Thermal Maturity

Thermal maturity is the extent of temperature–time driven reactions, which are

responsible for the conversion of sedimentary organic matter to oil and gas (Mani
et al., 2015a).

From: Shale Gas, 2017

Related terms:

Kerogen, Shale, Hydrocarbon, Sediment, Biomarker

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Learn more about Thermal Maturity

Geology of North American Coalbed

Methane Reservoirs
Jack C. Pashin, in Coal Bed Methane, 2014

3.2.5.3 Rank
Thermal maturity affects numerous fundamental coal properties, including gas
capacity and geomechanical properties, thus coal rank is an extremely important
coal quality parameter for the evaluation of coalbed methane reservoirs. Vitrinite
reflectance, volatile matter (dry, ash free), and moisture (ash free) are the most com-
monly used measures of coal rank in the coalbed methane industry. Rank parameters
track the coalification process from lignite through metaanthracite. Moreover, the
type and quantity of hydrocarbons generated and expelled from coal are closely
related to thermal maturity and can be gauged by determining coal rank.

The transformation of peat to lignite is complete when moisture falls below 75%,
carbon content (dry, ash free) is greater than 60%, and free cellulose is absent.
Lignin and the remaining cellulosic substances are transformed to humic com-
pounds as coal progresses through lignite and subbituminous rank. Below bitumi-
nous rank, the principal volatile compounds generated are water and carbon dioxide,
methane generation is dominantly biogenic, and the vast majority of the gas is
expelled by compaction (Levine, 1993). Oil, furthermore, can begin to be generated
from liptinite at lignite rank (Ro   0.35) (Paterson et al., 1997).

Devolatization emerges as the principal factor driving volumetric changes as coal

approaches bituminous rank. Moisture decreases from 15 to 1% as coal progresses
from high volatile C bituminous rank to medium volatile bituminous rank. The
lower boundary of the thermogenic oil window corresponds with the subbitumi-
nous–bituminous transition (Ro   0.50), and peak oil generation corresponds with
high volatile B and A bituminous rank (Ro   0.70–1.10) (Hunt, 1979). Most oil
generation occurs at temperatures between 50 and 150 °C, and large volumes of
carbon dioxide also can be generated. Major thermogenic generation of gaseous
hydrocarbons apparently begins at the boundary between high volatile B and A
bituminous rank (Ro   0.80) (Jüntgen and Klein, 1975). Most methane is generated
between temperatures of 100 and 225 °C, and significant volumes of nitrogen also
can be generated. Thermal cracking of hydrocarbons is an important process in the
thermogenic gas window, and hydrocarbon generation is thought to be effectively
complete at anthracite rank (Ro >3.00).

As mentioned previously, coal has the capacity to generate multiple times more
methane than can be held in matrix and is thus an important source rock for natural
gas. Although coal contains significant quantities of oil-prone organic matter, the
capacity of bright-banded coal to expel oil is uncertain (Wilkins and George, 2002).
Indeed, the aromatic network of coal has capacity to store significant amounts
of oil, and it is possible that much of this oil is cracked to gas as it is expelled.
Indeed, vitrinite commonly fluoresces and has suppressed reflectance within the oil
generation window, indicating retention of oil in coal matrix. This oil apparently
occludes gas storage, thereby adversely affecting the ability of coal to store and
transmit natural gas. This phenomenon is particularly common in Cretaceous and
Tertiary coal seams, and in the southern part of the San Juan Basin, coal seams
within the oil window typically exhibit poor reservoir performance (Clayton et al.,
1991; Meek and Levine, 2006). By contrast, production of gas from coal in the oil
window has proven successful in the underpressured Horseshoe Canyon play of
western Canada (Gentzis, 2010).

Cleating of coal is commonly rank dependent, reflecting progressive devolatization

as well as changing mechanical properties during thermal maturation (Ting, 1977;
Law, 1993). Lignite and subbituminous coal are commonly weakly cleated, whereas
cleat spacing in medium volatile bituminous and low volatile bituminous is typically
on the order of centimeters or millimeters. Pashin et al. (1999), for example, ob-
served that reservoir quality cleat systems in the Black Warrior Basin are restricted
primarily to coal within the thermogenic gas window, suggesting that gas gener-
ation was an important cleating mechanism. In North American basins, anthracite
generally lacks cleats, has conchoidal fracture, and appears glassy, suggesting that
cleats have annealed. By contrast, some Chinese anthracite is finely cleated (Su et al.,
2005), establishing that cleat systems can be preserved at elevated rank.

