chain components in the case of some terrigenous kerogens and
by oil stability in the case of marine kerogens. In the latter part of catagenesis, all source rocks
contain strongly enhanced proportions of hydrocarbon gases (wet gas). Throughout metagenesis,
source rock kerogens are strongly depleted in hydrogen and generated gases consist of methane
(dry gas) and sometimes hydrogen sulfide or nitrogen. Nevertheless, original oil potential can
sometimes be recognized. Thermal maturity level can be monitored using a wide array of parame-
ters. Steranes, hopanes, and other biological markers respond sensitively to thermal stress. Because
their pseudokinetic parameters are known, these reactions are frequently used in numerical simula-
tion to calibrate thermal history.

INTRODUCTION compounds are valuable means for registering the subtle

progress of diagenetic change. The succeeding stage of
Diagenesis, catagenesis, and metagenesis are three catagenesis corresponds to the main stage of oil
consecutive alteration stages within the carbon cycle that formation from kerogen and is characterized by the
irreversibly effect progressive changes in the composi- occurrence of (assumed) first order thermal cracking
tion of sedimentary organic matter. Collectively, they reactions whose overall rate is governed by kerogen
make up what is commonly termed the process of matura- structure and the extent of thermal stress over geologic
tion. Each stage is characterized by different types of time. Substantial transformation of oil into gas also
chemical processes, although the boundaries between occurs later in catagenesis. Metagenesis falls between
adjacent stages are gradational. Diagenetic processes catagenesis and rock (inorganic) metamorphism and is
occur early in sediment history and form the link characterized by dry gas generation. Being able to
between the biosphere and geosphere. Because kerogen recognize these zones and determine their occurrence in
plays a major role as a petroleum progenitor, its time and space is now accepted as a key consideration in
formation can be considered as the most important petroleum exploration strategy.
feature of this zone. Nevertheless, defunctionalization The subject of thermal maturation of source rocks has
and structural rearrangement of biologically inherited been thoroughly reviewed many times, and most
189
190 Horsfieldand Ruilkiitter

lESS HYDROGEN MORE HYDROGEN CONSIDERATIONS

KEROGEN FORMATION
DIAGENESIS • Precursor organisms
• Diagenetic reactions
• S8IeetIve preservstlon
Ro = 0.5% - - -

PETROLEUM GENERATION
CHARACTERISTICS

• Kerogen structure
• KInetic parameters

CATAGENESIS

* 011 versus gas

• Hlgh-low wax

• 'Uve' carbon

REMAINING POTENTIAL

• Recognmon of original 011

METAGENESIS potential
• Ga genendlon

Figure 10.1.The zonation of thermal maturation intodiagenesis, catagenesis, and metagenesis, a simplified representation
of the bulkresultant processes involved, and highlighted elements indicating the scope of this chapter.

petroleum geoscientists are familiar with its most funda- altered and!or degraded by biologicaland low tempera-
mental aspects. The reader is referred to the reviews of ture chemical transformation processes. This alteration
Hunt (1979) and Tissot and Welte (1984) for concise begins in the water column and extends via unconsoli-
descriptions of the fundamental processes involved in dated sediments to include some compacted sedimen-
thermal maturation and to Heroux et al. (1979) for a tary rocks (typically R, < 0.5%; T < 50 'c).
compilation and generalized correlation of inorganic and
organic thermal maturity parameters. This review sets Kerogen Precursors
out to describe the phenomena characterizing each stage
with balanced reference to both historical milestones and Microbial activity is highest at the sediment-water
the latest available literature to May, 1991. Contrary to interface and at shallow burial depths. This activity is
the popular view of 10 years ago that petroleum responsible for the degradation of a high proportion of
geochemistry must be stripped to its bare bones to be of the originally deposited organic matter into simple
any practical use to the explorationist, we have chosen to molecules such as CO2, N2' and H20 (aerobic condi-
discuss selected aspects of diagenesis, catagenesis, and tions), then NH3, H2S, and CHi (anaerobic conditions)
metagenesis in some geochemical detail because, far and causes the concomitant mobilization of mineral
from being of only academic interest, these subtleties species (Curtis, 1978). The rate of degradation of biologi-
impinge upon everyday decision-making in petroleum cally derived organic matter varies, with a selective frac-
exploration. The scope of this chapter is summarized in tionation in favor of nonhydrolyzable substances. The
Figure 10.1. major survivors of microbial degradation consist of three
chemically ill-defined macromolecular materials called
fulvic acids, humic acids, or humin depending on their solu-
DIAGENESIS bilities in acids and bases. All three are considered to be
potential precursors of kerogens (insoluble in nonoxi-
The term diagenesis, as applied to organic matter, dizing acids, bases, and common organic solvents),
refers to its earliest stage of alteration whereby the which are the major petroleum precursors in fine-
remains of aquatic and/ or terrestrial organisms are grained sedimentary rocks. Only a small proportion of
 10. Diagenesis, Catagenesis, and Metagenesis of Organic Matter 191

