TOC calculation of organic matter rich sediments using rock-Eval pyrolysis:
Critical consideration and insights

Bodhisatwa Hazra, Suryendu Dutta, Sumit Kumar

PII: S0166-5162(16)30414-1
DOI: doi: 10.1016/j.coal.2016.11.012
Reference: COGEL 2754

To appear in: International Journal of Coal Geology

Received date: 2 August 2016

Revised date: 16 November 2016
Accepted date: 18 November 2016

Please cite this article as: Hazra, Bodhisatwa, Dutta, Suryendu, Kumar, Sumit, TOC cal-
culation of organic matter rich sediments using rock-Eval pyrolysis: Critical consideration
and insights, International Journal of Coal Geology (2016), doi: 10.1016/j.coal.2016.11.012

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TOC calculation of organic matter rich sediments using Rock-Eval pyrolysis: critical consideration

and insights

Bodhisatwa Hazra, Suryendu Dutta, Sumit Kumar

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Department of Earth Sciences, IIT Bombay, Powai, Mumbai-400076, India

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Email: s.dutta@iitb.ac.in

Abstract

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The Total Organic Carbon (TOC) is one of the most important Rock-Eval pyrolysis derived parameters.
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The present study documents the suppression and underestimation of Rock-Eval TOC as a function of

sample amount being used for analysis. For the purpose of study, a manually isolated vitrain band,
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carbonaceous shale and two shales were analyzed at different weights using a Rock-Eval. For the vitrain
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band and the carbonaceous shale samples, a drop in TOC content was observed with increasing sample
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amount. In each of the case (vitrain and carbonaceous shale), although the S2 pyrograms were fairly
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similar at successive higher weight fractions, it was observed that increasing portions of the CO 2 released
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during Rock-Eval oxidation and represented by S4 oxidation graphics, was undercounted with increasing

sample charge, thereby underestimating the residual carbon (RC) and TOC content. The results indicate

that at lower sample weights the entire organic matter is oxidized below 650 °C (S4-S5 boundary).

However, at higher weights the organic matter is oxidized through a wider temperature range (beyond

650 °C) and consequently resulting in release of CO2 through a wider temperature range. The insights

developed in the paper indicate that sample amount should be around 5-10 mg and 30 mg for type III-IV

organic matter-bearing coals and carbonaceous shales respectively. However, when the grain size was

kept finer (<63 micron), it was observed that sample amounts can be kept around 15 mg for type III-IV
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organic matter-bearing coals. No change in TOC with increasing/decreasing sample charge was observed

in case of low TOC shales.

1. Introduction

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With the growing energy need and emergence of shale gas and coal bed methane as hydrocarbon

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reservoirs in the past few decades, initial geochemical screening involving assessment of these

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hydrocarbon reservoirs in terms of the quantity, quality, and maturity of the organic matter has appeared

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as a crucial step (Espitalié et al., 1977; Jarvie, 2012a, b). The Rock-Eval pyrolysis technique has seldom

been used widely as a geochemical screener because of its ability to rapidly generate information on the
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quantity, quality, and maturity of sedimentary organic matter (Espitalié et al., 1977; Lafargue et al., 1998;

Behar et al., 2001). Recently, Rock-Eval pyrolysis has also been extended to the analysis of organic
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matter in geologically recent sediments and soils (Di-Giovanni et al., 1998, 2000; Stein et al., 1999;
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Disnar et al., 2003; Sanei et al., 2005; Outridge et al., 2007; Carrie et al., 2010).
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Along with hydrogen index (HI), oxygen index (OI), Tmax and hydrocarbons released under S1 and S2
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curves of Rock-Eval pyrolysis, the Total Organic Carbon (TOC) is one of the most important Rock-Eval
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pyrolysis derived parameters. It is calculated by summing the pyrolyzable carbon (PC) and residual

carbon (RC). The PC (generated during the pyrolysis stage) is calculated from the pyrolysis stage derived

S1, S2 and S3 (partly) components, while the RC is derived from the oxidation phase by summing the

CO (S4CO peak) and CO2 (S4CO2 peak) generated due to oxidation of organic matter (Lafargue et al.,

1998; Behar et al., 2001). While considerable emphasis has been laid upon Rock-Eval S1 (Hunt, 1996),

S2 (Lafargue et al., 1998; Behar et al., 2001), and S3 (Katz, 1983) components, and their use in

predicting hydrocarbon plays more precisely (Peters, 1986; Peters and Cassa, 1994; Peters et al., 2005;
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Carvajal-Ortiz and Gentzis, 2015), little stress has been laid upon the RC component of TOC, although

ironically RC is the major portion of the TOC.

