International Journal of Coal Geology 229 (2020) 103570

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International Journal of Coal Geology

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

Optical parameters and microstructural properties of Solid Bitumens of high T

reflectance (Impsonites). Reflections on their use as an indicator of organic
maturity
Isabel Suárez-Ruiza, , Tatiana Juliaob, Sandra Rodriguesc, Ignacio Cameana
⁎

a
Instituto de Ciencia y Tecnología del Carbono (INCAR-CSIC), Francisco Pintado Fe 26, 33011 Oviedo, Spain
b
ICP-ECOPETROL, Km. 7 via Piedecuesta, Piedecuesta, Santander, Colombia
c
School of Earth and Environmental Sciences, The University of Queensland, St Lucia, QLD 4072, Australia

ARTICLE INFO ABSTRACT

Keywords: Six solid bitumen samples from Paja Formation (Cretaceous of Colombia) were optically, chemically and
Solid bitumen structurally characterized using bulk chemistry, reflectance indicating surface (RIS), micro-Raman and X-ray
Impsonites diffraction (XRD) parameters. The volatile matter and carbon contents and high random reflectance (Ro%)
Reflectance placed these solid bitumens in the category of cata-impsonites according to Jacob's classification. RIS axes (RMAX,
Anisotropy
RINT and RMIN) form almost a sphere, and consequently, the anisotropy (Ram or bireflectance values) of these
Structural order
Optical microscopy
materials is very weak, comparatively to other carbonaceous materials (coals) of similar degree of evolution. The
X-Ray diffraction weak anisotropy character of the solid bitumen is related to the absence of pressure in the system, which did not
Micro-Raman spectroscopy promote the orientation of the basic structural units (BSUs) in a three-dimensional arrangement. The degree of
Equivalent Vitrinite reflectance ordering evaluated by Raman parameters, such as full width at half maximum (FWHM) of the D1 and G bands,
and XRD parameters, including d002 and crystallite sizes Lc and La, showed that the solid bitumens of the Paja
Formation have a low structural order equivalent to high-rank coals, specifically anthracites B
(3.0% ≤ Ro < 4.0%), although their reflectance values placed them in a higher rank (Ro > 4.0%). The dis­
crepancy between high reflectance and low degree of structural order can explain why some of the equations
used to estimate equivalent vitrinite reflectance (Ro eq. Vite) from solid bitumens do not work universally.
Taking in consideration several equations available in the literature, Jacob's equation (Jacob, 1989) was the one
that fitted the Ro eq. Vite values in the range of 3.0% to 4.0%, which parallels with the degree of structural order
obtained for the solid bitumens. Consequently, Jacob's equation can now be extended to solid bitumen in the
range of cata-impsonites.

1. Introduction
Solid bitumens are natural carbon materials and a secondary or­
ganic product derived from the generation, migration and transforma­
tion of hydrocarbons and are found mainly associated to source-rocks
and reservoir rocks. Although solid bitumens usually occur as disperse
organic matter within the rock matrix, or filling fractures, voids, mi­
crofossil cavities and in recrystallized minerals, at times they may ac­
cumulate in great amounts, giving rise to large deposits that can be
mined and commercially exploited, as in the case of solid bitumens (of
high reflectance) found in the Paja Formation (Cretaceous age) of
Colombia (Etayo-Serna, 1968a, 1968b; García Castillo and Vargas
Escudero, 2015).
Whereas other natural carbon materials such as coals (particularly
high-rank coals), natural coke and graphites that display a peculiar
texture and structure related to the spatial arrangement of the poly­
aromatic basic structural units or BSUs induced by thermal and pressure
(oriented stress during tectonism) conditions during the coalification
process have been widely investigated by many authors (Hevia and
Virgos, 1977; Kwiecinska et al., 1977; Ragot, 1977; Ting, 1981; Lespade
et al., 1984; Beny-Bassez and Rouzaud, 1985; Deurbergue et al., 1987;
Kilby, 1988; Levine and Davis, 1989; Rouzaud and Oberlin, 1990;
Wopenka and Pasteris, 1993; Cuesta et al., 1994, 1998; Blanche et al.,
1995; Duber and Rouzaud, 1999; Duber et al., 2000; Beyssac et al.,
2002; Marques et al., 2009; Matuszwska et al., 2015, among many
others) using different analytical techniques (including transmission
electron microscopy (TEM), micro-Raman Spectroscopy (MRS), X-Ray
Diffraction (XRD) and optical anisotropy) almost nothing has been

⁎
Corresponding author.
E-mail address: isruiz@incar.csic.es (I. Suárez-Ruiz).