the surviving organic matter is in the form of monomole- components with only a relatively weak resistance to
cular species such as polar lipids or the hydrocarbons degradation (e.g., cellulose) may contribute significantly
that result from their defunctionalization. to kerogen formation if they are present in sufficient
Fulvic and humic acids are thought to form via the concentration to form fulvic and humic acids upon
random "repolymerization" or "condensation" of amino partial degradation. In contrast, the same starting
acids, sugars, and phenols that originate from the mixture may yield a kerogen richer in resistant biopoly-
microbial breakdown of proteins, polysaccharides, and mers in more oxygenated waters. This process may be
lignins (Stevenson, 1974). These processes have been operative during the sedimentation and early diagenesis
simulated in the laboratory (Maillard, 1913; Hoering, of both siliciclastic and carbonate source rocks (Gehman,
1973;Hedges, 1978;Rubinsztain et aI., 1984). Polyunsatu- 1%2; Horsfield, 1978;Jones, 1984).
rated lipids such as those found in certain algae (Knights The mode of kerogen formation, and hence the type of
et al., 1970; Blumer et al., 1971) may polymerize directly kerogen that results, is important because it can exert a
(Cane and Albian, 1973;Saxby, 1981)or via sulfur atoms strong influence on the oil- versus gas-generating
(Sinninghe-Damste and de Leeuw, 1990; Adam et al., potential of a source rock. This is particularly true in
1993) to form macromolecular organic matter in a similar deltaic depositional environments where, because
way. Fulvic and humic acids occur in the water column changing river courses are commonplace and tidal influ-
(Stuermer and Harvey, 1974) and in sediments (e.g., ences may be strong, humic substances can be flushed
Rashid and King, 1969;Orem et aI., 1986),and they act as from peats to flocculate elsewhere or be fully degraded,
a geochemical sink for all types of functionalized leading to the formation of a residue rich in oil-prone
compounds such as wax acids and wax alcohols from biopolymeric debris (Thompson et al., 1985). Kerogen
plant cuticles (Larter et al., 1983), isoprenoid moieties formed under these conditions is very different from that
from chlorophyll a (Larter et al., 1979), membrane formed from the same starting material but which was
constituents of archaebacteria (Michaelis and Albrecht, deposited and preserved in a stable peat bog where
1979), and tocopherols (Goossens et al., 1984). Decreases condensation products were more abundant (Karweil,
in the concentrations first of fulvic acids and then of 1966)and the coal was typically gas prone.
humic acids occur as a result of progressive combination
reactions with increasing diagenesis. There is a concur- Kerogen Types
rent elimination of heteroatomic moieties, such as N2'
H20, and notably C02 (Hue and Durand, 1977), as Molecular structural models are derived through
kerogen gradually forms (Nissenbaum and Kaplan, 1972; elemental analysis, spectroscopic methods (such as
Hue and Durand, 1977). Kerogen formation is consid- infrared, 13C nuclear magnetic resonance, and X-ray),
ered complete by the end of diagenesis because fulvic solvent extract data, and the results of oxidation and
and humic acid abundances are very low. pyrolysis experiments (Burlingame et aI., 1969;Yen, 1974;
Investigations have shown that some kerogens consist Oberlin et aI., 1980; Behar and Vandenbroucke, 1986).
largely of preserved resistant cell wall material rather These models give some valuable insights into the
than being newly formed during diagenesis (Philp and chemical constituents and variable complexity of
Calvin, 1976; Largeau et aI., 1986, 1990; Mycke and kerogen, especially when morphologic habit and optical
Michaelis, 1986; Nip et aI., 1986; Tegelaar et aI., 1989b) properties (e.g., Stach et aI., 1982) are also considered.
and occur in the humin fraction. Included in this Nevertheless, the detailed chemistry of kerogens is
category are morphologically structured phytoclasts, broadly viewed within the petroleum industry as being
such as spores and pollen that are readily identifiable by of only academic interest and of little practical value,
means of transmitted and reflected light microscopy, and especially as far as petroleum exploration is concerned.
extremely fine cell wall debris with morphology that is Indeed, kerogens are most often considered to fall into
discernible only under the electron microscope. one of only three basic types (I, II, or III) based either on
The proportion of kerogen resulting from either atomic HIC and OIC ratios from elemental analysis or
diagenetic reactions or direct preservation depends on on the correlated hydrogen index (HI) and oxygen index
the nature of the starting material and the depositional (Ol) from Rock-Eval pyrolysis yields (Tissot et aI., 1974;
environment. This is exemplified by variations in humic Espitalie et aI., 1977). While this simple scheme is
acid versus kerogen concentrations in different practical because it is directly linked to potential
Australian coal lithotypes of equal rank (Verheyen and petroleum yields and because parameters are easily
Johns, 1981; Verheyen et aI., 1983). Because the ratio of mappable (e.g., organic facies definitions of Jones, 1987),
resistant biopolymer to other cellular components varies its limitations should not be overlooked, especially with
according to plant species and climate (Tegelaar et aI., respect to predictive geochemistry. Namely, the types
1989b), original biota composition may impart a bias on and thermal stabilities of petroleum precursors vary
one mode of kerogen formation versus the other, significantly within any single elementally defined
although the final proportions of surviving materials is kerogen type (Horsfield et al., 1993). Hence, the type of
strongly dependent on the anoxic versus oxic nature of petroleum and the timing of its generation vary accord-
the sediment-water interface. Differences in biodegrad- ingly.
ability of the organic matter usually leads to a selective This point can be briefly illustrated here by the cases
preservation of nonhydrolyzable components. However, of sulfur-rich kerogens and certain types of land plant
under strongly reducing conditions, even those plant organic matter that may generate petroleum at low levels
192 Horsfieldand Rullkiitter