Behar et al (2001) discussed that the typical sample amount should range from 50 to 70 mg for bulk

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rocks, 10 to 30 mg for coals, 5 to 15 mg for isolated organic matter and 1 to 2 mg for high petroleum

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potential kerogens. Moreover, the Rock-Eval pyrolysis user‘s guide also suggests similar amount for bulk

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rocks, isolated organic matter, and high petroleum potential kerogens, and 10 to 20 mg for coals. In this

paper, the authors have tried to document and explain the drop in RC and TOC using a Rock-Eval 6

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pyrolyzer with increasing charge/amount in one vitrain band isolated manually from a coal sample and
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one carbonaceous shale sample, within the permissible limits. Consequently, considerable stress has been

laid upon the S4 CO2 oxidation graphics and their implications in underestimating TOC, which may
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eventually lead to improper source rock interpretations.

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2. Methodology
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2.1 Sample collection: For understanding the effect of sample weight on Rock-Eval pyrolysis TOC and
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RC, a vitrain band was separated manually from a Lower Permian Barakar Formation coal sample,
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collected from the South Karanpura basin, India. The vitrain was then crushed (60-110 mesh), measured

and collected in crucibles in different weight fractions to perform Rock-Eval pyrolysis. Similarly the two

shales and carbonaceous shale samples, collected from Early Eocene lignite-bearing sequences in the

Valia and Mangrol areas of the Cambay Basin, Western India, were crushed and subjected to Rock-Eval

pyrolysis analysis at different weight fractions.

2.2 Rock-Eval pyrolysis: The manually separated vitrain band, the carbonaceous shale and the two other

shale samples were analyzed at different weight fractions using a Rock-Eval 6, manufactured by Vinci

Technologies, for conducting pyrolysis experiments. In addition to these IFP 160000 standard was also
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analyzed at two different weights to determine if weight at all influences its standardized Rock-Eval

parameters. The details of Rock-Eval 6 functioning can be found in Lafargue et al (1998) and Behar et al

(2001). To compare the results and the effect of final oxidation temperature on TOC, two different final

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temperatures of 850 °C and 750 °C were used.

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3. Results and discussions

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3.1 Carbonaceous shale and vitrain:

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3.1.1 Analogies from S4 CO2 oxidation graphics: The results related to Rock-Eval pyrolysis of the

carbonaceous shale sample and vitrain lithotype are given in Table 1. Peculiarly, with increase in sample
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charge a decrease in TOC content was observed for both the samples. While for the carbonaceous shale

beyond 40 mg of sample weight a drop in values of TOC was observed, for the vitrain sample the drop
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was observed beyond 10 mg of sample weight (Fig. 1). The PC of the carbonaceous shale was observed

to be nearly similar at the different weight fractions (Fig. 2), while for the vitrain PC was observed to
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vary within a narrow range and showed slight increase with increasing sample weight (Fig. 2). Strikingly,
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the RC was observed to fall down from 65.54 wt % (at 5.2 mg) to 39.1 wt % (at 30 mg) for the vitrain
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and from 30.25 wt % (at 30 mg) to 20.46 wt % (at 70 mg) for the carbonaceous shale sample.

Consequently a negative relation was observed between RC and sample weight (Fig. 3). This fall in RC

eventually resulted in fall of TOC content with increasing sample charge (Fig. 3). Closer examination of

the S4 CO2 oxidation graphics reveals the reason why the RC and TOC were observed to fall for the

above-mentioned cases.

