Marine and Petroleum Geology 133 (2021) 105312

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Marine and Petroleum Geology

journal homepage: www.elsevier.com/locate/marpetgeo

The effect of oil-based drilling mud (OBM) on the assessment of

hydrocarbon charge potential
Norelis D. Rodriguez a, Barry Jay Katz b, *
a
Chevron Frontier Exploration and Appraisal, 1400 Smith Street, Houston, TX 77002, USA
b
Chevron Technical Center, 1500 Louisiana Street, Houston, TX 77002, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Foundational to source rock assessment in exploration is an understanding of organic enrichment and hydro­
Source rocks carbon generation potential. With an increased use of oil-based drilling mud, particularly in deep water drilling,
Drilling mud problems associated with contamination have complicated source rock assessment. Drilling fluid contamination
Organic-based drilling mud
is assumed to increase the apparent values of the basic screening source rock parameters such as total organic
Contamination
Petroleum
carbon (TOC) and total hydrocarbon generation (S1 + S2).
It has been commonly assumed that the effect of contamination can be reduced or eliminated by pre-treating
samples with organic solvents (i.e., extraction of the sample) prior to analysis. In this study, an attempt is made to
characterize this extraction process on a suite of simulated cuttings samples that were contaminated and
extracted prior to analysis to validate the assumptions presented in the literature.
Results from these experiments show significant differences between values measured on the original and oil-
based drilling fluid contaminated samples before and after extraction. After contamination and before extraction,
measured TOC and Rock-Eval parameters indicate that the oil-based drilling fluids appear to be acting as an
aggressive solvent, altering the apparent source rock potential. Contamination by oil-based drilling fluid appears
to reduce the total organic carbon content and the residual generation (S2) potential, while increasing the free
hydrocarbon content. This may be a result of the presence of solid bitumen or bituminite in the original sample,
which are acted on by the oil-based drilling fluid. Following extraction of the contaminated samples, the TOC and
residual generation potential undergo further reduction and the free hydrocarbons were nearly eliminated. It was
also observed that uncontaminated samples, when extracted, experienced an increase in TOC and the S3 (CO2)
peak. These increases may have resulted from the retention of small amounts of solvent.
Unlike the common assumption in the existing literature, these data indicate that once oil-based drilling fluids
contaminate a sample, pre-treatment extraction does not provide an accurate measure of either the original
organic carbon or residual generation potential. The data indicate that the use of Rock-Eval pyrolysis results from
extracted samples that have been contaminated by oil-based drilling fluid can result in a significant underesti­
mation of the system’s hydrocarbon source rock potential.

1. Introduction impact their characterization.

Drilling fluids are complex mixtures, with different base fluids such
as water or oil-based products, along with a series of additives to deal
with specific well requirements. McDermott (1973) has provided a
detailed summary of the uses of drilling fluids, which remains valid
today. Historically, diesel was the common base-oil, but now base-oils
can include highly refined low aromatic diesel products and low
toxicity synthetic oils. Both the base-oil and the fluid additives may
potentially contaminate cuttings samples recovered from a well and
Over the past several decades, there has been an increase in the use of
oil-based drilling fluids (OBM) because of their greater stability at high
temperatures, increased lubricity in deviated wells, greater penetration
rates, and improved hole stability when water-sensitive shales are pre­
sent (Boyd et al., 1987). Although there are a number of advantages to
using oil-based muds, drilling with these fluids has become problematic
when making geochemical and physical measurements on rock and fluid
samples (e.g., Hart and Fisher, 1998; Wenger et al., 2004; Ohm et al.,
2007 Petersen et al., 2017; Ratnayake and Sampei, 2019). The focus of

* Corresponding author.
E-mail address: barrykatz@chevron.com (B.J. Katz).