Coal rank also has a strong influence on the mechanical properties of coal. The
strength and brittleness of coal is dependent on rank and coal composition, and
the Hardgrove grindability index a commonly employed proxy for these properties
(Hower and Wild, 1988; Chelgani et al., 2008). In general, the grindability index of
coal is greatest in medium and low volatile bituminous rank (Esterle, 2008) (Figure
3.17). Accordingly, hydrofracturing appears to be most effective in coal seams with
high grindability index. In the San Juan Basin, moreover, cavity completions have
proven most effective in medium volatile bituminous to low volatile bituminous coal
(Young et al., 1994).

FIGURE 3.17. Relationship of Hardgrove grindability index to coal rank and coal
type.

After Esterle (2008).

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Large Coal-Derived Gas Fields and
Their Gas Sources in the Sichuan Basin
Giant Coal-Derived Gas Fields and their Gas Sources in China, 2016

1.2.2 Thermal Maturity

The thermal maturity of gas source rock in the Xujiahe Formation is dominated
by Indosinian-Yanshanian structures and burial (Wang et al., 1997b). Owing to the
generation and sustained uplift of Luzhou palaeohigh and Kaijiang palaeohigh in
the southeast Sichuan Basin at the end of the Indosinian, Xujiahe sedimentary
formations were thick in the northwest and thin in the southeast for a long period
(i.e., until the end of the Yanshanian). Therefore, Xujiahe source rock also shows high
maturity in the northwest and low maturity in the southeast.

Ro values (the vitrinite reflectance values) of Xu1 source rock range from 1.0–2.5%,
indicating a state of high-mature to postmature in most of the basin. The middle
section of Xu1 in Central Sichuan is of the highest maturity above 2.5%, indicating a
state of postmature; the maturity changes greatly with burial depth. High Ro values
over 2.0% occur in Dujiang, Xinchang and Fenggu areas, which gradually decrease
in the southwest and northwest directions to 1.3% in Longtai, Luodai, and Danleng.
Ro values in Wangcang in Northwest Sichuan exceed 2.0% and decrease in the
southeast direction to 1.3% near Quxian. Ro values in Central Sichuan are relatively
low compared with West Sichuan; source rock in Tongnan is of high maturity and
Ro is higher than 1.3%. Ro values of source rock in other districts in Central Sichuan
and South Sichuan are generally between 1.0% and 1.3% (Figure 3.5).
Figure 3.5. Maturity of the source rock from the Xu1 member in the Sichuan Basin

Xu3 source rock is less mature than Xu1 and Xu2 source rock and Ro ranges from
1.0–1.9%. The maturity of source rock is high in West Sichuan and North Sichuan;
it decreases from north to south and from west to east and reaches a trough in the
southeast. Ro values of source rock are higher than 1.3% from Zitong, Zhongjiang,
and Mianzhu to Lushan in southwest Sichuan. The maturity is relatively high in
Nanjiang, Tongjiang, and Bayou in Northeast Sichuan and decreases to the south to
1.3% around Cangxi, Yilong, and Yihan. Source rock in Central Sichuan and South
Sichuan already reached a state of mature and Ro basically changes from 1.0% to
1.3%. Ro exceeds 1.3% around Suining and Nanchong (Figure 3.6).
Figure 3.6. Maturity of the source rock from the Xu3 member in the Sichuan Basin

Ro values of Xu5 source rock range from 0.9% to 1.5%. Except in the south and
north sections of West Sichuan with high maturity, Ro generally changes from
0.9% to 1.2% in most of the basin with little variation. Source rock in Zitong and
Mianyang already reached a state of high mature with Ro over 1.3%, which decreases
in the south and northeast directions to 0.7% near Jintang. Source rock in Xindu
is high mature. Ro in Southwest Sichuan goes beyond 1.3% and decreases to the
east. Source rock is mature in Yingshan, Nanchong, Tongnan, and Dazu in Central
Sichuan. In Weiyuan and Rongxian in South Sichuan, source rock is of low maturity
and Ro ranges from 0.5–0.7%.