Fig. 4 shows the Rock-Eval S4 CO2 oxidation graphics of the carbonaceous shale sample at weights of

30, 35.1, 40, 49.9, 60, and 70 mg. As already mentioned, RC is calculated by summing the organic

carbon which is oxidized to CO (S4CO peak) and CO2 (S4CO2 peak). While Lafargue et al. (1998)
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previously indicated 650 °C to be the boundary between S4 and S5 (organic carbon and mineral carbon),

Behar et al. (2001) mentioned that for rocks containing few carbonates, S4 CO2 stretches between the

starting of oxidation (300 °C) to a minimum between 550 and 720 °C. In the present study, the S4-S5

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boundary was observed to be placed at 650 °C for all the weight fractions. In Fig. 4, the bold green line

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represents the 650 °C S4-S5 boundary.

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It can be clearly seen that beyond 40 mg sample weight, the zone to the right of the green line (shaded

zone) increases with increasing sample charge (Figs. 4D, 4E, and 4F). The shaded zone represents the

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area, which is not included in the calculation of RC and TOC. When the green line at 650 °C was
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extended to the end (end of oxidation temperature of 750 °C), the TOC content at the different weight

fractions were also observed to increase. While initially at 40, 49.9, and 60 mg weight fractions the TOC
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content was observed to be 33.88, 31.63, and 26.93 wt % respectively, the revised TOC content after
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extending the line to the end were observed to be 33.92, 33.73 and 33.27 wt % respectively i.e. now the

TOC contents were observed to be fairly similar. The small differences in TOC can be attributed to the
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in-homogeneity within the carbonaceous shale sample. For the 70 mg weighed sample, TOC content was

further lowered. In the present study the carbonaceous shale used does not contain any carbonate
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minerals (Supplementary Fig. 1). Hence, it can be assumed that the CO2 generated must be of organic

origin and thus for the RC and TOC calculation, the entire area till 750 °C in the S4 CO2 oxidation

graphic should be considered. Closer look of the S4 CO2 oxidation graphics also reveals that for 30 and

35.1 mg sample weights the entire area under S4 CO2 oxidation graphics is considered for TOC

calculation (Figs. 4A and B). However, for the 40 mg sample weight (Fig. 4C) only a small area was

under-estimated and hence even after re-positioning the boundary to the end, the TOC was observed to be

similar (Table 1). Although the Rock-Eval 6 user‘s guide suggests use of 50-70 mg of samples for bulk

rocks, the results indicate that beyond 35 mg, the Rock-Eval TOC may be underestimated for
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carbonaceous shales. In addition, it would not be out of place to mention that the nature of the

carbonaceous shale can also influence the Rock-Eval parameters. The carbonaceous shale used here was

collected from a lignite mine and is marked by presence of huminitic organic matter showing HI value of

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42 mg HC/g rock (at 10 mg). Earlier, Carvajal-Ortiz and Gentzis (2015) demonstrated that for a Green

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River Shale sample bearing type I-II organic matter, by using smaller sample amounts (5.2 mg) a more

precise TOC and HI was obtained.

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Similarly, for the vitrain at different weight fractions, a strong decrease in TOC content was observed

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beyond 10 mg sample weight. Fig. 5 shows the S4 CO2 oxidation graphics of the vitrain at weights of
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15.1 mg (Fig. 5A), 20 mg (Fig. 5B), and 30.1 mg (Fig. 5C). The final oxidation temperature for the

vitrain was kept at 850 °C. Similar to the observations made on the carbonaceous shale sample, when the
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boundary line at 650 °C was repositioned at 850 °C for 15.1 mg, 20 mg, and 30.1 mg weights, the revised
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TOC contents were observed to be fairly similar (Fig. 5; Table 1). The small differences in TOC values

can be attributed to the in-homogeneity of the vitrain lithotype. Like the carbonaceous shale sample, the
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vitrain band or the coal from which the band was separated does not contain any carbonate minerals

(Supplementary Fig. 2) and hence the entire area within 850 °C in the S4 CO2 oxidation graphic should
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be considered. For the above mentioned set of analyses, the authors used IFP ‗basic method‘. Previously