https://doi.org/10.1016/j.marpetgeo.2021.105312
Received 29 March 2021; Received in revised form 25 August 2021; Accepted 26 August 2021
Available online 28 August 2021
0264-8172/© 2021 Published by Elsevier Ltd.
N.D. Rodriguez and B.J. Katz
many of these studies has, in general, not been on the basic source rock
screening measurements but on how biomarker signatures have been
altered by the presence of oil-based drilling fluids or organic drilling
additives that leads to erroneous interpretations of age, depositional
environment, correlations between source rock and oil, and thermal
maturity. The impact of the fluid may be complex and variable. For
example, Ohm et al. (2007) reported that OBM contamination may
impact one biomarker group without impacting another.
Although not the primary focus of prior studies, problems associated
with OBM drilling contamination may be quite pronounced on basic
source rock screening analyses, in some cases rendering these data, at
best open, to misinterpretation or, at worst, meaningless. Basic source
rock screening analyses include total organic carbon (TOC) and tem­
perature programmed pyrolysis, typically Rock-Eval (Espitalié et al.,
1977). TOC is considered foundational to source rock assessment,
establishing the amount of organic matter present and is often used to
determine whether the samples should undergo further analysis. Addi­
tional analyses, including Rock-Eval pyrolysis, are often limited to
samples containing greater than 0.5 or 1.0 wt% TOC (Bissada, 1982).
The Rock-Eval parameters measured are: 1) free hydrocarbons (S1)
present; 2) generatable hydrocarbons (S2); and 3) “organic” oxygen
present (S3) as measured by the generated CO2 and trapped at temper­
atures up to 390 ◦ C. The S1 and S2 values are presented in mg HC/g rock.
S3 is presented as mg CO2/g rock. In addition, Tmax, the temperature of
peak hydrocarbon generation is determined, and is often utilized as an
indicator of thermal maturity. These measured parameters are used to
calculate the hydrogen (S2*100/TOC) and oxygen (S3*100/TOC)
indices, which are used to identify organic matter type, with some
limitations when carbon content is low (Katz, 1983), or the oil satura­
tion index (S1/TOC) for potential resource identification (Jarvie, 2012).
Contamination is known to dramatically increase the S1 value.
Contamination is also often thought to be represented by a low tem­
perature shoulder on the S2 peak resulting in an increase in the S2 yield
and hydrogen index and a decrease in Tmax (Petersen et al., 2017).
Ratnayake and Sampei (2019) stated that removal of contaminants is
thus essential for meaningful interpretation as is the identification of any
residual contaminants.
While not directly addressing contamination by oil-based drilling
fluid, Clementz (1979) suggested that free hydrocarbon content (S1) and
the heavy-end bitumen fraction, appearing as part of the S2, can be
removed by solvent treatment. This conclusion led to the suggestion that
solvent washing or “cleaning” of contaminated cuttings samples could
improve the organic carbon assessment (Ratnayake and Sampei, 2019).
After such treatment the S1 value is rendered meaningless due to
removal of the original free hydrocarbons in addition to the removal of
the contaminants. It has been largely accepted that the in situ total
generation potential (S1 + S2) would, therefore, be reduced by solvent
treatment and the degree of reduction would be a function of kerogen
type and thermal maturity. However, the S2 value was thought to still be
largely reflective of the rock’s original residual generation potential, as
was possibly the total organic carbon (Wenger et al., 2004). This was
assumed to be typically the case when the source rock’s organic matter
was dominated by the kerogen fraction (Hunt, 1972). It has, however,
been shown that the S2 peak includes and can be dominated by solid
bitumen and asphaltenes when rocks are examined (Clementz, 1979).
Thus, the impact of solvent treatment may be especially significant for
oil-prone and thermally mature samples where the greatest reduction in
total generation potential would occur because of their more elevated in
situ bitumen values under such conditions. Hackley and Cardott (2016)
have reported that solid bitumen can dominate the organic matter at
thermal maturity equivalent to peak oil generation and beyond for type
I/II kerogens. Nevertheless, uncertainties remain regarding the potential
effects of the extraction process on the other parameters used during the