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Exploration Technique
A.M. Dayal, ... A.K. Varma, in Shale Gas, 2017

5.2.3 Basic Geochemical Information Required for Shale Gas

Exploration
1. thermal maturity of shales containing different type of kerogens and organic
content,
2.
the lithological, petrophysical, and mineralogical character of shale that con- 3.
trols the fractures,
ratio of free gas versus adsorbed gas

Geochemistry of shales helps us understand the source rock characterization. For

source rock characterization, the following information is required:

▪ organic richness

▪ thermal maturity

▪ type of kerogen

Organic richness is measured by a TOC analyzer in the shale and expressed as

percent of rock. TOC percent in the shale sample is an indicator of the presence
of hydrocarbon as given next:

TOC < 0.5% = no hydrocarbon
TOC 0.5–1% = some chances for hydrocarbon
TOC 1–2% = good chances of hydrocarbon
TOC > 25 = very good chances
TOC decreases with thermal maturity

There are four types of kerogen: Type I (oil prone), Type II (gas prone or oil prone),
Type III (gas prone), and Type IV (no hydrocarbon) (Tables 5.2.1 and 5.2.2). Rock Eval
pyrolysis and TOC for the source rock provide the following information:

Table 5.2.1. Type of Kerogen Based on Element Ratio

Type of Kerogen H/C Ratio O/C Ratio H/C Ratio O/C Ratio
Type I 1.9–1.0 0.1–0.02 – –
Type II 1.5–0.8 0.2–0.02 – –
Type III – – 1.0–0.5 0.4–0.02
Type IV – – 0.6–0.1 0.3–0.01

Table 5.2.2. Classification of Kerogen and Their Potential Environment

Type of Kero- Maceral HI (mg Thermal Ma- Generated Depositional

gen Composition HC/gm TOC) turity (%) Hydrocarbon Environment
Type I Algal and &gt;700 0.6–0.9 Oil Highly
amorphous anoxic/lacus-
organic trine shallow
matter marine lagoon
environment
0.9–1.3 Gas condensate
1.3–2.6 Gas generation
Type II Amorphous 400–700 0.5–0.9 Oil Anoxic marine
organic basin, lacus-
matter and trine subtidal,
lipids
 supratidal en-
vironment
0.9–1.3 Gas condensate
1.3–2.6 Gas generation
Type II/III Mixed organic 200–400 0.6–1.0 Oil/gas cond. Swamp and
matter (amor- delta complex
phous organ-
ic matter and
vitrinite)
1.0–1.3 Gas cond. and gas Low to medium anoxic lagoon
1.3–2.6 Gas
Type III Mainly vitri- 50–200 0.6–1.0 Gas/cond. Brackish water
nite swamps
1.0–2.6 Gas
Type IV Initernite &lt;50 No sources of Little gas Oxic swamps
hydrocarbons and oxic ma-
rine basins

S1 = free hydrocarbon from C1 to C23 thermally liberated from the rock sample
at 300°C
S2 = hydrocarbon cracked from kerogen or from C24 bitumen’s in rock sample
between 300 and 600°C
S3 = organic CO2 released form rock sample between 300 and 400°C
Tmax = the temperature for the highest yield of S2 hydrocarbons
Hydrocarbon index (HI) = (S2/TOC) × 100
Oxygen index (OI) = (S3/TOC) × 100
Production index (PI) = S1/(S1 + S2)
S1/TOC is the migration index

Calculation of Original TOC

where F is the fraction of hydrocarbon generated = (HIoriginal − HImeasured)/HIoriginal;

dVTOC = Max TOC convertible to kerogen type.

Type I = 62.5%, Type II = 48.2%, and Type III = 25.2%

Calculation of original HI = HIoriginal = HImeasured/(1−F)

Geochemical Modeling for Gas Generation and Retention in Shales

Free gas and adsorbed gas can provide better resource assessment of shale gas.

1. thermal extraction using gas chromatograph

2. free gas from gas chromatograph and isotope characterization

These data can be plotted in a Bernard diagram (Whiticar, 1994). 13C1 versus C2+
can provide information about the characterization and origin of gas. 13C1 versus
Hmethane can provide information about the characterization and origin of gas.
 13C1, 13C2, 13C3,
and 13C4 versus C1, C2, C3, and C4 can provide information
about the maturity of thermogenic gas. It is important to know the content and
volume of the gas in the shale formation. In a shale formation, gas is associated as
free gas and also adsorbed gas. For the estimation of total gas in shale formations,
the volume of gas with time can be measured in a core sample from a well. For an
adsorbed gas, the sample is pulverized, and methane is measured with the function
of time in a high-pressure condition. The gas adsorbed by a shale formation is
presented in standard cubic feet per ton. Besides geochemistry, petrophysical and
mineralogy are important parameters.