Behar et al (2001) mentioned that for coals generating late methane i.e. for mature coals and containing

few carbonate minerals, instead of carrying out analysis using ‗basic method‘, ‗pure organic matter

method‘ should be preferentially used. The essential difference in the two methods lies on the final

pyrolysis temperature and the oxidation temperature upto which S4 CO2 is considered for RC and TOC

calculation. While in the ‗basic method‘ the S4-S5 boundary lies generally at 650 °C and S4 CO2 is

considered upto the S4-S5 boundary, in case of ‗pure organic matter method‘ as no minerals are present,

the S4 CO2 is considered till the end of the final oxidation temperature (850 °C). As already mentioned,
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the vitrain/coal sample used here is devoid of carbonates and analysis using the ‗pure organic matter

method‘ would have resolved the problems related to the under-estimation of TOC with increasing

sample weight. However, for samples bearing carbonate minerals, using ‗pure organic matter method‘

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would generate higher RC and TOC values. Hence, interpreters should have prior knowledge about the

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presence/absence of carbonate minerals within the rock or should routinely remove carbonate minerals

before analysis. It must be understood that over the last few decades Rock-Eval pyrolysis has been the

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‗workhorse‘ and ‗geochemical screener‘ of the energy industry while evaluating hydrocarbon source rock

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potential due to its rapid evaluation technique, requirement of only small amounts of material, and

production of reliable data (Carvajal-Ortiz and Gentzis, 2015). Instead of eliminating carbonate minerals
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or knowing about the presence/absence of carbonate minerals, a more rapid and convenient way would

be to use lesser sample amounts (5-10 mg; discussed below) for reliable data generation.
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This above-mentioned problem of under-estimation of TOC content is not encountered when 5 mg

weight of vitrain was subjected to pyrolysis. Fig. 6 shows the Rock-Eval S4 CO2 oxidation graphics of
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the sample at 5 and 10 mg weights. Two experiments for each of the 5 mg and 10 mg samples were

carried with final oxidation temperatures of 750 °C and 850 °C. When the final temperature in the
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oxidation chamber was kept at 850 °C, the 5.2 mg weighted vitrain shows a TOC content of 76.11 wt %

(Fig. 6A). When the green line at 650 °C was extended to the end (end of oxidation temperature of 850

°C), the TOC content for the 5.2 mg sample was observed to be similar (76.17 wt %; Fig. 6A'; Table 1).

However some minimal difference was observed in case of the 9.9 mg weighed sample with the TOC

increasing from 77.44 wt % (650 °C; Fig. 6B) to 77.73 (850 °C; Fig. 6B'). Hence, it can be inferred that

when samples weighing around 5-10 mg are used for TOC calculation, the entire CO2 released from

organic matter during oxidation takes place below 650 °C, thereby causing the entire area of the S4

oxidation graphics to be considered for TOC calculation. The under-estimation of TOC (wt %) with
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increasing sample charge (both in case of the carbonaceous shale and vitrain) can be attributed to the

oxidation of organic matter at higher weights through a wide temperature range thereby causing the CO 2

(from organic matter) to be generated for a wider range of temperature even beyond 650 °C [organic

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carbon- mineral carbon boundary].

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Figs. 6A'' and 6B'' shows the S4 CO2 oxidation graphics for the 5 mg and 10 mg weighted samples, with

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the final oxidation temperature of 750 °C. It has been suggested that oxidation temperatures upto 850 °C

improves TOC determination by complete combustion of coals (Lafargue et al., 1998; Sykes and

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Snowdon, 2002). However, since the sample studied is immature in nature [Tmax (avg.): 425 °C; Table 1]
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and devoid of carbonates, even final oxidation temperatures of 750 °C results in complete generation of

organic CO2 at lower weights. Similar to when samples were heated upto 850 °C, here also it can be seen
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that in case of the 5 mg weighted sample the entire area of the S4 CO2 oxidation graphic is considered for
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TOC calculation (Fig. 6A''). On the other hand, for the 10 mg sample only a small portion of the area

falls beyond the 650 °C boundary (Fig. 6B'').