source rock evaluation process.
Standard preparation or cleaning methods for contaminated samples
consist of washing lightly contaminated cuttings samples with either a
2
Marine and Petroleum Geology 133 (2021) 105312
surfactant or detergent, solvent or solvent mixture, often dichloro­
methane or a combination of dichloromethane and methanol. The
washing process may utilize multiple washes with the solvent and the
use of an ultrasonic cleaner (Ratnayake and Sampei, 2019). This
approach will commonly remove light contamination or surficial coat­
ings on cuttings. Alternatively, Soxhlet extraction is employed to elim­
inate more severe contamination, including that within pore spaces.
Such treatments may result in a sample being visually free of oil (Rat­
nayake and Sampei, 2019), however, low molecular weight hydrocar­
bons may have penetrated the interior of the cuttings. This issue was also
noted by Brocks et al. (2008) who suggested that surficial treatment with
solvents is an ineffective means of removing contaminants. Petersen
et al. (2017) also noted that core samples taken from wells drilled with
oil-based fluids are generally thought to be less prone to the effects of
contamination, especially if the interior is sampled although drilling
mud may invade a core. Wenger et al. (2004) further implied that the
nature of the base-oil and/or the additive may dictate the nature of the
solvent used for the extraction of the contaminant. They also stated that
some additives, such as glycol compounds, are extremely difficult to
remove even after multiple extractions, potentially because of bonding
with clays.
Because of the limitations of solvent cleaning of oil-based drilling
fluids from samples alternative approaches were sought after for source
rock characterization in contaminated samples. Sanei et al. (2020)
suggested that solvent cleaning of OBM contaminated samples may be
effective, but suggested that an alternative pyrolysis approach,
involving changing the temperature ramp, may provide meaningful
source rock screening data. A thermo-vaporization technique has also
been introduced by Ïnan et al. (2018) where extractable organic con­
taminants are removed at temperatures of 350 ◦ C for 60 min or 375 ◦ C
for 30 min. Petersen et al. (2017) also suggested that pyrolysis gas
chromatography could be used for characterization with the results not
dramatically impacted by contamination and may effectively charac­
terize the organic matter present.
The aim of this study is to evaluate the potential effects of drilling
fluid contamination and extraction on the main parameters used for the
evaluation of source rock presence, quality and organic matter type
using OBM contaminated simulated cuttings samples and to determine
how representative “cleaned” samples are of the original rock character
and how any changes may impact source rock assessment.
2. Experimental
Experiments were carried out on sub-samples of an outcrop sample of
the Eagle Ford Formation, collected near Waco, Texas. This sample was
crushed to drill cuttings size rock chips. These chips were mixed to
homogenize and subsequently split to 50-g aliquots. Samples were
analyzed: (1) as collected, (2) following Soxhlet extraction prior to
contamination, (3) following contamination, and (4) following
contamination and after extraction.
Five untreated sample splits were subjected to the basic source rock
screening analyses (TOC and Rock-Eval pyrolysis). The observed varia­
tion in the analytical results among these sample splits provides guid­
ance on the uncertainty associated with the sample preparation and
analysis. Three sample splits were analyzed following extraction but
prior to contamination. Four samples were analyzed following
contamination but prior to extraction. Four samples were analyzed
following contamination with OBM and extraction.
To simulate contamination during drilling, the cutting-size sample
splits were placed in a 1.5 L pressure vessel (manufactured by Parr In­
strument Company) along with the drilling fluid. To the approximately
50 g of rock chips sufficient drilling fluid was added to cover the sample.
The vessels were evacuated and then heated to 200 ◦ C and pressurized to
500 psi for 4 h. These conditions were chosen to simulate the temper­
ature, pressure, and exposure time to drilling fluids experienced by
cuttings while drilling. The conditions were estimated taking into
N.D. Rodriguez and B.J. Katz Marine and Petroleum Geology 133 (2021) 105312