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Coalification, Gasification, and Gas

Storage
Romeo M. Flores, in Coal and Coalbed Gas, 2014

Limitations of Vitrinite Reflectance

Determination of thermal maturity of coal beds and other source rocks may be
compromised by anomalously low vitrinite reflectance or suppressed compared to a
“typical” vitrinite that has undergone similar coalification processes (e.g. temper-
ature, pressure). Suppression of vitrinite reflectance may be from 0.1% to 0.4%
depending on the rank and maturation conditions (Levine, 1993). However, vitrinite
reflectance values can also be suppressed and caused by prevalence of perhydrous
vitrinites and lack of orthohydrous vitrinites. The most serious impact of vitrinite
reflectance suppression is the underestimation of heat flow, thus the maturity
of source rocks lead to errors in predictions of transformations and quantity of
hydrocarbons (Samuelsson & Middleton, 1998). Suppressed vitrinite reflectance is
frequently caused by organic petrographers having problems in finding and mea-
suring appropriate vitrinite materials in hydrogen-rich kerogens, extracting organic
matter for analysis and analytical procedure (Barker, Lewan, & Pawlewicz, 2007;
Bostick, 2011; Lo, 1993). Vitrinite reflectance suppression is commonly developed
in many sedimentary basins and may happen more frequently than recognized.

Carr (2000) defined vitrinite reflectance suppression as the reduction in reflectance

resulting mainly from the maceral composition of the source rock. Thus, suppres-
sion of vitrinite reflectance is due to (1) high liptinites associated with vitrinite, (2)
occurrence of litptinite-derived aliphatic lipids and bitumens, (3) production of per-
hydrous (hydrogen/aliphatic-rich) vitrinite in anaerobic and/or alkaline depositional
environments, and (4) presence of hydrogen- and aliphatic-rich vitrinite originating
from a particular flora. Vitrinite reflectance suppression occurs on deposition of
sediments and reflectance is reduced through burial until the hydrogen/bitumen
is removed from the structure. In contrast, Carr (2000) defined vitrinite reflectance
retardation, by contrast, as thermochemical reduction resulting from the effects of
overpressure in a sedimentary basin. Suppression occurs at depth in a basin due
to the development of a pressure seal in contrast to retardation, which continues to
occur as long as the overpressure remains. The presence of overpressured sediments
in many sedimentary basins means that vitrinite reflectance retardation may occur
more frequently than is commonly recognized. How does guesswork on vitrinite
reflectance suppression affect coalbed gas exploration? For example, vitrinite re-
flectance of the Upper Cretaceous Ferron coals in Utah was found to be higher in the
north than in south of the coalfield (Quick & Tabet, 2003). These vitrinite reflectance
variations were determined inconsistent to the coalfield-wide coal rank. In the Ferron
coalbed, gas fairway indicates that coals in the north are of higher rank than coals in
the south. Measured vitrinite reflectance does not accurately show this variation of
coal rank. In addition, suppressed vitrinite reflectance is observed in the north where
gas contents are relatively high; thus, suppression may affect coalbed gas yield.
Quick and Tabet (2003) related the suppressed reflectance to burial history where
overpressure developed during the coalification stage, which continued until recent
uplift and cooling. This finding may provide a model for developing prospective
coalbed methane targets elsewhere.

What does it take to get the conjecture out of the analysis of vitrinite reflectance to
solve the suppression problem? Newman (1997) and Newman, Eckersley, Francis,
and Moore (2000) suggested the following techniques: (1) diagnose and correct
vitrinite reflectance suppression using bulk chemistry for coals and (2) petrologic
approach for dispersed organic matter in sedimentary rocks. These techniques are
developed to combine reflectance with quantitative vitrinite fluorescence, whose plot
and graphical relationships allow objective differentiation of Types III and IV organic
matter into suppressed vitrinite, normal vitrinite, recycled vitrinite, and inertinite.
Newman (1997) suggested that measurements should be made in a nitrogen atmos-
phere to avoid fluorescence alteration. Other detection and replacement methods
for vitrinite reflectance were proposed by Fedor and Vido (2003), Lis, Mastalerz,
Schimmelmann, Lewan, and Stankiewicz (2005), Petersen et al. (2009), Wilkins,
Wilmshurst, Hladky, Ellacott, and Buckingham (1995), and Zhong, Sherwood, and
Wilkins (2000).