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As evidenced from the present study using the ‗basic method‘, calculation of RC and TOC is largely
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dependent upon the S4 CO2 oxidation graphics and the portion of its area below 650 °C, which is

counted. Although for the 60 and 70 mg weighed carbonaceous shale sample (Fig. 4) final oxidation

temperature of 850 °C would have resulted in complete generation of CO2, but this would not have

influenced the TOC/RC content at those weights. Hence for a carbonaceous shale containing type III/IV

organic matter sample weights can be kept at 30-35 mg, while for coal samples containing type III-IV

organic matter the sample weight should be around 5-10 mg.

3.1.2 Analogies from S4 CO2 oxidation graphics:

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Generally, FID responses higher than 125 mV are known to saturate the FID detectors of Rock-Eval 6

(Behar et al., 2001; Vinci Technologies, 2003; Carvajal-Ortiz and Gentzis, 2015). In the present study,

barring the 30 mg weighed vitrain FID responses of all the samples were below the saturation limit (Fig.

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7). The comparatively lower FID signals even at such higher weights (15-25 mg) can be attributed to the

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lower hydrocarbon generation potential of typical type III organic matter. Moreover, as previously

mentioned, the PC at different weight fractions is nearly similar (Fig.1; Table 1). The near similar

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Gaussian shape of the S2 pyrograms at successively higher weight fractions can also be explained

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similarly. As previously mentioned under methodology the final pyrolysis temperature for the above

experiments were kept at 650 °C. Although the desired final pyrolysis temperature for coals is 800 °C
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(Lafargue et al., 1998; Behar et al., 2001), however as the sample studied here is essentially immature in

nature, so final pyrolysis temperatures of 650 °C resulted in generation of almost complete S2 signals at
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the different weight fractions. Closer examination of the S2 pyrograms show that the pyrolysis curve

almost returned to the baseline indicating generation of almost complete S2.

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Earlier, Carvajal-Ortiz and Gentzis (2015) demonstrated that for a Green River Shale sample bearing type

I-II organic matter, by using smaller sample amounts (5.2 mg) a more precise TOC and HI was obtained.
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When 60 mg sample amount was used, the TOC was reduced by 11% and S2 reduced by 42%, causing

the S2 pyrograms to be broader than a tighter Gaussian shape due to FID saturation. While the above-

mentioned paper using S2 pyrograms showed that sample amount should be kept smaller for shales

containing type I-II organic matter, the present exercise emphasizing the S4 CO2 oxidation graphics

reveal that even for lower hydrocarbon yielding carbonaceous shales (containing type III-IV organic

matter), the sample amount should be kept at around 35 mg instead of 50-70 mg. The low hydrocarbon

generation potential of the studied carbonaceous shale is also manifested by their lower S2 values (Table

1) and lower FID signals (Fig. 8). Similar to the S2 pyrograms of the vitrain band, the carbonaceous shale
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also displays near similar Gaussian shape of the S2 pyrograms at successively higher weight fractions.

Thus as seen in both the cases (vitrain and carbonaceous shale), although the S2 pyrograms at different

weight fractions are similar and much below the FID saturation limits, the TOC gets underestimated at

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higher weight fractions due to oxidation of organic matter through a wide temperature range thereby

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causing the CO2 (from organic matter) even beyond 650 °C. This hence calls for closer examination of

Rock-Eval S4 CO2 oxidation graphics.

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3.2 Analogies from shales and IFP standard: Two shale samples (Sh1 and Sh2) were analyzed using

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Rock-Eval at different weight fractions (30-90 mg). Similar to the vitrain band and the carbonaceous
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shale, these two shale samples were also devoid of any carbonate minerals (Supplementary Figs. 3 and

4). TOC values for both the shales were observed to be constant throughout the entire weight range
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(Table 1) with the values between 2.02-2.11 wt % for Sh1 and 7.24-7.31 wt % for Sh2. Similarly, when
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the IFP 160000 standard was analyzed at two different weights (Table 1), the TOC was observed to be

similar. Although it is suggestive to use 50-70 mg of bulk rock samples and IFP 160000 standard (Rock-
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Eval user‘s guide), the other Rock-Eval parameters like S1, S2, Tmax were also observed to be within the

allowable limits given by Vinci Technologies (2003) at the two different weights. Hence, for shales/bulk
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rocks with lower organic matter content, the Rock-Eval TOC is more precisely estimated at different

weight fractions as the volume of organic matter is low and is oxidized within the limits of S4-S5

boundary.