consideration lag time, temperature, and pressure conditions encoun­

tered by a source rock while drilling off the coast of West Africa. The
conditions were insufficient to induce any appreciable amount of hy­
drocarbon generation (Lewan, 1985). The samples were exposed to
three different oil-based drilling fluids: Fluid-A (Sample 1), Fluid-B
(Sample 2); Fluid-C (Sample 3). Sample 4 also used Fluid-A, but with
additives. The three drilling fluids utilized are low aromatic synthetic
oils and are commonly used while drilling deepwater West Africa.
The “cuttings” samples, untreated, contaminated, and extracted
were powdered to 60 mesh (250 μm) for analysis. The powdered samples
were subject to the standard protocol for TOC measurement, where
samples were acidified with 10% HCl to remove carbonates and then
combusted to measure organic carbon using a LECO carbon analyzer.
Pyrolysis was conducted using a Rock-Eval-2 instrument following the
protocols of Espitalié et al. (1977).
Between 20 and 50 g of sample were extracted using a Soxhlet system
with ~250 ml of dichloromethane as the solvent. The samples were
refluxed for about 16 h at a temperature of 39.6 ◦ C.

3. Results

The analytical results obtained on the original or untreated splits are

presented in Table 1 and Figs. 1–5. The variations among these sample
are similar to those observed when multiple analyses are performed on
the same sample by the same laboratory (Katz and Lin, 2021). The mean
values and standard deviations for these analyses are also presented in
Table 1. Some of the differences in measured values may result from the
complexities associated with the homogenization of cuttings-sized
samples as opposed to powders. Prior comparative studies (e.g., Dem­
bicki, 1984; Issacs, 2001) were largely performed on well-homogenized
powdered samples.
The source rock screening analyses performed on the extracted
samples prior to OBM contamination are presented in Table 2. The
solvent extracted samples display the expected reduction in the S1;
measured values have been reduced by ~96.5% compared to the orig­
inal samples. No systematic changes in S2 values were observed to have
resulted from extraction. Samples showed variations of up to approxi­
mately 6% of the untreated value (Fig. 2). These variations are slightly
greater than observed among the untreated sample splits. There are,
however, several unanticipated, but consistent, observations in this
sample series, which indicate that solvent treatment by itself alters
source rock screening parameters independent of drilling fluid
contamination. When the original untreated samples are compared with
the extracted samples a slight increase in TOC appears to have taken
place as a result of solvent treatment. Organic carbon content of the
extracted samples was increased to as much as 115.8% of the original
value. Unexpectedly, there were also increases in the S3 values (Fig. 3).
The extracted S3 values could be more than 600% greater than the
original untreated samples. Together these changes resulted in a slight
reduction in the hydrogen index values and a slight increase in the ox­
ygen index values (Fig. 4). Even though the S2 yields were not
Fig. 1. Comparison of the relationship between organic carbon content and
free hydrocarbons (S1 peak) as determined by Rock-Eval pyrolysis.
consistently effected, the Tmax values were all reduced by more than
20 ◦ C (Fig. 5). All of the reported changes in TOC, S1, S3, and Tmax
exceed one standard deviation of the measured values obtained on the
untreated samples, indicating that the differences reflect the impact of
the solvent on the sample and not either sample or analytical in nature.
The analytical results for the contaminated samples are presented in
Table 3. The contaminated samples display the expected increase in the
S1 peak (Fig. 1). The increase in Sample 4 (Fluid-A with additives) was
less than observed in the other samples. These values may be as much as
650% of the original untreated value. Both the TOC values and S2 yields,
however, display unanticipated reductions relative to the original
samples (Fig. 2). These reductions are significantly greater than one
standard deviation of the values obtained on the untreated samples,
indicating that this is more than would be associated with either
analytical precision or sample preparation. Sample 4 (Fluid-A with ad­
ditives) appears to display the least decrease in yield. The contaminated
samples displayed as much as a 23.5% reduction in TOC from the un­
treated sample and up to almost an 18% reduction in S2 from the original
untreated sample. The S3 values show only minor differences (i.e., less
than one standard deviation) when compared with the original samples
(Fig. 3), with Sample 4 (Fluid-A with additives) displaying an increase
relative to the untreated sample that is greater than one standard de­
viation. Together these results for the contaminated samples produce
increases in the hydrogen indices and little change in the oxygen indices

Table 1
Screening analyses performed on original or untreated samples.
Sample Split No. TOC (wt%) S1a S2a S3b Tmax (◦ C) Hydrogen Indexc Oxygen Indexd

1 6.03 4.10 33.92 0.38 436 563 6

2 5.68 4.03 32.73 0.36 433 577 6
3 6.08 4.07 34.62 0.31 437 570 5
4 5.81 4.04 33.38 0.27 436 575 5
5 5.71 3.12 30.76 0.51 434 539 9
Mean 5.86 3.87 33.61 0.37 435.2 549.4 6.2
Standard Deviation 0.18 0.42 1.47 0.09 1.64 15.4 1.6
a
mg HC/g ro ck.
b
mg CO2/g rock.
c
mg HC/g TOC.
d
mg CO2/g TOC.