https://doi.org/10.1016/j.coal.2020.103570
Received 13 January 2020; Received in revised form 28 July 2020; Accepted 28 July 2020
Available online 31 July 2020
0166-5162/ © 2020 Elsevier B.V. All rights reserved.
I. Suárez-Ruiz, et al.
reported about these aspects in relation to solid bitumens.
It is well known that the structural ordering of carbon materials
(e.g., coals and graphites) and their optical properties including texture,
anisotropy/isotropy and reflectance are closely interrelated (Duber
et al., 2000; Pusz et al., 2002; Pusz et al., 2014). This is an important
point bearing in mind that often in the absence of vitrinite, the re­
flectance of solid bitumens is applied to estimate the equivalent vi­
trinite reflectance in order to obtain the degree of maturity of strati­
graphic sequences and of petroleum-bearing basins (Tissot and Welte,
1984; Gentzis and Goodarzi, 1990; Suárez-Ruiz et al., 2012; Petersen
et al., 2013; Hackley and Cardott, 2016; Lewan and Pawlewicz, 2017;
Abarghani et al., 2019, among others). Consequently, empirical re­
lationships that transform the reflectance of solid bitumens into
equivalent vitrinite reflectance have been developed, such as those
described by Jacob (1989), Riediger (1993), Landis and Castaño
(1995); Schoenherr et al. (2007); Schmidt et al. (2019) among others
included in Mastalerz et al. (2018). In other cases, some parameters
obtained from analytical techniques such as Raman Spectroscopy ap­
plied to coal, kerogen and solid bitumens have been used to determine
the maturity degree of the organic substances (Kelemen and Fang,
2001; Liu et al., 2013; Zhou et al., 2014; İnan et al., 2016; Schmidt
Mumm and İnan, 2016; Sauerer et al., 2017; Henry et al., 2019; Al-
Hajeri et al., 2020). However, the problem is that most of these equa­
tions and/or parameters are not universally applicable and in many
cases they do not work for different sedimentary basins or even for a
specific sedimentary sequence of thousand meters thick (Juliao et al.,
2015, 2017). To date the potential origins of this problem have not been
duly clarified.
Taking into account the background described above, this work
investigates the optical properties of high reflectance solid bitumens in
relation to the development of their microstructural ordering and the
variation in their chemical composition during their natural evolution.
For this purpose a detailed characterization of all these properties by
optical microscopy, X-Ray Diffraction (XRD) and micro-Raman
Spectroscopy (MRS) has been carried out and, where possible, the re­
sults obtained have been compared with those from high rank coals and
other carbon materials reported in the literature.
2. Samples and analytical procedures
2.1. Samples
For this research six samples of solid bitumens (SB) from the Paja
Formation (Hauterivian to Aptian in age according to Etayo-Serna,
1968a, 1968b) in central Colombia were selected. These solid bitumens
come from dykes, veins and streaks located in the Cretaceous sedi­
mentary sequence of the Velez-Bolivar sectors (central part of Co­
lombia). In these sectors several mines of solid bitumen have been
under commercial exploitation for a number of years. According to
García Castillo and Vargas Escudero (2015) the solid bitumens of the
Paja Formation are long and short-distance migrated bitumens from the
formations of the lower Cretaceous sediments including the Paja For­
mation itself.
2.2. Analytical procedures
All the samples were prepared following the appropriate procedures
or currently accepted standards of analyses as described below.
2.2.1. Chemical analysis
Aliquots of the solid bitumens (ground less than 212 μm) were
prepared and subsequently analysed for proximate and ultimate de­
terminations following the ISO 562 (1998) norm and using a LECO CHN
2000, respectively. However, their oxygen contents were directly de­
termined on dried (80 °C / 2 h) samples by means of a LECO TruSpec
Micro-O apparatus. For this work, only the following parameters are
2
International Journal of Coal Geology 229 (2020) 103570
considered: Volatile Matter and Carbon contents, and the H/C - O/C
atomic ratios.
2.2.2. Optical microscopy
Optical characterization of the samples was performed on pellets
(prepared according to the ISO 7404/2, 2009 norm) with randomly
oriented particles using a MPV-Combi (Leitz) microscope equipped with
a 50× magnification oil immersion objective and in reflected white
light for random reflectance measurements following the ISO 7404/5
(2009) standard. For the reflectance measurements made to calculate
the maximum and minimum apparent reflectances polarized light was
used. For each particle three reflectance points (R1, R2 and R3) were
measured by rotating the microscope stage 45° from each point (Ting,
1981). The maximum and minimum apparent reflectances (R'max%
and R'min%, respectively) were calculated using Ting's equations (Ting,
1981). On the basis of these values the RIS (Reflectance Indicating
Surface), the main axes (RMAX%, RINT%, and RMIN%) and the RIS
parameters (Ram, Rev, and Rst) were determined following the pro­
cedures described by Kilby (1988, 1991) and later modified by Duber
et al. (2000). Optical photomicrographs were taken on a Leica DM 4500
P microscope equipped with a Leica DFC 420C camera and the corre­
sponding software to capture and analyse the images.
2.2.3. Micro-Raman spectroscopy
The Raman scattering measurements were performed on a Jobin
Yvon LabRam HR UV 800 spectrometer with a laser wavelength of
Argon 532 nm (2.4 mW) using the same sample preparation as for the
optical reflectance measurements (the samples were re-polished after
the optical measurements to remove the immersion oil). It is known
that polishing can lead to an increase in observed Raman disorder,
therefore all the spectra were acquired at a penetration depth ranging
from 60 to 150 nm. A microscope equipped with a 100× lens was used
to focus the excitation laser beam onto the particle and to collect the
Raman signal. For each section and/or particle 10 accumulations (scans
per spectrum) were obtained. These spectra were recorded in the range
of 1000–1800 cm−1 in the first-order region and from 2300 to
3500 cm−1 in the second-order region. Each spectrum was subjected to
peak fitting using LabSpec software in order to resolve the curve using
Lorentzian line shapes and/or Lorentzian/Gaussian combination line
shapes. The parameters obtained from the deconvolution of the spec­
trum include: the peak position (frequency, cm−1), full width at half
maximum (FWHM, cm−1) of the identified bands, the ratios related to
the relative intensities of the different identified bands and the area
ratios in both spectra, first and second order. The values of the Raman
parameters are the mean values obtained from the deconvolution of the
spectra of each sample (ten particles measured per sample).
2.2.4. X-Ray Diffraction
Diffractograms were recorded on a Bruker D8 Advance powder
diffractometer equipped with a monochromatic Cu KαX-ray source
according to an internal silicon powder standard. Diffraction data were
collected by step scanning using a step size of 0.02° 2θ and a scan step
of 2 s. For each sample (a representative fraction ground less than
70 μm), three diffractograms were obtained, employing a different re­
presentative batch of sample for each run. The mean interlayer spacing,
d002,was determined from the position of the (002) peak by applying
Bragg's equation. The crystallite sizes, Lc and La, were calculated by
measuring the FWHM (full width at half maximum) of the (002) and
(110) peaks, respectively, and by applying Scherrer's equation
Dhkl = Kλ/βcosθ, where K is the coefficient (0.89 for Lc and 1.84 for
La), λ is the X-ray wavelength, and β is the broadening of the diffrac­
tion peak measured at half its maximum intensity (in radians) (Biscoe
and Warren, 1942). The average number of aromatic layers < N > was
determined in the stacks as < N > = Lc/d002, following the procedure
described by Laggoun-Defarge et al. (1994). The broadening of the
diffraction peaks due to instrumental factors was corrected by using a
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Table 1 confirm that these solid bitumens are impsonites, in the range of cata-
Volatile matter and Carbon contents (dry-ash-free basis), and atomic ratios H/C impsonites.
and O/C for the high reflectance solid bitumens. In addition to the random reflectance, the optical parameters de­
Samples Volatile Matter (%, daf) C (%, daf) H/C O/C termined in this work included the RIS axes, RIS parameters and
parameters of anisotropy (Table 2). The relationships between the dif­
67007 3.6 95.2 0.152 0.017 ferent optical parameters (in terms of reflectance values) are shown in
67010 4.6 95.2 0.218 0.022
Fig. 3. The RIS axes (RMAX, RINT) show a positive linear relationship
67011 6.7 93.4 0.235 0.035
67012 5.1 92.7 0.284 0.022 with an increase in the random reflectance values (Ro) of SB (r = 0.94
67013 4.6 92.9 0.300 0.020 and r = 0.93, respectively) similar to that of coals of varying rank
67014 4.5 92.8 0.303 0.023 (Marques et al., 2009). There is also a good correlation between RMAX
and RINT (r = 0. 99) for SB as in the case of coals, although the SB show
a slightly deviation from the trend line towards lower values of RMAX%
silicon standard. The d002 values show standard errors to be lower than (Fig. 3). The evolutionary trend of RMIN with the increase in Ro in both
0.1%. the coals and solid bitumens (Fig. 3) is significant because the RMIN of
SB does not follow the same trend as that of high-rank coals and gra­
3. Results and discussion phites. In solid bitumens the RMIN increases with the increase in random
reflectance instead of showing a reversal behavior for values of Ro of
3.1. Chemical and optical parameters in high reflectance solid bitumens: around ~4.0–4.5% (94% daf. of C content according to Ragot, 1977) as
significance and relationships in the case of high-rank coals (meta-anthracites) and graphites. This
behavior of RMIN in coals and graphites is related to the refractive index
3.1.1. Bulk chemistry which tends to decrease, whereas the absorption index, the RMAX and
The chemical and optical results for the solid bitumens (SB) are the bireflectance rise significantly (Teichmüller and Teichmüller,
shown in Tables 1 and 2, respectively. These SB have low volatile 1982). Such behavior, not usually observed in solid bitumens, explains
matter contents ranging between 3.6 and 6.7 (%, wt., dry-ash-free basis, the weak anisotropy shown by these materials (Table 2, parameters B
−daf-) and in the range (< 8%) for those reported by Jacob (1989) for and AI discussed below) and confirms that, although normally an in­
cata-impsonites. The minimum value for volatile matter is shown by the crease in the thermal evolution of organic materials leads to an asso­
solid bitumen with the highest carbon content and the highest re­ ciated increase in anisotropy, this relationship between the two prop­
flectance value (Fig. 1 and Tables 1, 2). Carbon contents are high in all erties is not a strict one.
cases (from 92.7 to 95.2%, daf) and at the top of the range of Jacob's
impsonites. There is a positive relationship (r = 0.94) between the in­ 3.1.3. Rev RIS parameter
crease in C content and the increase in reflectance of the SB (Fig. 1). The With respect to the RIS Parameters, Rev, which is related to the RIS
atomic H/C and O/C ratios are low which would place the SB in the volume and, according to Kilby (1988), “represents the radius of a sphere
lower part of van Krevelen's diagram corresponding to highly evolved with a volume equal to that of the RIS ellipsoid”, shows a positive linear
organic matter (i.e., that have random reflectances higher than 2.0%). correlation with Ro (r = 0.94), RMAX (r = 0.99) and RINT (r = 0.99),
A good (negative) relationship was found between the H/C ratio and and even more so than in the case of some coals included in the figure
the reflectance trend of these materials with a correlation coefficient of (Fig. 4). This is because Rev is related to the chemical structure of the
0.97 (Fig. 1), indicating that a reduction in the H/C ratio values entails basic structural units (BSUs) in high rank coals (Duber et al., 2000) and
a substantial increase in their reflectance. there is an increase in the Rev. values with the increase in the rank of
coals and with the degree of evolution of solid bitumens, as shown in
3.1.2. Random reflectance and RIS axes Fig. 4. Consequently, there is a close relationship between the increase
In optical microscopy, these solid bitumens appear as organic in Rev values and the decrease in the H/C atomic ratio (Fig. 4) even
components with high reflectance and a relatively homogeneous sur­ though the slopes of the linear correlations are different between high
face. They also contain some irregularly distributed pores (macropores) rank coals and solid bitumens. According to Duber and Rouzaud (1999)
as well as fissures and cracks (Fig. 2). In general, the solid bitumens this is due to degassing and the removal of chemical groups during
display high mean statistical values of reflectance, varying from 4.25% organic evolution. This is confirmed by the relationship that exists
to 5.23%. They do not show any fluorescence properties when sub­ between the decrease in volatile matter content in coals with the in­
jected to either blue-violet excitation or UV radiation. The values of crease in their rank and the increase in Rev values. This trend is also
random reflectance obtained and Jacob's Classification (Jacob, 1989) observed in solid bitumens but the variation in volatile matter content