3.3 Effect of grain size and weight on Rock-Eval TOC: The Rock-Eval 6 user‘s guide suggests using

samples grinded within the range of 100 microns to 2 mm. The influence of sample grain size on

different Rock-Eval parameters had been previously studied by Inan et al. (1998). They documented that

many Rock-Eval parameters are affected by increasing grain size of the sample being pyrolyzed.

Pyrolysis of many samples from different lithologies showed that S1, S2, even S3 were adversely
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affected (were less than expected compared to values obtained on powder split; ≤106 micron) as the

grains size of the sample used for pyrolysis was increased. However, the effect of grain size on Rock-

Eval TOC was not investigated and was determined only on 106-micron grain size split of the samples.

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For understanding the influence of sample grain size on Rock-Eval TOC, we separated a vitrain band

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from a coal sample of Upper Permian age (Raniganj Formation) collected from Jambad colliery,

Raniganj basin, India. The sample was crushed into four size fractions: <500 micron (35 mesh), <250

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micron (60 mesh), < 105 micron (140 mesh), and < 63 micron (230 mesh). For each size fraction, the

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experiments were again carried out at three different weights viz. 10 mg, 15 mg, and 20 mg. Fig. 9 shows

the S4 oxidation graphics of the vitrain sample crushed to < 63 micron, < 105 micron, <250 micron, and
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<500 micron sizes at the above mentioned three weight fractions. It can be clearly seen that when 10 mg

sample weight was used at each size fraction, the entire area of the S4 CO2 oxidation graphic almost
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completely is considered for TOC calculation. At 15 mg weight, interestingly for the <63 micron sized

particles, nearly the entire area of the S4 CO2 oxidation graphic is to the left of the 650 °C boundary i.e.
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almost the entire area is considered for RC and TOC calculation. Significantly, with increasing grain size
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the S4 CO2 oxidation curve can be observed to move towards right i.e. towards and beyond the 650 °C
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boundary. Correspondingly at 15 mg weight, the area undercounted for RC and TOC calculation i.e. the

area of the S4 CO2 oxidation curve to the right of the 650 °C boundary, can be observed to sequentially

increase from the < 105 micron size fraction to the <500 micron size fraction (Fig. 9). This essentially

indicates the importance of the size of particles of the sample that is being analyzed. Decreasing the

particle size to finer levels (<63 micron in the present study), provides additional surface area, and hence

gets almost entirely combusted even at higher sample weights of 15 mg. At 20 mg sample weight, for all

the size fractions, the S4 CO2 oxidation curve was observed to move beyond the 650 °C boundary, and

less amusingly, the area to right of the boundary was observed to sequentially increase with increasing
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grain size, with the least being for the <63 micron sized particles (Fig. 9). Hence while using finer sized

particles (<63 micron, as seen in the present study), sample weights can be kept around 15 mg, preferably

lower. However, closer examination of S4 CO2 oxidation graphics appears to be an extremely critical

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step for precise data generation and interpretation. In the Rock-Eval ‗basic method‘ during the oxidation

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stage, the heating rate is maintained at 20 °C/min (Vinci Technologies, 2003). It is likely that heating at

lower oxidation rates (for example 10 °C/min) may result in complete combustion of organic matter at

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temperatures below 650 °C and allow usage of greater amounts of sample. The effect of sample grain

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size on Rock-Eval parameters, is also evident from the increase in S1, S2, and Tmax values for the <63

micron and <105 micron sized particles compared to the <250 and <500 micron sized particles, and can
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similarly be inferred to be caused due to the increased surface area of the finer sized particles (Fig. 10).

Similar to the earlier observation (Fig. 2), here also it can be observed that at each specific grain size
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there is an increase in S2 with increasing sample weight (Fig. 10). For the above-mentioned set of

analyses, the final oxidation temperature was kept at 750 °C.