3
N.D. Rodriguez and B.J. Katz Marine and Petroleum Geology 133 (2021) 105312

Fig. 2. Comparison of the relationship between organic carbon content and

generatable hydrocarbons (S2 peak) as determined by Rock-Eval pyrolysis.

Fig. 4. Comparison of the hydrogen and oxygen indices placement on a

modified van Krevelen-type diagram.

Fig. 3. Comparison of the relationship between organic carbon content and

carbon dioxide yield (S3 peak) as determined by Rock-Eval pyrolysis.

(Fig. 4). The Tmax values (Fig. 5) are similar to those of untreated orig­
inal samples.
Table 4 presents the screening analyses on the contaminated samples
following extraction. The extracted samples following contamination
showed a decrease in TOC by as much as 28% compared to the
contaminated sample and as much as 42% from the original untreated Fig. 5. Comparison of the relationships between the hydrogen index and Tmax.
sample (Figs. 1–3). The S1 values were also all reduced relative to both
the contaminated samples and the original samples (Fig. 1). The contamination were greater than expected (i.e., the S1 value remained
reduction could exceed 99% compared to the contaminated samples and somewhat elevated; 1.14 mg HC/g rock vs 0.05–0.08 mg HC/g rock for
up to ~98% compared to the original untreated sample. It is worth the other samples studied). All post-contaminated extracted S2 values
noting that the S1 yield of Sample 1 following extraction and

4
N.D. Rodriguez and B.J. Katz Marine and Petroleum Geology 133 (2021) 105312

Table 2 fluids, but trace amounts of free hydrocarbons remain. This is consistent
Screening analyses performed on extracted samples prior to OBM with Ratnayake and Sampei’s (2019) observation that some residual
contamination. contamination may remain after solvent cleaning. Furthermore, the
Sample TOC S1a S2a S3b Tmax Hydrogen Oxygen changes in TOC, S3, and Tmax appears to support the retention of solvent
Split No. (wt (◦ C) Indexc Indexd by the samples. The available data do not permit a determination as to
%) whether the remaining free hydrocarbons more closely represent the
2 6.34 0.12 34.84 1.40 411 550 22 original material or the contaminant. The data clearly indicate that
3 6.49 0.14 32.74 1.81 413 504 28 following the extraction of an OBM-contaminated sample neither the
4 6.73 0.16 33.53 1.84 412 498 27
organic carbon nor the S2 yields are accurate representations of the
a
mg HC/g rock. rock’s original character. Both parameters are significantly less than the
b
mg CO2/g rock. original rock values. The TOC values following OBM contamination and
c
mg HC/g TOC. extraction could represent approximately 59% of the original untreated
d
mg CO2/g TOC. values, with the S2 values being approximately 60% of the original
values. This does not appear to be simply a result of the solvent cleaning
but appears to include interaction with the drilling fluid, which appears
Table 3
to act as an aggressive solvent at the temperatures and pressures of the
Screening analyses performed on post-OBM contaminated samples.
experiment and the presence of solid bitumen throughout the Eagle Ford
Sample TOC S1a S2a S3b Tmax Hydrogen Oxygen
independent of thermal maturity (French et al., 2020).
Split No. (wt (◦ C) Indexc Indexd
%)
The observed changes in Tmax appear to reflect a series of rock fluid
interactions. The decrease in Tmax with the initial solvent treatment
1 4.79 12.50 27.85 0.30 431 581 6
suggests that there was retention of solvent, reducing Tmax values.
2 4.87 25.99 27.12 0.34 433 557 7
3 4.69 21.95 28.66 0.29 433 611 6 Typically, it is assumed that Tmax increases following solvent treatment,
4 4.45 7.27 29.65 0.56 432 666 13 bitumen removal and the elimination of the S2 shoulder. Following
a
mg HC/g rock.
contamination, before and after extraction, the Tmax values are higher
b
mg CO2/g rock. than those of the original samples that were extracted prior to
c
mg HC/g TOC. contamination. As a result of the significant reductions in S2 in the
d
mg CO2/g TOC. contaminated samples these values appear to better reflect the maturity
of the kerogen.
These results indicate that the simple extrapolation of Clementz’s
Table 4 (1979) study, which dealt with naturally stained rocks, is not valid for
Screening analyses performed on extracted sample post-OBM contamination. anthropogenically contaminated samples. At best, it appears that
Sample TOC S1a S2a S3b Tmax Hydrogen Oxygen following the extraction of a drilling mud contaminated sample, the
Split No. (wt (◦ C) Indexc Indexd source rock parameters should be considered minimums. The extraction
%) of OBM-contaminated samples may be most impactful on marginal
1 3.52 1.14 17.99 0.18 432 511 5 source rocks, where source rock attributes are only slightly above
2 3.48 0.05 19.83 0.33 435 570 9 accepted threshold values. The overall impact of oil-based drilling fluid
3 3.79 0.08 21.16 0.24 434 559 6
contamination and extraction should be further confirmed with rocks
4 3.47 0.08 20.62 0.48 434 595 14
containing different kerogens and at different thermal maturity levels as
a
mg HC/g rock. well as with a broader suite of oil-based drilling fluids and additives.
b
mg CO2/g rock. Differences between the Fluid-A sample with and without additives
c
mg HC/g TOC.
d indicates that not only does the base drilling fluid impact the screening
mg CO2/g TOC.
results but so does the additives present.