Table 2
Optical parameters for the high reflectance solid bitumens.
Samples Ro (%) RIS Axes RIS Parameters B (%) AI (%) Flinn's Parameters

RMAX (%) RINT (%) RMIN (%) Ram Rev Rst a b k

67007 5.23 5.490 5.301 4.588 0.036 5.111 −18.613 0.90 1.20 1.04 1.16 0.23
67010 4.93 5.148 4.978 4.167 0.042 4.744 −20.816 0.98 1.24 1.03 1.19 0.18
67011 4.68 5.038 4.724 4.236 0.034 4.653 −8.793 0.80 1.19 1.07 1.12 0.57
67012 4.23 4.632 4.412 3.691 0.045 4.224 −17.170 0.94 1.25 1.05 1.20 0.25
67013 4.17 4.368 4.082 3.251 0.058 3.870 −15.330 1.12 1.34 1.07 1.26 0.27
67014 4.25 4.841 4.634 3.743 0.051 4.379 −19.816 1.10 1.29 1.04 1.24 0.19

Ro: statistical mean random reflectance.

RMAX, RINT, RMIN: RIS Axes: Parameters calculated according to Kilby (1988) and Duber et al. (2000).
Ram, Rev., Rst: RIS Parameters: Parameters calculated according to Kilby (1988) and Duber et al. (2000).
B: bireflectance: RMAX-RMIN.
AI: anisotropy index: RMAX/RMIN. Calculated according to Ragot (1977).
a, b, k: Flinn's Parameters: a = RMAX/RINT, b = RINT/RMIN, k = (a-1)/(b-1), calculated according to Flinn (1956).