of thermal maturation. For the vast majority of marine and Roberts, 1984), until Ni- or VO-desoxophylloery-
kerogens containing degraded algal and bacterial throetioporphyrins (DPEP) are the dominant species at
remains and nonmarine kerogens containing sporinite, the end of diagenesis. Phytane (C20), pristane (C19), and
vitrinite, and cutinite, it can be said that the zone of some lower carbon number isoprenoids are formed as
diagenesis corresponds to the immature zone. Heavier saturated hydrocarbons fairly early during diagenesis.
early oil generation, starting at a late stage of diagenesis, The pristane/phytane ratio is often referred to as an
appears to be common in carbonates, evaporites, phos- indicator of depositional conditions (redox potential).
phorites, and siliceous rocks (diatomites). Cross-linking This assumes that carbon skeleton is preserved during
sulfur bridges, incorporated during early diagenesis, are anoxic transformation of phytol (C20, from chlorophyll a
broken before carbon--earbon bond cleavage starts. This side chain) and that pristane is formed by oxidative alter-
leads to asphaltene- and resin-rich heavy bitumens and ation involving loss of one carbon atom by decarboxyla-
eventually to a mobile oil phase. Similarly, early genera- tion (Powell and McKirdy, 1975; Didyk et al., 1978). The
tion has been invoked for condensate formation from scheme may not apply to hypersaline environments
organic matter rich in resinite (Snowdon and Powell, because alternative sources of phytane, such as archae-
1982; Nissenbaum et al., 1985), although this has also bacterial lipids, must be considered (ten Haven et al.,
been questioned (Lewan and Williams, 1987). Likewise, 1987).
suberinite, formed from the corky tissue of land plants, Much is known about the reactions, intermediates,
has been found to undergo major structural transforma- and products of the diagenesis of steroids and hopa-
tions during diagenesis, ostensibly to generate oil noids, of which many hundreds of compounds are docu-
(Khorasani and Murchison, 1988). mented (Mackenzie et al., 1982; Ourisson et al., 1979;
Practically oriented molecular characterization of Ourisson, 1990). During diagenesis, steroids undergo a
kerogens can give some insight into these additional series of defunctionalization, isomerization, and aromati-
source rock attributes and is therefore discussed in the zation reactions (Brassell et al., 1984;de Leeuw and Baas,
section Catagenesis and Metagenesis. 1986; de Leeuw et al., 1989; Peakman and Maxwell,
1988a, b; Peakman et al., 1988, 1989; Rechka et al., 1992).
Biological Markers While most of these reactions involve unsaturated
sterenes, their saturated hydrocarbon analogs dominate
A small portion of sedimentary organic matter is in sediments at the end of diagenesis. Where not directly
soluble in organic solvents and contains lipid involved in double bond isomerization reactions, the
compounds that are either directly inherited from the chiral centers in the steranes still have the steric configu-
biological precursor organisms or cleaved by hydrolysis ration of the biogenic precursor molecules. In the
from larger cellular units such as cell walls or aromatic hydrocarbon fraction, monoaromatic steroid
membranes. Most are functionalized polar lipids that hydrocarbons are predominant.
undergo decarboxylation and dehydration reactions As in the case of steroids, defunctionalization of
during early diagenesis to produce saturated and olefinic oxygen-bearing precursors in hopanoids leads to
hydrocarbons, of which the latter are progressively hopenes that are then hydrogenated to saturated
hydrogenated into their saturated analogs during diage- hopanes. Important stereochemical reactions of
nesis. These hydrocarbons essentially have the same hopanoids occur earlier than those of steroids during
carbon skeletons and steric configurations as their func- diagenesis (Seifert and Moldowan, 1980).
tionalized biogenic precursors, although structural
rearrangements of carbon skeletons, catalyzed by clay
minerals, may also occur as side reactions. These carbon CATAGENESIS AND METAGENESIS
skeletons that retain their biogenic characteristics are
biological markers and are useful for conducting Catagenesis follows diagenesis and constitutes the
oil-source rock correlations. Their progressively principal stage of oil formation. Catagenesis is defined by
changing stereochemistry is also a valuable means of vitrinite reflectance values of 0.5% < Ro < 2.0% and is
calibrating thermal histories. characterized by thermaldegradation of kerogen and the
The strong preference for n-alkanes with odd accompanying formation of petroleum. The zone of
numbers of carbon atoms falls dramatically during metagenesis is one of even higher thermal stress,
diagenesis (e.g., decrease of carbon preference index, extending up to the onset of greenschist metamorphism.
CPD from the high values seen in higher plant waxes Only methane, hydrogen, and highly carbonized solid
(Eglinton and Hamilton, 1963) because of reactions organic matter are stable (2.0% < Ro < 4.0%). The oil
involving the reduction of even carbon numbered window is often generalized as 0.5% < Ro < 1.3% and the
alcohols and fatty acids with retention of their carbon gas window as 1.3% < R, < 4.0, with the threshold from
skeletons (Bray and Evans, 1961; Brooks and Smith, wet to dry gas being 2.0% Ro. The ensuing chemical and
1967). Also, the central magnesium ion of chlorophyll a is physical changes involving kerogen have been studied
lost during earliest diagenesis to form phaeophorbides or using numerous chemical, microscopic, and spectro-
to be replaced by other metal ions, particularly Ni 2+ or scopic approaches, and indices of maturation have been
V()2+ (Baker and Louda, 1986). Dehydrogenation of the formulated (e.g., Heroux et al., 1979; Durand, 1980). The
chlorins to porphyrins, accompanied by loss or reduction abundance and composition of generated compounds
of the oxygen functionalities, are the next steps (Barwise and compound classes may also be used for this
 10. Diagenesis, Catagenesis, and Metagenesis of OrganicMatter 193