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Interpreting Crude Oil and Natural Gas
Data
Harry Dembicki, Jr., in Practical Petroleum Geochemistry for Exploration and Pro-
duction, 2017

The Maturity of Thermogenic Natural Gas

Determining a more precise thermal maturity for thermogenic natural gas is im-
portant to understanding its origin as well as a being a clue to its source. Thermal
maturity estimates for natural gas are based on the carbon isotope data of the indi-
vidual hydrocarbon gases, specifically the methane, ethane, and propane. Because
of low concentration, it is sometimes difficult to obtain accurate isotopic analysis
of propane. In these instances, maturity assessments rely solely on the methane and
ethane and are more tentative without corroboration from the propane.

The relationship between the carbon isotope ratios of methane, ethane, or propane
in a natural gas and the vitrinite reflectance of the source was established initially by
Stahl and Koch (1974) with later refinement by Stahl (1977) and Faber (1987). These
relationships are shown in Fig. 4.31. A common way of using these relationships
to estimate the maturity of a natural gas is by cross-plotting two trends, typically
methane versus ethane and propane versus ethane as shown in Fig. 4.32. Natural
gas samples that have not been altered and are not the product of the mixing of
two or more gases should plot along these trends within a zone of about ± 1.5‰
(Berner and Faber, 1988). There should be a general agreement between the maturity
estimates of the two trends to confidently assign a maturity to the gas. Because of
possible variations in the carbon-isotopic signature of the original source organic
material, the maturity assessments of natural gases based on these trends should
only be considered approximate.
Figure 4.31. The observed relationship between the 13C of methane, ethane, and
propane versus vitrinite reflectance, based on the equations of Stahl (1977).

Figure 4.32. Cross-plots of the 13C of methane versus ethane and propane versus
ethane form estimating the thermal maturity of natural gases in equivalent vitrinite
reflectance, % Ro, based on the equations of Stahl (1977). These cross-plots can also
be used to indicate biodegradation and mixing of gases.

Some carbon isotope data for natural gases are observed to plot off these trends.
These deviations from the trends are usually due to the mixing of two or more gases
of different origin or different maturity. Samples deviating by plotting above the
methane–ethane trend suggest mixing of a biogenic gas with a thermogenic gas,
while deviating by plotting below the trend indicates the mixing of two thermogenic
gases (Berner and Faber, 1988). Deviation below the propane–ethane trend is also
indicative of the mixing of two thermogenic gases (Berner and Faber, 1988).

Deviations from these trends may also be signaling alteration of the gas. Biodegra-
dation of an associated crude oil would be expected to contribute isotopically lighter
(more negative) biogenic methane (Head et al., 2003) to the gas also resulting in data
points plotting above the methane–ethane trend. In contrast, microbial alteration of
the gas itself would initially focus on the wet gas components and the likely outcome
would be isotopically heavier (more positive) ethane and propane (James and Burns,
1984), resulting in data points plotting below the trends.

> Read full chapter

Source Rock Evaluation

Harry Dembicki, Jr., in Practical Petroleum Geochemistry for Exploration and Pro-
duction, 2017

Thermal Maturity Interpretations

Compositional changes in gas chromatograms with increasing thermal maturity
were discussed in detail in Chapter 2. As a brief review here, an example of changes
in the gas chromatograms of saturated hydrocarbons with maturity is shown in
Fig. 3.22. The immature stage shows a bimodal envelope of unresolved material
beneath the peaks, and there is an odd carbon number predominance in the C25–C35
n-paraffins. In the moderately mature sample, there is a noticeable reduction in
the higher molecular weight “hump” of unresolved material, and the odd carbon
number predominance is gone. In the chromatogram of the mature sample, the
higher molecular weight “hump” of unresolved material has been eliminated and
there is a substantial increase in the n-paraffins in the C15–C18 range making the
saturate fraction look more like crude oil.
Figure 3.22. Progressive changes in the source rock extract gas chromatograms due
to increasing maturity from a series of samples with Type II dominated kerogen.

In addition to looking at the gas chromatograms, the height of the n-paraffin peaks
can also be used to track changes with maturity. One method is to calculate the
Carbon Preference Index, or CPI, as shown in Fig. 3.23. The CPI was developed by
Bray and Evans (1961) to help distinguish immature n-paraffin distributions from
more mature n-paraffin distributions in source rock and crude oils. Most immature
source rocks exhibit CPIs greater than 1.0, while mature source rocks and crude oil
have CPIs of about 1.0 (Bray and Evans, 1965).
Figure 3.23. Equation for the calculation of CPI as defined by Bray and Evans (1961).