3
I. Suárez-Ruiz, et al.
Fig. 1. Relationship between the increase in the random reflectance of the solid
bitumens and their corresponding volatile matter and carbon contents and the
H/C atomic ratio. Sample within the circle is slightly oxidized. For comparative
purposes data from coals reported in González et al. (2004), Suárez-Ruiz and
García (2007), Marques et al. (2009), Rodrigues et al. (2011) and Matuszwska
et al. (2015) are included.
is small (Fig. 4 and Tables 1, 2).
On the other hand, the Rev of the solid bitumens shows an excellent
linear correlation with RMIN (Fig. 4) which is dissimilar to that shown
by high rank coals, whose RIS shape is an ellipsoid (Fig. 5). In the case
of the solid bitumens and bearing in mind the existing relationships
between Rev and RMAX, RINT and RMIN, and that the values of these
parameters are relatively close (Table 2), the shape of the RIS lies be­
tween a quasi-sphere and an ellipsoid with very little eccentricity, as
4
International Journal of Coal Geology 229 (2020) 103570
can be seen in Fig. 5. This figure shows the cross-sections of the RIS
along the principal axes, RMAX and RMIN, for some selected high rank
coals and solid bitumens. The shapes of the RIS for the high rank coals
with random reflectances (from 4.0% to 5.0%) in the range of those
shown for solid bitumens are ellipsoids with different degrees of ec­
centricity. The consequence of all this is the very weak anisotropy
shown by the solid bitumens, that is sometimes imperceptible to the
naked eye and only detectable from reflectance measurements, while
the high rank coals (their vitrinites) included in this work are all ani­
sotropic, and some of them are highly anisotropic (see works of
Murchison, 1978; González et al., 2004; Suárez-Ruiz and García, 2007;
Marques et al., 2009; Rodrigues et al., 2011 and Matuszwska et al.,
2015).
3.1.4. Anisotropy
The weak anisotropy of these solid bitumens is confirmed by the
small values of the bireflectance (B parameter), Anisotropy Index (AI)
and Ram (textural anisotropy) parameters (Table 2). Fig. 6 shows the
relationships between these anisotropy parameters for the high rank
coals and solid bitumens. In the case of the solid bitumens they are
located in the lower part of the curves Ram vs. B and Ram vs. AI, due to
their very weak anisotropy, even though they show a high degree of
random reflectance. Although SB are thermally evolved up to the de­
gree of the impsonites, and they display high random reflectances
(> 4.0%) and high RMAX, the behavior of RMIN in these SB is different to
that of RMIN in the high rank-coals. RMIN in the solid bitumens evolves
in parallel (Fig. 3) with RMAX (and RINT), and therefore the RMIN does
not show any reversal behavior for values of random reflectance of
around ~4.0–4.5% (94% of C content). This explains the weak aniso­
tropy of these SB.
Fig. 6 also shows the relationship that exists between the anisotropy
parameters Ram and B with the atomic ratio H/C for the high rank
coals. The location of the solid bitumens in this figure is anomalous,
since a decrease in H/C results in a substantial increase in anisotropy
(in the values of Ram and B) for the high rank coals. In the case of the
solid bitumens the values of the anisotropy parameters are relatively
similar for different H/C atomic ratios. Although their random re­
flectance values are high and they are materials with a significant
thermal evolution, in terms of anisotropy the solid bitumens are located
in the area of anthracites with a random reflectance of between 2.1%
and 3.0% and a low anisotropy (Fig. 7). With the exception of RMIN (as
expected), there are good relationships between all of these parameters
in the high rank coals but not in the case of the solid bitumens.
As mentioned above, there is no strict relationship between an in­
crease in rank or maturity of the organic substances and anisotropy.
Optical anisotropy is a physico-optical property that develops as a
consequence of physico-structural coalification which is linked to the
effect of pressure during the organic evolution in sedimentary basins,
and this is especially evident in case of high rank coals. However, ac­
cording to the results obtained here, these SB were not subjected to any
significant pressure after their accumulation in the Paja Formation, and,
consequently, they have not developed anisotropy. This is confirmed in
Fig. 8. Chandra's diagram is based on coals that have naturally evolved
and coals that have evolved under experimental conditions with and
without pressure. The solid bitumens are located in an area of thermally
evolved materials subjected to no significant pressure which is related
with the rearrangement of the BSUs. Despite the high reflectance va­
lues, the lack of tectonic stress does not promote the alignment of the
polyaromatic units, and therefore there is not an increase in the ani­
sotropy of the solid bitumens. This is the reason by which these SB do
not follow the behavior of high-rank coals and despite their high
thermal evolution they are still disordered materials.
3.1.5. Optical character
The Rst parameter reflects the optical character of RIS (Kilby, 1988).
According to the values of this parameter (Table 2) the solid bitumens
I. Suárez-Ruiz, et al.
Fig. 2. Photomicrographs of solid bitumens from the Bolivar-Velez sectors of Colombia. Images taken in reflected white light, and oil immersion. Long side of the
image: ~ 660 μm.
display a biaxial negative optical character. A biaxial negative character
is typical of high rank coals that have been subjected to high tectonic
pressures and have developed a marked anisotropy, which is not the
case of the SB studied in this work. The optical character (Rst para­
meter) is calculated by using values of RMIN and, as in the case of SB,
this axis evolves following a different trend to that of high rank coals
(Fig. 3). Therefore Rst is a valid parameter for coals and graptolites
(Rantitsh, 1995) but without any apparent validity or, of very limited
applicability, for solid bitumens or organic materials of high reflectance
that have thermally evolved in the absence of pressure. All of this is
confirmed by the position of the solid bitumens in the axial ratio dia­
gram (Levine and Davis, 1989), using the a, b, k parameters (Table 2)
described by Flinn (1956) and shown in Fig. 9. According to the values
of the a and b parameters for the SB and represented in the diagram of
Levine and Davis (1989) it can be seen that their location is displaced
from the axial origin. The values of parameter b are always higher than
those of the parameter a. This property in high rank coals is coincident
with their high anisotropy, but not in the case of solid bitumens. The
values of the k parameter (between 0 and 1 in Table 2) for the solid
bitumens also confirm their biaxial negative optical character as well as
the proposed shape of RIS (Fig. 5).
3.2. Structural order of the high reflectance solid bitumens
The optical properties of the high-reflectance SB from the Paja
Formation suggest that they are disordered materials despite their high
random reflectance values. To confirm this hypothesis, the structural
order of the solid bitumens was directly investigated by micro-Raman
spectroscopy and X-Ray Diffraction, taking into account that both
analytical techniques are complementary (Cuesta et al., 1998).
3.2.1. Micro-Raman spectroscopy
The Raman spectra of organic materials or carbon materials are
usually interpreted by comparing them with the Raman spectrum of
graphite which is a highly ordered substance with a well defined G
band located at about 1580 cm−1 in the first order spectrum of graphite
edge planes (e.g., Tuinstra and Koening, 1970; Nemanich and Solin,
1979; Lespade et al., 1984; Wopenka and Pasteris, 1993; Beyssac et al.,
2002; Rodrigues et al., 2013). When measurements are made on the
graphite edge planes two more bands may appear, D1 and D2 bands
around 1350 and 1620 cm−1, respectively, (Compagnini et al., 1997;
Katagiri et al., 1988; Kawashima and Katagiri, 1999; Tan et al., 2004;
Wang et al., 1989; Rodrigues et al., 2013; Henry et al., 2019) indicating
discontinuities in these planes. In the case of organic materials with a
low degree of structural order, in addition to the G and D1 bands, other
bands (D2, D3 and D4) may appear in the first order spectrum (Tuinstra
and Koenig, 1970; Nemanich and Solin, 1979; Lespade et al., 1984;
Beny-Bassez and Rouzaud, 1985; Wopenka and Pasteris, 1993; Cuesta
5
International Journal of Coal Geology 229 (2020) 103570
et al., 1994; Jawhari et al., 1995; Beyssac et al., 2002, 2003; Sadezky
et al., 2005; Hackley and Lunsdorf, 2018; Henry et al., 2019) as a
consequence mainly of their disorder. Moreover, disordered organic
materials also show a second order spectrum but with poorly defined
bands.
Fig. 10 shows the raw first- and second-order spectra for high re­
flectance solid bitumens. After performing first-order spectra decon­
volution and for most of the SB, five bands (G, D1, D2, D3 and D4) were
identified and selected characterizing parameters are included in Tables
3 and 4.
The G band, which is the most intense and narrowest in all cases
(Fig. 10), is centered at around 1596–1603 cm−1. This band is pre­
dominant in the spectra of SB, as can be seen from the R1 ratio (Table 3)
and IG/It (%) ratio in Table 4. The exception is the sample 67011 with a
R1 > 1 (predominance of the D1 band intensity). Its higher volatile
matter values and atomic ratio O/C (Table 1) suggest that this sample
might be slightly oxidized and therefore more structurally disordered.
With respect to intensity, the second more intense band is band D1,
which in the SB is relatively wide and located at 1333–1338 cm−1. In
poorly ordered or in disordered carbon materials this band is attributed
to in-plane defects such as heteroatoms (the presence of O, H, N) or
structural defects, as indicated by Beny-Bassez and Rouzaud (1985),
Cuesta et al. (1994), and Beyssac et al. (2002), and to the effect of the
finite size of the crystallites. The D2 band (centered at 1677–1698 cm−1
in SB) is visible as a shoulder of the G band in only four samples
(Fig. 10, Table 4). In the disordered materials the G and D2 bands are
difficult to separate and appear as one broad band (Beyssac et al.,
2002). The D3 band (centered at 1521–1539 cm−1 in the SB) is present
in poorly ordered materials. It appears as a very wide and low intense