purpose, but this has been deemphasized more recently normal type II kerogen of the same maturity (Tissotet al.,
because yields are more strongly influenced by 1987) because of the presence of weak carbon-sulfur
migration than was thought earlier (Larter, 1988). linkages. Sulfur is therefore lost from kerogen mainly
during early catagenesis as these bonds rupture (see
Kerogen Evolution Sinninghe-Damste and de Leeuw, 1990, for review). The
petroleum potential of type I kerogen is distributed
During catagenesis, kerogen aliphaticity decreases across a narrow range of activation energies and has a
and its aromaticity increases, with the absolute values higher generation threshold than do commonly
being dependent on the kerogen type. Coals of occurring type II kerogens. Type III kerogens also have a
increasing rank (thermal maturity) yield pyrolysates that relativelyhigh overall stability.
are progressively enriched in total and low molecular While the onset of thermal maturity varies according
weight aromatic compounds (Romovacek and Kubat, to kerogen type, it is important to note that there is no
1968; McHugh et al., 1976; Larter and Douglas, 1980), single "magic Ro value" at which the onset of thermal
reflecting the aromatization of the coal macromolecule. maturity occurs for any given kerogen type. This is
Increasing aromaticity is manifested physically as an because the kinetics of kerogen decomposition differ
increase in vitrinite reflectance. The contemporaneous from that of vitrinite reflectance change, a fact that is
decrease in phenolic structures associated with the loss of manifested in a rapidly subsiding source rock where the
oxygenated species during catagenesis (van Graas et al., overburden rock is of Tertiary age. Here Ro may under-
1980; Senftle et al., 1986) has been used to build a kinetic estimate the extent of petroleum generation.
model for vitrinite reflectance prediction (Larter, 1989).
The loss of H20, C02, (CH2)n, and C~ from vitrinite Gross Petroleum Composition Inherited
form the basis of an alternative model (Sweeney and from Kerogen
Burnham, 1990). Other changes taking place during cata-
genesis include the loss of aliphatic groups and an Natural unaltered oils vary in bulk composition
increase in the ratio of CH3/CH2, as revealed by 13C- because of broad differences in paraffinic, naphthenic,
NMR and IR spectroscopy (Witte et al., 1988). Stable aromatic, and asphaltic components (Tissot and Welte,
radicals formed in the kerogen during bond rupture 1984). These variations are largely governed by the types
increase in concentration as petroleum generation takes of parent structures in the kerogen (Larter and Senftle,
place (Pusey, 1973; Durand, 1980). Free radical concen- 1985; Horsfield, 1984, 1989). Empirical compositional
trations are both dependent on kerogen type and relationships therefore exist between oils and kerogen
maturity. During metagenesis, aromatic stacks aggregate pyrolysates (Horsfield, 1989), making it possible to assess
and a decrease occures in aromatic C-H infrared spectral the potential to generate condensate, high- and low-wax
vibrations (Rouxhet and Robin, 1978). Stabilized free varieties of mixed base (paraffinic-naphthenic-aromatic)
radicals formed during catagenesis pair up, bringing crude oil, and high- and low-wax varieties of paraffinic
about a reversal in their concentration (Retkofsky et al., crude oil. These relationships may be substantially
1968). modified by displacement phenomena and phase
As catagenesis proceeds, the three kerogen types (I, II, behavior (England and Mackenzie, 1989). Indeed,
and III) become progressively more hydrogen deficient because the composition of petroleum in the subsurface
and depleted in volatilizable components (Dormans et is dependent on phase behavior (England and
al., 1957; McIver, 1967; Tissotet aI., 1974). The proportion Mackenzie, 1989), it is desirable to go one stage further
of residual or "dead" carbon increases from its original and quantify these relationships in terms of gas-oil ratio,
value, low for type I to high for type III kerogens, to for example, so as to serve as input parameters for
overall higher values as thermally labile, volatilizable migration models (England and Mackenzie, 1989). It is,
carbon species are generated and released from macro- however, difficult to assess gas-oil ratios of petroleums
molecular structures (Gransch and Eisma 1970; Connan directly in the subsurface using pyrolysis methods
et al., 1975). Masses of generated and expelled petroleum because of the abundance of high molecular weight,
can be calculated using such data, provided that polar reaction intermediates in laboratory experiments
thermally mature samples and their immature equiva- (Larteret al., in press).
lents can be confidently identified (Goff, 1984; Larter, Interestingly, average carbon chain lengths for many
1985; Cooleset al., 1986; Rullkotteret al., 1988). algal kerogens appear to remain essentiallyconstant over
The progressive loss of components from the kerogen a broad range of thermal maturation, suggesting that this
structure proceeds according to bond strengths, with homogeneous pool of precursor structures in the
weaker bonds breaking before stronger bonds. For type kerogen and other macromolecular components is a
II and type III kerogens, there is a progressive increase in potentially powerful oil-source rock and oil-oil correla-
Rock-Eval pyrolysis Tmax values with increasing thermal tion tool (Horsfield et a1., 1989; Duppenbecker and
maturity (Barker, 1974; Espitalieet al., 1977) as a result of Horsfield, 1990; Muscio et al., 1991). A shortening of
petroleum generation and a switch to higher mean average chain length was found to take place only
values of activation energy for residual kerogens (Tissot during the very early stages of thermal maturation of
et al., 1987; Schaefer et al., 1990). The distribution of Green River Shale and Posidonia Shale kerogens
petroleum potentials for immature sulfur-rich type II (Horsfieldand Diippenbecker, 1991). Furthermore, based
kerogen has a lower mean activation energy than does on the pyrolysis results of Dungworth and Schwartz
194 Horsfield and Rullkiitier