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4. Conclusions: While Carvajal-Ortiz and Gentzis (2015) discussed the significance and control of S2

pyrograms on different Rock-Eval parameters including TOC, the present work indicates the importance
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and influence of Rock-Eval S4 CO2 oxidation graphics on TOC measurement. It thus calls for

interpreters to have closer examination of Rock-Eval pyrolysis data, S2 pyrograms, and S4 CO2 oxidation

graphics together. Together these two works can serve as a guideline about how much sample weight

should be used (depending upon the type of material) for precise data generation. The undercounting of

TOC even for type III-IV organic matter-bearing coals and carbonaceous shales indicates that the sample

weight used for carrying out analysis is critical and should be kept preferably around 5-10 mg and 35 mg

respectively. Moreover, the present study also documents the importance and role of sample grain size on
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Rock-Eval TOC determination, and indicates that when grain size is kept finer (<63 micron), weight of

type III-IV organic matter-bearing coal samples can be kept upto 15 mg.

Acknowledgements

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The authors would like to thank the reviewer Dr. Sedat Inan and the Editor-in-Chief Dr. Özgen Karacan,

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for their suggestions and comments which have largely improved the quality of the manuscript. S. Dutta

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would like to thank the OIDB, Government of India for providing financial support to procure the Rock-

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Eval 6 equipment at IIT Bombay. IIT Bombay is also acknowledged for providing research scholarships

to B. Hazra and S. Kumar. MA

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Sanei, H., Stasiuk, L.D., Goodarzi, F., 2005. Petrological changes occurring in organic matter from recent
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List of Figures
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Fig. 1: Plot between sample amount (mg) and TOC (wt %) / RC (wt %) contents of the vitrain A sample
at different weight fractions.

Fig. 2: Plot between sample amount (mg) and PC (wt %) contents of the vitrain A and carbonaceous
shale sample at different weight fractions.

Fig. 3: Plot between sample amount (mg) and TOC (wt %) / RC (wt %) contents of the carbonaceous
shale sample at different weight fractions.

Fig. 4: Rock-Eval S4 CO2 oxidation graphics of the carbonaceous shale sample at weight fractions.

Fig. 5: Rock-Eval S4 CO2 oxidation graphics of the vitrain A sample at weights of 15.1, 20, and 30.1 mg.

Fig. 6: Rock-Eval S4 CO2 oxidation graphics of the vitrain A sample at weights of 5.2 and 9.9 mg with
final oxidation temperatures of 850 °C (A, A', B, and B') and 750 °C (A'' and B'').
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Fig. 7: Rock-Eval pyrograms of the vitrain A sample at different weight fractions.

Fig. 8: Rock-Eval pyrograms of the carbonaceous shale sample at different weight fractions.

Fig. 9: Rock-Eval S4 CO2 oxidation graphics of vitrain B sample at different size and weight fractions.

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Fig. 10: Plot between sample amount (mg) and S2 (mg HC/g rock) contents of the vitrain B sample at
different weight and size fractions.

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Table 1: Rock Eval parameters of isolated vitrain, one carbonaceous shale, two shale samples and IFP