band (Fig. 10, Tables 3, 4). This band has been attributed (Beny-Bassez
and Rouzaud, 1985) to out-of-plane defects which are released early in
the graphitization process of carbon materials or the evolution of or­
ganic matter. Nemanich and Solin (1979) have also attributed this band
to the small size of crystallites.
Finally there is another band which is a secondary band called the
“I” band and was identified by Cuesta et al. (1994) in activated carbons.
According to these authors, this band, which is centered at around
1330 cm−1, “represents a difference regarding other bands typical for de­
fects rather it corresponds to defects of a non-homogeneous nature which in
solids are usually due to impurity ions” (adsorbed ions, inorganic species).
In the present work, this band is called the D4 band and represents the
same concept. This band has been identified in the first-order spectra
for all the solid bitumens. It is centered at 1191–1225 cm-1 and shows a
low intensity in all cases.
As mentioned above, the D1 band in the first-order spectrum re­
presents defects in the structure of carbon or organic materials, whereas
the G band represents graphitic order (Tuistra and Koening, 1970). The
relationship between the intensities of both bands is proportional to the
I. Suárez-Ruiz, et al.
Fig. 3. Relationships between optical parameters of high reflectance solid bi­
tumens. For comparative purposes data from coals and graphites reported in
González et al. (2004), Suárez-Ruiz and García (2007), Marques et al. (2009),
Rodrigues et al. (2011) and Matuszwska et al. (2015) are included.
degree of structural order (Cuesta et al., 1994) with respect to the
graphite structure and as such this ratio has been used in the literature,
particularly when no other bands apart from D1 and G are present in
the first-order spectra of the materials under study. However, in the
present work, bands other than D1 and G have been identified (Tables
3, 4) and, as in the work of Cuesta et al. (1994), the ID4/It, ID1/It, ID3/
It, IG/It, ID2/It,ID1/(ID1 + IG) ratios, expressed as percentages have
been calculated (Table 4). According to these authors, the ID1/
(ID1 + IG) ratio is also considered as a reference parameter indicative
of disorder. Fig. 11 shows the relationships between the relative in­
tensities of the bands with respect to the disorder parameter for the
solid bitumens in comparison with other carbon materials discussed in
Cuesta et al. (1994). The intensities of the D1 and D2 bands in the
overall spectrum for carbon materials linearly increase with increasing
6
International Journal of Coal Geology 229 (2020) 103570
degree of disorder, but the opposite occurs in the case of the G band. In
the case of the solid bitumens this is true for bands D1 and G, though
the relationship with band D2 is not so clear. As in the case of the D4
and D3 bands, their intensities do not show any relationship with the
ID1/(ID1 + IG) disorder parameter for the solid bitumens. The in­
tensity of the D4 band does not depend on the degree of structural order
of the materials (Cuesta et al., 1994) and in case of the D3 band, its
position in the spectrum coincides with the valley between the D1 and
G bands, where the effects of both bands would be summed.
The values for the ID1/It (%) and IG/It (%) ratios (Table 4) of the SB
are relatively similar to those reported by Cuesta et al. (1994, 1998)
and Lespade et al. (1984) for carbon materials with a low level of
structural ordering. This is also confirmed by the values obtained for R2
ratio (Table 3) which is related to the areas of the bands and which also
reflects the structural ordering of carbon materials. All the solid bitu­
mens show values higher than 0.5 which indicates that these SB are
materials with a low degree of crystallinity. This ratio decreases with
the increase in the degree of crystallinity and the advance of graphiti­
zation (Altuve et al., 2007).
In summary, the high reflectance solid bitumens studied in this
work are disordered materials despite their high random and maximum
reflectance values. However, the question arises: how disordered are
these high reflectance SB? A comparison of the FWHM values for the D1
and G bands with their respective positions in the spectra for the solid
bitumens together with data obtained for coals (high-rank coals) and
graphites is depicted in Fig. 12. According to this figure, the degree of
order/disorder shown by the D1 band for these solid bitumens is
equivalent to that of high-rank coals, intermediate between anthracites
A (random reflectances between 4.0 and 6.0%) and anthracites C
(random reflectances between 2.0 and 3.0, according to ISO 11760,
2005). As to the position of the G band (Fig. 12), the solid bitumens are
located in the same field as high-rank coals (anthracites). However, the
position of the G band shows a tendency to be displaced towards higher
frequencies (cm-1) overlapping the field of anthracites C. This dis­
placement confirms the disordered structure of these SB.
The second order spectra of the solid bitumens show three relatively
defined bands (Fig. 10). From the deconvolution of the spectra the most
intense and predominant band is the 2900 cm−1 band, which in the
solid bitumens appears centered at 2914–2923 cm−1 (Table 5). This
band is followed by the 2700 cm−1 band, which in the SB is centered in
the range of 2631–2653 cm−1. The third and less intense identified
band is a secondary band (3240 cm−1) located in the 3167–3165 cm−1
range. The appearance of these last bands in the second order spectra
again confirms that the solid bitumens are disordered materials despite
their high reflectance values. With respect to the ratios (Table 5) ob­
tained from the second order spectra, all them, but particularly the
A2900/A2700 ratio which is related to the areas of the two prominent
bands with values higher than 1, reflect the predominance of the 2900
band. This result is similar to that obtained by Rodrigues et al. (2011)
for high rank coals (anthracites) which are materials with a low
structural ordering.
3.2.2. X-Ray Diffraction
X-ray dDiffraction was also used to assess the structural organiza­
tion of the high reflectance solid bitumens. The corresponding X-ray
spectra are shown in Fig. 13 while the crystalline parameters, related to
interlayer spacing (d002) and the crystallite sizes Lc and La, are pre­
sented in Table 6. An analysis of the XRD profile of the SB indicates
that: (i) band 002 is asymmetric in all cases, (ii)- band 10 is very little
pronounced and does not appear to be split, with the exception of
sample 67007 where this band is somewhat more pronounced and
shows a certain unfolding, whereas (iii)- band 110 is absent and only
seems to appear in the solid bitumen 67007. Diffractograms of this type
are characteristic of carbon materials with a low degree of crystallinity.
With respect to the crystalline parameters in Table 6, the values
corresponding to the d002 > 0.34 nm (from 0.3523 to 0.3484 nm) are
I. Suárez-Ruiz, et al.
Fig. 4. Relationships between Rev parameter with Ro, RMAX, RINT and RMIN, the atomic ratio H/C and volatile matter content for solid bitumens. For comparative
purposes data from coals and graphites reported in González et al. (2004), Suárez-Ruiz and García (2007), Marques et al. (2009), Rodrigues et al. (2011) and
Matuszwska et al. (2015) are included.
in the range of the values described for high rank coals (anthracites
CeB according to the ISO 11760, 2005 nomenclature) by Marques et al.
(2009), Rodrigues et al. (2011), and to anthracites and petroleum-based
cokes (sponge and needle) by Cuesta et al. (1998). This shows that these
SB are disordered materials or have a low degree of structural organi­
zation in comparison with natural or synthetic graphites. The same
applies to the crystallite sizes, Lc and La parameters, whose values
range between 1.7 and 2.2 nm and 3.6–4.2 nm, respectively. Conse­
quently the number < N > of aromatic layers is very small and si­
milar in all cases. In general, crystalline structures with values of
d002 ≥ 0.344 are considered turbostratic (Bourrat, 2000), that is, they
consist of a group of basic units (BSUs) made up of aromatic layers that
are arranged more or less parallel to each other and equidistant, but
randomly oriented (Biscoe and Warren, 1942) as seems to be the case
with these SB. However, there are slight differences between the var­
ious solid bitumens.
Samples 67012, 67013 and 67014 according to the values of the
interlayer spacing have a structure that is slightly more crystalline than
that of the 67007, 67019 and 670011 solid bitumens which have higher
7
International Journal of Coal Geology 229 (2020) 103570
d002 parameter values. This is also confirmed by the values of Lc
and < N > and by the decrease in the ID1/It and ID1/(ID1 + IG)
(disorder index according to Cuesta et al., 1994) Raman parameters
(Tables 3,4) for samples 67012–67014. Moreover, this seems to be in
agreement with their bireflectance data (Table 2). Therefore, these solid
bitumens have a slightly higher degree of bi- and tridimensional or­
dering in their structure, as can be deduced from the decrease in the
values of the interlayer spacing (d002) and the slight increase in crys­
tallite size in the “c” direction of space (Lc) and the increase
in < N > (Table 6). These facts seem to be in agreement with the bi­
reflectance data obtained for samples 67012–67014, especially for
samples 67013–67014 that show a visible and measurable anisotropy
(see anisotropy parameters in Table 2). However, at the same time and
for these samples there is a discrepancy in the values of the random and
maximum reflectances which are comparatively lower than those of
samples 67007, 67010 and 67011 that in principle have a slightly lower
structural ordering. From the La values of the 67007–67011 solid bi­
tumens it could be inferred that the crystallite size increases in the “a”
direction. This together with the slightly higher increase in crystallite
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Fig. 5. Cross-section of the RIS along the principal axes RMAX and RMIN for some selected high rank coals with random reflectance (Ro) between 3.63 and 6.92% (top)
and for solid bitumens (bottom) with Ro between 4.17 and 5.23% (Table 2). Data for high rank coals are from the works by González et al. (2004), Suárez-Ruiz and
García (2007), Marques et al. (2009), Rodrigues et al. (2011) and Matuszwska et al. (2015).