Another way of using the peak heights of the n-paraffin to track changes with
maturity is to plot the peak heights versus carbon number, as shown in Fig. 3.24.
The shallow, immature n-paraffin distribution exhibits a saw-toothed pattern with
the odd carbon number n-paraffins dominating the C25–C33 range. As the sediments
get deeper and more mature, the saw-toothed pattern diminishes and the maximum
of the distribution of n-paraffins shifts down to the lower molecular weight range,
becoming more like crude oil. CPI values for these n-paraffin distributions are also
included in Fig. 3.24 to demonstrate how they change with increasing maturity.

Figure 3.24. Progressive changes the n-paraffin distributions and CPI due to increas-
ing maturity for a series of source rocks samples with similar kerogen type.

> Read full chapter

Biogeochemistry
J.J. Brocks, R.E. Summons, in Treatise on Geochemistry, 2003

8.03.3.1 Biomarkers as Maturity Indicators

One of the most widely used applications for biomarkers is for the measurement of
thermal maturity of organic matter to estimate the petroleum-generation potential
and temperature history of sedimentary basins (e.g., Mackenzie, 1984; Radke et
al., 1997). A large number of biomarker parameters that are sensitive to different
stages of maturity have been developed and are reviewed in Peters and Moldowan
(1993). Two examples are described further below. For the interpretation of maturity
parameters in the literature, it is important to note that the thermal evolution of
biomarkers, and organic matter in general, might be widely different in rocks of
different lithological compositions and from different basins and formations. Clay
minerals, for example, provide catalytic sites for degradation and isomerization
reactions and strongly influence the type and extent of isomer conversion (e.g.,
Moldowan et al., 1991a). Moreover, the range of biological inputs, presence of
organic sulfur compounds and a host of other factors might cause disparate maturity
values from the outset. Therefore, considerable caution has to be applied when
comparing maturity parameters across disparate sample sets. Similar caution is
necessary for the interpretation of conventional organic geochemical nomenclature
for hydrocarbon thermal maturity (Figure 2). The generation and maturation process
of petroleum can follow markedly different pathways between different samples
and between different components of the same sample (e.g., Radke et al., 1997).
Thus, the description of the preservation state of petroleum and bitumen using
such terminology as “peak oil generation” or “overmature” is quite vague and clearly
qualitative. It does not necessarily correlate with kerogen maturity data (e.g., vitrinite
reflectance) or absolute temperatures unless calibrated for each sample set. Figure
2 should therefore only be used as a visual indicator of the relationships between
bitumen descriptions expressed in words, temperatures, and vitrinite reflectance
data.
Figure 2. Terminology for bitumen maturity commonly used in the literature (e.g.,
Peters and Moldowan, 1993). The “modified temperature scale” pertains to hydro-
carbon preservation under ideal conditions and was derived from data in Table 1.

As an example of a typical biomarker maturity parameter, the ratio of 20S/(20S+20R)

isomers in a sterane measures the relative abundance of the S and R configurations
at C-20 of sterane hydrocarbons with 5 , 14 , 17 (H) stereochemistry (Figure
3; for sterane nomenclature see Section 8.03.5.11). In living organisms, sterols
exclusively possess the 20R configuration, but during diagenesis and catagenesis
steranes are gradually transformed to a mixture of 20R and 20S isomers. The
thermal equilibrium value of 0.55 for the 20S/(20S+20R) ratio is apparently reached
close to the peak of oil generation (Peters and Moldowan, 1993). Ratios based on
triaromatic steroids (TA) (68a) and (68b) are an example of parameters sensitive at
higher thermal maturities, i.e., the late stage of petroleum generation (Riolo et al.,
1985). Triaromatic steroids (68) form apparently predominantly by aromatization of
monoaromatic steroid precursors (Mackenzie et al., 1981). Thermal cleavage of the
side chain of intact C26 to C28-TAs (68b) (TA-II) leads to the generation of degradation
products with 20 to 21 carbon atoms (TA-I (68a)). Consequently, in the transition
from immature through mature to overmature petroleum, the ratio TA-I/(TA-I+TA-II)
increases from <5% to close to 100% (Figure 4).

Figure 3. Equilibration between the biological 20R epimer and the geological 20S
epimer of cholestane 66a.
Figure 4. Distribution of triaromatic steroids (68) in GC-MS m/z=231 selected ion
chromatograms in (a) a Phanerozoic oil of low thermal maturity, (b) a mature
Phanerozoic oil, and (c) an overmature bitumen from the late Archaean Fortescue
Group in Western Australia. The inset in (c) is a 20×magnification of the elution
range of C26 to C28 triaromatic steroids (68b) (Brocks et al., 2003a,b) (reproduced by
permission of Elsevier from Geochim. Cosmochim. Acta 2003, in press).