(1972), McKirdy et a1. (1980), and Jackson et a1. (1984) for Random thermal cracking in most cases generates n-
highly mature Proterozoic and lower Paleozoic source alkanes without odd-even carbon number predomi-
rocks, it appears that long chain substituents inherited nance (for exceptions, see earlier discussion). Because of
from biological organisms may be preserved even into the high abundance of these newly formed compounds,
metagenesis. This means that original oil potential can be this dilutes the biologically inherited odd carbon number
recognized in some instances, even where levels of preference maintained through diagenesis. Kerogen
thermal maturity have been exceedingly high. cracking also favors the formation of pristane, thus
Because no preferred depletion of long alkyl chains increasing the pristane / phytane ratio as thermal
occurs during the main phase of petroleum generation, it maturity increases. In a similar fashion, pristane/n-C 17
can be speculated that the base of their oil window is and phytane / n-C 18 ratios decrease with thermal
likely to be defined by oil stability. It should be noted, maturity due to the preferential generation of n-alkanes.
however, that significant changes in chain length distrib- These parameters can only be applied to rock sequences
ution may occur during the maturation of heterogeneous with nearly identical starting organic material because
and algal kerogens such as oil-prone coals as they readily changes in kerogen facies influence the mechanisms of
lose long alkyl chains from their apparently nucleated the maturity-dependent alterations.
structure (Horsfield, 1989). In this case, the base of the oil Steroid hydrocarbon isomer ratios are the most
window is likely to be brought about by depletion of the widely applied biological marker thermal maturation
kerogen's long chain components. Depletion would parameters. When these parameters were first estab-
appear to occur far in advance of the generalized oil lished (Mackenzie et al., 1980), steranes were thought to
phase (Ro = 1.3%).A distinctly separate phase of gas and undergo an epimerization reaction at C 20 in the side
condensate generation may occur at elevated thermal chain, thus transforming the biogenic 20R configuration
maturities, this being quantitatively significant in the into the geologically occurring 20S configuration. This
case of coals. reaction continued until an equilibrium ratio of 0.54 was
Late in catagenesis and within metagenesis, either reached (van Graas et a1., 1982). In a similar way, the
hydrogen sulfide or nitrogen may be generated from biogenic configuration of steranes at C14 and C 17 in the
heterocyclic kerogen moieties in carbonates and coals, ring system is apparently altered, resulting in the
respectively (Le Tran et al., 1974; [untgen and Klein, formation of the thermodynamically most stable sterane
1975). isomers, 5a(H),14~(H),17~(H)-steranes(20S + 20R)
The n-alkanes in many paraffinic oils exhibit an (Mackenzie et al., 1980). Later it was shown that sterane
odd-even carbon number predominance, typically isomer ratios are not always related to thermal maturity
between 1.2 and 1.5. This periodicity is inherited from but are dependent on kerogen facies (ten Haven et al.,