size of these 67007–67011 solid bitumens in the parallel section or the
basal planes direction may be related to the highest RMAX of these
samples. These relationships suggest that La is related with the increase
in RMAX, decrease of the FWHM G and ordering of the chemical struc­
ture, that is the growth in the basal plans; whereas Lc is related with
Ram (or B) and ID1/IG and associated with the stacking of the BSUs.
However, because of the small number of solid bitumens included in
this study, these results need to be tested using a larger amount of
samples.
Relatively similar results in behavior and evolutionary trends were
previously obtained by Suárez-Ruiz and García (2007) in a study on the
microstructural evolution of anthracites subjected to high thermal

8
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Fig. 6. Top left and right) Relationships between parameters of anisotropy and the Ram parameter of RIS for solid bitumens. Bottom left and right) relationship
between anisotropy parameters and the atomic ratio H/C for solid bitumens. For comparative purposes data from coals and graphites reported in González et al.
(2004), Suárez-Ruiz and García (2007), Marques et al. (2009), Rodrigues et al. (2011) and Matuszwska et al. (2015) are included.

Fig. 7. Relationships between parameters of anisotropy (B and Ram) and the optical parameters (Ro, RMAX and RMIN) for solid bitumens. For comparative purposes
data from coals and graphites reported in González et al. (2004), Suárez-Ruiz and García (2007), Marques et al. (2009), Rodrigues et al. (2011) and Matuszwska et al.
(2015) are included.

9
I. Suárez-Ruiz, et al.
Fig. 8. Location of solid bitumens (and the high rank coals) in the Chandra's diagram. (Modified from Chandra, 1965). Data from coals are from González et al.
(2004), Suárez-Ruiz and García (2007), Marques et al. (2009), Rodrigues et al. (2011) and Matuszwska et al. (2015).
treatment (up to 2600 °C) in the absence of pressure. For the high
thermally treated anthracite (ATOC sample) between 2200 and 2400 °C
the d002 parameter showed values of about 0.34 nm and, whereas Lc did
not increase (values from 5.5 to 6.6 nm), the La parameter increased
significantly (from 10.7 to 19.5 nm). This sample also showed the
highest RMAX and RMIN values and a slightly lower anisotropy (B
parameter).
The fact that the 67012–67014 solid bitumens may be slightly more
ordered (although the structure is still turbostratic) could be due to
their higher H content (see H/C atomic ratio in Table 1) in comparison
to that of samples 67007–67011, which would favor the process of
molecular orientation and the arrangement of the BSUs in the
67012–67014 solid bitumens and the subsequent development of a
slightly higher textural anisotropy (Table 2). The influence of H on the
process of molecular orientation has been previously reported for coals
and other carbon materials (e.g., see summaries in Taylor et al., 1998;
González et al., 2004, and references therein).
10
International Journal of Coal Geology 229 (2020) 103570
Fig. 9. Axial ratio diagram for solid bitumens (using a, b, k parameters
defined by Flinn, 1956 and the diagram from Levine and Davis, 1989).
For comparison data of coals from González et al. (2004), Suárez-Ruiz
and García (2007), Marques et al. (2009), Rodrigues et al. (2011) and
Matuszwska et al. (2015), were calculated and included in this dia­
gram.
3.3. Relationships between structural, optical and chemical parameters in
high reflectance solid bitumens
To establish the relationships between the structural and chemical
and optical parameters in these high reflectance solid bitumens the
main significant parameters are now discussed in comparison.
A positive relationship was found between the FWHM of the G band
and the interlayer spacing d002 (Fig. 14) Raman and XRD parameters.
The location of the solid bitumens in the area of high rank coals in­
dicates a similar structural ordering (disordering). This is confirmed in
Fig. 14 (FWHM of the G band vs. Lc parameter) by the location of the
solid bitumens in the area of the high-rank coals (anthracites). Worth
noting is the slight displacement of samples 67013 and 67014 to the top
of the trend due to a slightly higher structural ordering where the G
band shifts towards higher wavenumbers and becomes narrower (see
FWHM in Table 3). Moreover, although the variation in Lc and d002
values is small, the parameter Lc shows the highest and d002 the lowest
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Fig. 10. First and second-order micro-Raman spectra of the solid bitumens.