Hydrocarbons with typical “overmature” compositions and isomer distributions are

characteristically found in rocks with deep-burial history, e.g., in Archean sequences
(Brocks et al., 2003a). Adamantanes and diamantanes, for example, are diagnostic
classes of “diamondoid” hydrocarbons that persist and become concentrated at
extreme levels of thermal maturity (Chen et al., 1996; Dahl et al., 2002, 1999). In
contrast to burial metamorphism, hydrocarbons may also be generated over short
timescales at very high temperatures such as those prevailing at recent hydrothermal
vents (e.g., Simoneit and Fetzer, 1996; Simoneit et al., 1992), in shales proximal
to centers of hydrothermal ore formation (e.g., Brocks et al., 2003d; Chen et al.,
2003; Gize, 1999; Landais and Gize, 1997; Püttmann et al., 1988) or near-volcanic
intrusions (e.g., Farrimond et al., 1999; George, 1992). Bitumens that form in these
extreme environments also have very distinctive hydrocarbon distribution patterns.
> Read full chapter

Organic Matter in Gas Shales

D. Mani, ... A.M. Dayal, in Shale Gas, 2017

3.2.3 Thermal Maturity of Kerogen

The amount of heat experienced by the source rock in the subsurface is critical for
the generation of hydrocarbons. Thermal maturity is the extent of temperature–time
driven reactions, which are responsible for the conversion of sedimentary organic
matter to oil and gas (Mani et al., 2015a). Vitrinite reflectance (Ro%) and Rock Eval
pyrolysis temperature (Tmax) are popularly used parameters to assess the thermal
maturity of kerogen. Thermally immature source rocks do not have a pronounced
effect of temperature (<0.6%Ro) (Mani et al., 2015a). Thermally mature organic
matter generates oil (0.6–1.35%Ro), whereas the post-mature organic matter is in
wet and dry gas zones (Tissot and Welte, 1984; Mani et al., 2015a). The Tmax values
<435°C indicate an immature stage for generation of hydrocarbons; the temperature
range between 435 and 465°C suggests a mature stage, and those >465°C show
a post-mature stage, suitable for generation of gas (Tissot and Welte, 1984;Hunt,
1996; Mani et al., 2015a).

> Read full chapter

Environmental Concerns of Shale Gas

Production
A.M. Dayal, in Shale Gas, 2017

8.1 Introduction
Carbonaceous shale is a fine-grained, organic-rich sedimentary rock. The technically
recoverable gas depends on a large number of parameters like thermal maturity,
mineralogy, amount of silica content, water source in a nearby area, and a facility for
disposal of flowback water. Shale is also the source rock for conventional hydrocar-
bon. So far, we have been exploring and exploiting conventional oil and gas as they
migrated from source rock to the reservoir rocks, and it was easy to explore them
from such rocks. Geologist knew about the presence of free and adsorbed gas in
organic-rich shale formations, but the exploitation technique was not available. With
the increasing cost of oil and also declining sources of conventional hydrocarbon, it
was necessary to look for an alternate source of energy. Solar, wind, and nuclear are
alternate sources but cannot replace conventional oil and coal as a major source of
energy. The United States took the lead to develop an alternate source of energy and
set up the Shale Research Institute in the year 2000 to develop hydraulic fracturing
and horizontal drilling. Initially, these techniques were used at a small scale, and with
necessary improvement in 2008 onward the petroleum industry could take up the
shale gas project on a large scale. This new source of energy has changed the total
scenario of the world oil market. With this revolution the prices fell, and within four
years the prices were 25% of the earlier prices. The large-scale production of shale
gas in the United States has reduced the import of gas from Canada, and overall
there is excess supply of oil and gas in the global market, which was responsible for
the fall of oil prices.

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Large Coal-Derived Gas Fields and

Their Gas Sources in the Ordos Basin
Giant Coal-Derived Gas Fields and their Gas Sources in China, 2016

3.4.2 Source
The origin analysis discussed up to this point shows that the origin type of natural
gas in the Yulin gas field is mainly coal-derived gas. The thermal maturity (Ro) of the
corresponding source rock ranges from 1.6%–2.0%, having reached substantial gas
generation. The gas generated from coal measure source rock that is interbedded
with sandstone creates favorable conditions for accumulation nearby and provides
an abundant material basis for the formation of the Yulin gas field. However, apart
from this gas source, whether there is any gas input from other areas, it is an issue
worthy of concern. In the following text, the gas source of the Yulin gas field is
explored based on the relationship between 13C1 and Ro, as well as the carbon
isotope characteristics of coal measure gas source rock.