biologically derived molecular structures in the source 1986; Moldowan et al., 1986; Rullkotter and Marzi, 1988)
rock (van de Meent et al., 1980;Reed et al., 1986;Douglas because specific precursor molecules lead to the early
et al., 1991). Precursors in the case of high-wax oils were formation of the geologic epimers. This effect is particu-
previously thought to be wax esters or free hydrocarbons larly important in carbonate and evaporite source rocks
derived from leaf cuticles (Brooks and Smith, 1967). (ten Haven et al., 1986; Rullkotter et a1., 1985) where
Because carbon number preferences approach unity in sterane isomer ratios usually fail as thermal maturation
most thermally mature source rocks and "marine" oils indicators. In contrast to this, steroid aromatization, i.e.,
(Bray and Evans, 1961; Brooks and Smith, 1967; the transformation of monoaromatic to triaromatic
Leythaeuser and Welte, 1969), it was logical to conclude steroid hydrocarbons (Mackenzie et al., 1981),appears to
that high-wax crude oils were generated at a low level of be kerogen facies independent and has been successfully
thermal maturity. This may still be the case for some used as a thermal maturity indicator for carbonate source
coals (see below). However, the discovery that aliphatic rocks and genetically related crude oils (Rullkotter et al.,
biopolymers of plant cuticular membranes yield n- 1985).
alkanes with a pronounced odd carbon number predom- For both sterane isomerization and aromatization
inance, even at high degrees of thermal conversion reactions, however, recent studies have shown that our
(Tegelaar et al., 1989a), indicates that there is more than understanding of the reaction mechanisms involved is
one type of high-wax oil precursor and that the latter far from adequate and that the chemical basis for some of
may be generated late in catagenesis. the systematic changes observed is more complex than
previously thought (Rullkotter and Marzi, 1989; Abbott
Molecular Maturation Parameters et al., 1990;Peters et al., 1990;Marzi and Rullkotter, 1992).
While, the related thermal maturity parameters should
The progress of thermal maturation can be monitored be applied with the necessary caution, it is clear that they
in the bitumen fraction by the use of so-called molecular constitute an important means for calibrating thermal
maturation parameters ranging from the relatively history.
simple CPI of n-alkanes (Bray and Evans, 1961)to sophis- Changes of hopane composition in source rocks
ticated geochemical reactions of biological markers (see during catagenesis involve an increase in the 17a(H)-
Mackenzie, 1984, for overview). While these are most hopane/moretane ratio (Seifert and Moldowan, 1980)
useful in the early to peak oil generation range, aromatic and in the amount of 22,29,30-trisnomeohopane relative
hydrocarbon parameters can also be applied at higher to its C27 17a(H)-hopane counterpart (Seifert and
levels of thermal maturity (see Radke, 1987, and Moldowan, 1978). Both parameters, however, show
Alexander et al., 1988,for overviews). significant variations with organic facies in addition to
 10. Diagenesis, Catagenesis, and Metagenesis of Organic Matter 195