were reduced compared to the contaminated non-extracted and un­

5. Summary and conclusions
treated samples (Fig. 2), with reductions as much as 31% and as great as
47% compared to the original unaltered samples. As with the S1 peak,
A series of experiments were conducted to examine the impact of
the impact on the S2 peak was greater following OBM contamination and
OBM contamination and the “cleaning” of a sample through extraction
extraction than by solvent extraction alone. All of these differences were
on source rock screening. The analytical results reveal that the basic
greater than one standard deviation of the untreated data, indicating
source rock screening data are impacted in ways both expected and
that these differences are not reflecting analytical precision or sample
unexpected. The analytical results raise questions concerning the use of
preparation. The S3 values for all samples except Sample 4 were also
extracted samples that had been contaminated by OBM to gain an ac­
reduced (Fig. 3) compared to the contaminated and original samples by
curate understanding of the rock’s original organic richness and source
up to 40% and 53%, respectively. However, not all of these changes in
potential. The results following cleaning of the contaminated samples
the S3 value exceeded the one standard deviation benchmark. Sample 4
reveal lower organic carbon contents and residual generation potential
(Fluid-A with additives) display an increase in S3, which is greater than
than the original samples. The organic matter type based on the
one standard deviation. Together these results produce hydrogen indices
hydrogen and oxygen indices appears largely unchanged as does the
similar to the original untreated values (Fig. 4). The extracted contam­
Tmax value. At best, it appears that contaminated samples would provide
inated samples also yielded comparable oxygen index values to both the
a minimum sense of source rock richness and generation potential, as
original and the contaminated samples (Fig. 4). The Tmax values were
well as a reasonable representation of the kerogen type.
also similar to both the untreated and the post-contamination samples
Extraction of the original samples appears to increase the TOC con­
(Fig. 5).
tent and S3 values and reduces the Tmax. This appears to be a result of
either incomplete solvent removal or absorption of the solvent by the
4. Discussion
cuttings. Following OBM contamination, the S1 peak increased signifi­
cantly, but unexpectedly the organic carbon content and residual gen­
Extraction of the OBM-contaminated samples was very effective in
eration potential (S2) both decreased, suggesting that the drilling fluid
removing the free hydrocarbons introduced by the organic based drilling
may act as an aggressive solvent.

5
N.D. Rodriguez and B.J. Katz
A determination whether similar results would be observed with
different drilling fluids, additives, kerogens or at different maturity
levels should be made.
Author credit statement
Norelis D. Rodriguez – idea initiation, oversight or analytical pro­
gram, and presenter of initial study. Barry Jay Katz – primary author of
submitted document.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors express thanks to Chevron Corporation for permission to
publish. A version of this paper was presented at AAPG Annual
Convention and Exhibition, April 2017, in Houston, TX. Drs. Melanie
Everett and Mei Mei provided technical review of an earlier version of
this manuscript. Comments provided by three anonymous reviewers
improved the overall manuscript quality. Dr. Marcus Wigand provided
assistance with the preparation of the contaminated sample suite.
Analytical work was performed by Stratum.
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