3.4.2.1 Relationship Between 13C1 and Ro

Previous studies have showed a correlation between 13C1 and Ro of corresponding
source rock (e.g., Stahl & Carey, 1975; Dai et al., 1985; Xu & Shen, 1985; Liu &
Xu, 1999). The reservoirs in the Yulin gas field are interbedded with coal measure
source rock; if 13C1 composition of natural gas in the Yulin gas field is similar
to that of gas generated from coal measure source rock, the natural gas would
be mainly proximal; otherwise, distal source rocks might be contributed. Among
various 13C1-Ro formulas, Stahl’s formula is based on the geological settings of
basins in Central Europe, the North Sea, and the United States, in which there are
secondary gas generation characteristics due to their subsidence-uplift-subsidence,
and the gas belongs to instantaneous gas generation at a high evolution stage.
The formula of Xu et al. mainly reflects the fractionation characteristic of 13C1 in
coal-derived gas at low evolution stage; whereas those of Dai et al. (1985) and Liu and
Xu (1999) basically reflect the continuously evolved coal-derived gas characteristics
of source rocks of Mesozoic and below at the high evolution stage. The Yulin gas field
experienced tectonic subsidence; because the tectonic thermal event occurred in the
Late Jurassic–Early Cretaceous period, the source rock rapidly became mature and
entered the high evolution stage, generating large amounts of gas prior to uplift.
Such a gas generation process is similar to the geological models of Dai et al. (1985)
and Liu and Xu (1999). Therefore, these formulas are used to calculate the natural
gas maturity of the Yulin gas field based on the methane carbon isotope value of the
samples (Table 2.4). The Ro corresponded by natural gas of the Yulin gas field figured
out by the Dai et al. (1985) formula ranges from 0.9%–2.1%, 1.3% on average; on
the other hand, that figured by Liu and Xu (1999) formula ranges from 0.9%–1.7%,
1.2% on average; and they are all lower than the Ro of present source rocks in the
Yulin gas field.

3.4.2.2 Carbon Isotope Kinetics Characteristics

Studies into the kinematic similarity of carbon isotopes have looked at simulating
the carbon isotope fractionation of natural gas in the course of generation under
geologic conditions based on research into hydrocarbon generation kinetics, and
these results can be used to quantitatively describe the generation, migration, and
accumulation of natural gas (Tang et al., 1996, 2000; Cramer et al., 2001; Li et al.,
2004). The methanogenesis carbon isotope kinetics of source rocks in the Yulin gas
field is calculated using the thermal history data of the basin (Ran & Chen, 2008)
and the gas generation kinetics parameters of typical coal measure source rocks
and carbon isotope kinetics parameters in the GOR-Isotopes kinetics software. The
results of these calculations are shown in Figure 2.29. The substantial gas generation
stage occurred in the Late Jurassic–Early Cretaceous period, and Ro is about 1.8%.
As shown in the evolution curve of methane, ethane, and propane carbon isotopes,
when Ro reaches 1.8%, the 13C value of the C1-3 component is less than that of
current gas reservoirs of the Yulin gas field, indicating that the carbon isotope of
natural gas generated from in situ source rocks is lighter than that of natural gas in
the gas field.
Figure 2.29. Gas generation history and carbon isotope evolution curve of source
rocks in the Yulin gas field

The study of the relationship between 13C1 and Ro of natural gas in the Yulin
gas field, as well as of the gas generation carbon isotope kinetics of source rocks,
shows that the carbon isotope of natural gas in the Yulin gas field is heavier than
that of natural gas generated in in situ source rocks, indicating that apart from
the contribution of natural gas generated in in situ source rocks, the Yulin gas
field also captured the natural gas generated by distal, high-maturity source rocks.
Based on the spatial distribution of organic maturity of Carboniferous-Permian
coal measure source rocks (Gan et al., 2007), the maturity is very high in the south
and southwest of the Yulin gas field (Figure 2.6), indicating that there might be a
contribution of gas that migrated over a great distance from these areas. The natural
gas generated in in situ source rocks and distal, high-evolution source rocks has
provided an abundant material basis for the formation of the Yulin gas field. The
lithologic reservoir interbedded with coal measure source rock has good proximal
gas supply conditions, whereas the migration and infusion of distal gas are more
favorable for gas accumulation and concentration, thus forming a large lithologic
gas field.

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