the dependence on thermal maturity. On the other hand, secondary migration models, utilizing compositional
because epimerization of extended hopanes (C31--C3S) is information on generated petroleums, require informa-
complete before catagenesis starts, they are of little use as tion that kerogen types I, II, and III are unable to provide.
thermal maturity parameters (Mackenzie et al., 1980). On a more fundamental note, there is still a need to
Porphyrins respond to increasing thermal stress by clarify the degree to which pressure and mineral
the loss of the five-membered isocyclic ring, so that catalysts affect the rates of petroleum-forming chemical
DPEP porphyrins are progressively transformed into reactions in the subsurface. This will best be acheived by
etioporphyrins (Barwise and Roberts, 1984; Sundara- using the combined approach of regional studies,
raman et al., 1988).This parameter has been shown to be process simulation, and numerical modeling.
useful beyond the peak of oil generation.
Aromatic hydrocarbon maturity parameters monitor
the thermally induced changes in the isomer distribu-
tions of methylated biphenyls, naphthalenes, and
phenanthrenes (Radke, 1987; Alexander et aI., 1988). Acknowledgments We would like to express our gratitude
These parameters have been calibrated using coals or to A. G. Douglas for critically reviewing anearlier draft of the
sedimentary rocks containing mainly terrigenous organic manuscript.
matter. The application range extends up to 1.5% R, or
higher. The correlation with vitrinite reflectance is
excellent for coaly organic matter such that the molecular
parameters are often used to calculate vitrinite
reflectance equivalents. Application to marine organic
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