Table 3
Micro-Raman parameters (mean values) related to position (Frequency) and full width at half maximum (FWHM) and Ratios R1(Intensities) and R2 (Areas) for the
identified bands in the first-order spectrum of solid bitumens.
Samples D4 band D1 band D3 band G band D2 band R1 R2

Freq. FWHM Freq. FWHM Freq. FWHM Freq. FWHM Freq. FWHM ID1/IG AD1/AD1 + AG + AD2
(cm−1) (cm−1) (cm−1) (cm−1) (cm−1) (cm−1) (cm−1) (cm−1) (cm−1) (cm−1)

67007 1192 103 1335 115 1539 132 1599 42 0.98 0.73
67010 1194 117 1333 126 1531 140 1596 45 1677 35 0.89 0.70
67011 1200 152 1336 128 1539 164 1596 45 1.01 0.74
67012 1214 138 1336 121 1527 153 1598 43 1695 48 0.73 0.65
67013 1225 119 1338 111 1521 151 1603 39 1698 32 0.63 0.63
67014 1225 118 1338 112 1524 148 1603 38 1693 16 0.64 0.64

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I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Table 4
Relative intensities of the different identified bands and proportion in which
they participate in the first-order spectrum of solid bitumens.
Samples ID4/It ID1/It ID3/It IG/It ID2/It ID1/(ID1 + IG) (%)
(%) (%) (%) (%) (%)

67007 6.0 40.7 11.9 41.4 49.5

67010 7.0 37.4 12.8 42.1 0.7 47.0
67011 8.0 38.0 16.3 37.7 50.2
67012 8.6 33.2 11.6 45.6 0.9 42.1
67013 8.8 31.4 9.0 50.0 0.7 38.6
67014 8.5 31.8 9.0 50.0 0.6 38.8

It: total integrated intensity of the bands identified in the first order spectrum.

values (Table 6) for these two solid bitumens.

As for the relationships between the Raman and the optical para­
meters there is a negative relationship between RMAX and the FWHM of
the G band (Fig. 15). As was also observed by Marques et al. (2009) the
relationship between these two parameters for high-rank coals and
graphites showed a marked negative trend in their full width at the half
maximum (FWHM) of the G band from the anthracites C to the an­
thracites A and graphite. The solid bitumens are located in an inter­
mediate position between the anthracites C and the anthracites A,
which would be equivalent to Anthracites B (Anthracites B display a
random reflectance between 3.0 and 4.0% according to ISO 11760,
2005). This intermediate position is shown in Fig. 12 (relationship
between the D band position and the D band FWHM). As for the re­
lationship between the G band FWHM and the Rev optical index it is
similar, confirming the structural ordering of the solid bitumens as
being that of high rank coals (Fig. 15).
The relationship between the interlayer spacing (d002) and the RMIN Fig. 12. Relationship between between micro-Raman parameters. Location of
is also shown in Fig. 15. For comparison with high rank coals and solid bitumens in a set of high rank coals and graphites using D1 and G bands
graphites, anthracites C are included as they are the only available data parameters. Data of high –rank coals and graphites are from Marques et al.
related to d002 and RMIN. As can be seen, the higher RMIN values lead to (2009).
higher d002 values in the case of the solid bitumen which is due to the
non-reversal behavior of the RMIN in the SB (Fig. 3) as mentioned in
correlation found between the crystalline (XRD) and the chemical
previous sections of this work. This, in its turn, is due to the structural
parameters of these samples.
ordering of these solid bitumens, which is equivalent to that of the
The structural order of the high reflectances of the solid bitumens is
antracites B, contrary to what their reflectance values might suggest.
equivalent to that of the high rank coals (anthracite B in rank), as re­
This could be the reason why the RMIN does not show a reversal be­
flected in the evolution of the optical, chemical and structural para­
havior. In addition, this also explains the type of the RIS shown in Fig. 5
meters. The small differences in their structural order could be partly
for the solid bitumens, which is different to that developed by materials
conditioned by the small variations in hydrogen.
with similar reflectance values of RMAX but low RMIN displaying sig­
nificant anisotropy.
With respect to the chemical parameters, the solid bitumens are 3.4. The solid bitumen reflectances and their transformation into equivalent
located in the logarithmic trend between the H/C atomic ratio and the vitrinite reflectance in order to measure organic maturity
Raman FWHM of the G band (Fig. 16). In this relationship the position
of the samples (67012–67014) with a high hydrogen content and It is well known that in the absence of vitrinite (e.g., carbonate rocks
narrow FWHM in the G band and that of the slightly more ordered of or pre-Devonian rocks) the reflectance of solid bitumen among other
solid bitumen set can be clearly seen. This might also explain the types of organic components, such as vitrinite-like particles, graptolites,

Fig. 11. Relationships between the relative intensities of the D1 and G bands bands and the disorder parameter. For comparison, the data set of carbon materials are
from Cuesta et al. (1994).

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I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Table 5
Micro-Raman parameters (mean values) related to position (Frequency) and full width at half maximum (FWHM) and Ratios for the identified bands in the second-
order spectra of solid bitumens.
Samples 2700 band 2900 band 3240 band Ratios

Freq. (cm−1) FWHM (cm−1) Freq. (cm−1) FWHM (cm−1) Freq. (cm−1) FWHM (cm−1) I2900/I2700 A2900/A2700

67007 2653 274 2923 189 3173 119 1.33 1.73

67010 2634 254 2914 211 3170 121 1.61 1.78
67011 2642 267 2920 211 3167 128 1.42 1.70
67012 2631 247 2917 216 3177 117 1.69 1.80
67013 2631 240 2918 216 3184 110 1.79 1.84
67014 2628 237 2918 218 3185 108 1.80 1.84

etc. has been used as a parameter to determine organic maturity by Table 6

applying the corresponding transformation equations to obtain the X-Ray Diffraction parameters of the high reflectance solid bitumens.
equivalent vitrinite reflectance. However, it is also well known that Samples d002(nm) Lc (nm) La (nm) < N > = Lc/d002
these equations are not universal, they cannot be applied to all basins,
or even to an entire stratigraphic sequence. This is an issue of special 67,007 0.3523 1.7 4.2 5
interest in hydrocarbon exploration, particularly (e.g.,) in the case of 67,010 0.3512 1.9 3.7 5
67,011 0.3499 1.9 4.1 5
shale gas (and other related systems) exploration. In these deposits and 67,012 0.3492 2.0 3.9 6
in the absence of vitrinite, the organic matter is so mature that organic 67,013 0.3484 2.2 3.7 6
geochemical parameters are not effective (e.g., Tmax, biomarkers), and 67,014 0.3486 2.1 3.6 6
there are many reports in the literature of equivalent vitrinite re­
flectance being obtained from the measurements of solid bitumen re­
flectance in order to establish organic maturity (Jacob, 1989; Bertrand, the evolutionary pattern shown by vitrinites of similar random re­
1993; Riediger, 1993; Landis and Castaño, 1995; Schoenherr et al., flectance because the structural order of the solid bitumens is lower
2007; Juliao et al., 2015; Mählmann and Le Bayon, 2016; Schmidt than that of vitrinites of similar random reflectance. The high re­
et al., 2019, among others). flectance of the solid bitumens from the Paja Formation shows that,
Temperature and time, (as in the case of most carbon materials), despite their high random reflectance, they have a structural order and
and pressure are the most important factors for the maturation of solid crystalline structure equivalent to that of anthracites B (high rank coals
bitumens (Jacob and Wehner, 1981; Jacob, 1989). During the organic with a random reflectance from ≤3.0% to < 4.0%, according to ISO
maturation process (evolution) in nature the reflectance of solid bitu­ 11760, 2005).
mens increases and in some cases, as has been pointed out by Jacob The random reflectance of the solid bitumens increases markedly
(1989) among other authors, a more or less intense optical anisotropy but the structural ordering does not increase at the same rate as the
might develop. In the present work, the solid bitumens investigated structural ordering of the vitrinites of similar random reflectance. This
showed a weak anisotropy despite their high random reflectance fact is significant when transforming the random reflectance of solid
(> 4%). As explained above, this is due to RMIN,which does not follow bitumens into values of equivalent vitrinite reflectance. It might also
explain why not all the equations proposed to transform the reflectance

Fig. 13. Powder X-Ray Diffraction patterns of the high reflectance solid bitumens.