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160000 at different weights

Sample Weight S1 S2 Tmax MAS3 S4 CO2 PC RC TOC TOC* HI OI

(mg) (mg (mg (°C) (mg (mg/g (wt (wt (mg (mg
HC/ HC/ g CO2/ rock) %) %) HC/ CO2/
g rock) g g g
rock) rock) TOC) TOC
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5.2 1.07 114.14 429 6.98 1465.13 10.57 65.54 76.11 76.17 150 9
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5.1750 0.99 113.06 427 7.49 1476.33 10.48 66.05 76.53 76.60 148 10
Vitrain A 9.9 0.85 126.64 424 7.33 1473.56 11.55 65.89 77.44 77.73 164 9
10.2750 1.08 118.23 424 7.48 1465.59 10.85 65.82 76.67 76.92 154 10
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15.1 1.04 130.44 424 6.56 1223.36 11.73 58.84 70.57 75.18 185 9
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20.0 1.03 133.91 424 6.8 1003.16 11.92 52.48 64.40 76.07 208 11
25.1 1.06 130.95 425 6.75 859.35 11.77 45.54 57.31 74.86 228 12
30.1 0.94 138.04 422 6.88 723.45 12.34 39.10 51.44 76.46 268 13
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30.0 1.38 16.19 402 34.41 914.58 3.48 30.25 33.73 33.75 48 102
35.1 1.22 14.85 403 35.11 923.69 3.27 30.37 33.61 33.64 44 104
Carbonaceous 40.0 1.11 14.93 403 35.51 956.06 3.18 30.70 33.88 33.92 44 105
shale 49.9 1.12 15.03 402 35.65 901.65 3.30 28.33 31.63 33.73 48 113
60.0 1.11 15.15 404 35.75 778.56 3.23 23.70 26.93 33.27 56 133
70.0 1.18 16.72 404 36.68 681.24 3.35 20.46 23.81 29.86 70 154
30 0.05 0.86 431 2.00 53.34 0.19 1.84 2.03 - 42 99
45 0.05 0.76 433 2.04 53.96 0.17 1.86 2.03 - 37 100
Shale (Sh1) 60.1 0.04 0.77 430 2.06 54.40 0.17 1.85 2.02 - 38 102
90 0.03 0.7 431 2.01 57.18 0.18 1.93 2.11 - 33 95
30 0.08 14.4 428 3.64 177.92 1.42 5.82 7.24 - 199 50
45 0.07 14.18 429 3.54 186.78 1.4 5.84 7.24 - 196 49
Shale (Sh2) 60 0.07 14.32 429 3.59 187.44 1.4 5.88 7.28 - 197 49
90.1 0.07 14.06 428 3.66 192.25 1.38 5.93 7.31 - 192 50
IFP 160000 30 0.2 12.27 413 0.99 63.56 1.1 2.15 3.25 - 378 30
59.9 0.19 12.4 415 0.99 65.31 1.1 2.17 3.27 - 379 30
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Note: 5.1750 and 10.2750 represents the two coal samples for which the final Rock Eval oxidation
temperatures were kept at 750 °C. TOC* (wt %) represents the TOC content when the S4-S5 boundary
line (650 °C) was stretched to the end of the final oxidation temperature. See text for further discussions.

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Table 2: Effect of grain size and weight on Rock-Eval TOC

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Sample Size Weight S1 S2 (mg Tmax S3 S4 CO2 PC RC TOC HI OI
(micron) (mg) (mg HC/ g (°C) (mg (mg/g (wt (mg (mg
HC/ g rock) CO2/ rock) %) HC/ CO2/

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rock) g g g
rock) TOC) TOC

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10.50 3.65 126.87 432 6.91 1587.31 12.00 65.83 77.83 163 9
15.00 3.46 132.94 431 6.89 1545.69 12.39 64.65 77.04 173 9
<63 20.30 3.27 142.38 431 6.63 1436.46 13.08 61.02 74.10 192 9
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10.20 2.13 115.4 432 6.58 1585.09 10.86 66.58 77.44 149 8
15.50 2.05 127.59 430 6.37 1526.21 11.74 65.02 76.76 166 8
<105 20.00 2.17 132.75 430 6.22 1269.65 12.12 56.84 68.96 193 9
Vitrain
10.00 1.71 114.09 427 6.61 1594.96 10.67 68.42 79.09 144 8
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15.20 1.68 117.35 427 6.45 1409.02 10.83 62.86 73.69 159 9
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<250 20.00 1.62 121.41 428 6.39 1135.11 11.10 53.84 64.94 187 10
10.40 1.49 113.86 423 7.15 1543.90 10.45 66.83 77.28 147 9
15.30 1.1 116.84 423 6.69 1389.70 10.72 63.45 74.17 158 9
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<500 20.30 1.24 120.72 423 6.63 1119.91 11.00 53.58 64.58 187 10
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HIGHLIGHTS

 Influence of sample weight on Rock-Eval TOC calculation of organic rich sediments

 Significance of Rock Eval S4 CO2 oxidation graphics on RC and TOC determination
 Oxidation of organic matter at higher weights through a wide temperature range

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