13
I. Suárez-Ruiz, et al.
Fig. 14. Correlation between FWHM of the G band and the interlayer spacing d002, and XRD Lc parameters for solid bitumens. For comparison, data of coals and
graphites are from Marques et al. (2009) and Rodrigues et al. (2011).
of solid bitumens into equivalent vitrinite reflectance are universal and
why they are not effective for all basins or sedimentary sequences.
Assuming that these SB are materials with structural order similar to
that of the anthracites B, different equations available in the literature
to obtain the equivalent vitrinite reflectance, by using (i) the random
reflectance of SB and, (ii) the micro-Raman parameters (such as the RSB
parameter) have been applied to determine what reflectance values
provided by the transformation equations would be most consistent
with the described structural order of the solid bitumens. The results
obtained are shown in Table 7 and, as can be observed, they are quite
different.
Only the Jacob (1989) and Liu et al. (2013) equations, the latter for
post-mature samples, provide values of equivalent vitrinite reflectance
ranging from ~3.0 to 4.0%. However, if the values obtained with the
Liu et al. (2013) equation (Raman Band Separation parameter, RSB) are
examined closely, the highest equivalent vitrinite reflectance values
correspond to sample 67011 (Table 7, Fig. 1), which is described as a
slightly altered/oxidized sample, and in addittion it is the sample with
the greatest degree of structural disorder (see ratio R2 in Table 3 and
the disorder parameter ID1/(ID1 + IG) in Table 4). Consequently, the
equation proposed by Jacob (1989) is the only one to provide equiva­
lent vitrinite reflectance values, in the range of ~3.0–4.0% of re­
flectance (Table 7), that fit the structural ordering determined for the
SB investigated in this work.
Jacob's equation (Jacob, 1989) for equivalent vitrinite reflectance
14
International Journal of Coal Geology 229 (2020) 103570
was established for solid bitumens ranging from asphaltites to meso-
impsonites. With the data obtained in the present work from the high
reflectance solid bitumens the range of application of this equation
could be enlarged to include cata-impsonites, as is shown in Fig. 17, so
that it covers all solid types of bitumen, or at least the solid bitumens
investigated in this work, which have a high random reflectance and a
low structural order probably due to thermal evolution in the reservoir
rock in the absence of pressure, as shown in Figs. 8 and 5.
4. Conclusions
From the study of the chemical, optical and microstructural prop­
erties and their corresponding inter-relationships in high reflectance
solid bitumens from the Paja Formation (Cretaceous from Colombia)
the following main conclusions may be drawn:
1. According to the chemical (volatile matter and C contents) and
optical parameters (random reflectance) and following the Jacob's
classification these high reflectance solid bitumens are impsonites,
in the range of cata-impsonites.
2. Despite the high random reflectance of these SB (values equivalent
to those of high rank coals or meta-anthracites), they show a weak
anisotropy. This weak anisotropy is explained as being a con­
sequence of the increase in RMIN in parallel with RMAX and RINT
during their thermal evolution in the reservoir rock. In high rank
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Fig. 15. Correlation between RMAX and FWHM of the G band (top), Rev RIS parameter and FWHM of the G band (middle) and the interlayer spacing d002 and RMIN
RIS axis (bottom) for solid bitumens. For comparison, data of coals and graphites are from Marques et al. (2009) and Rodrigues et al. (2011).

coals and graphites RMIN shows a reversal behavior (i.e., it de­
creases) at around 94% C content and 4.0–4.5% vitrinite random
reflectance, leading to anisotropy in these materials. This behavior
was not observed in the solid bitumens studied in this work and
explains their weak anisotropic properties.
3. These findings in solid bitumens confirm the claim that with the
increase in organic evolution (coalification, maturation), anisotropy
develops but this relationship between coalification and anisotropy
is not strict.
4. The absence or minimum participation of pressure (third factor in

15
I. Suárez-Ruiz, et al. International Journal of Coal Geology 229 (2020) 103570

Fig. 16. Relationship between FWHM of the G band and the H/C atomic ratio for solid bitumens. For comparison, data of coals and graphites are from Marques et al.
(2009) and Rodrigues et al. (2011).

Table 7
Equivalent vitrinite reflectance calculated from the solid bitumen random reflectance using the Jacob (1989), Riediger (1993), Schoenherr et al. (2007), Landis and
Castaño (1995) and Schmidt et al. (2019) equations (1–5), and equivalent vitrinite reflectance from the solid bitumens micro-Raman parameters using the Liu et al.
(2013) equations (6a,b).
Solid Bitumens Ro eq. Vite Ro eq. Vite Ro eq. Vite Ro eq. Vite Ro eq. Vite Ro eq. Vite Ro eq. Vite

1 2 3 4 5 6a
Samples Ro (%) ID1/IG d(G-D1) (%) (%) (%) (%) (%) (%) (%)6b

67007 5.23 0.98 264 3.63 2.02 5.22 5.18 5.22 3.90 2.97
67010 4.93 0.89 263 3.45 1.94 4.93 4.90 4.94 3.80 2.91
67011 4.68 1.01 260 3.29 1.87 4.69 4.67 4.70 3.94 2.75
67012 4.23 0.73 262 3.01 1.74 4.27 4.26 4.28 3.61 2.86
67013 4.17 0.63 265 2.98 1.73 4.21 4.21 4.23 3.49 3.02
67014 4.25 0.64 265 3.03 1.75 4.28 4.28 4.30 3.50 3.02

1
Jacob (1989) equation: Ro eq. Vitrinite = 0.618 * RB (%) + 0.40.
2
Riediger (1993) equation: Ro eq. Vitrinite = 0.277 * RB (%) + 0.57.
3
Schoenherr et al. (2007) equation: Ro eq. Vitrinite = (RB % + 0.2443) / 1.049.
4
Landis and Castaño (1995) equation: Ro eq. Vitrinite = (RB % + 0.414) / 0.086.
5
Schmidt et al. (2019) equation: Ro eq. Vitrinite = (0.938 * RB %) + 0.3145.
6a
Liu et al. (2013): vRo eq% = 1.1659 ∗ (ID1/IG) + 2.7588 for post − mature samples.
6b
Liu et al. (2013)): vRo eq% = 0.0537*d(G-D)-11.21 for mature to highly mature samples.

the coalification process which promotes physico-structural coalifi­
cation and the subsequent development of anisotropy) during the
thermal evolution of these SB in the reservoir rock is confirmed as
the cause of the anomalous behavior of RMIN (which increases in­
stead of decreasing) in these SB. The increase in random reflectance
in these materials is due only to thermal evolution.
5. Consequently, the RIS shape for these solid bitumens is almost a
sphere or ellipsoid with very little eccentricity. This model of RIS is
typical of disordered materials and hence these solid bitumens are
disordered materials despite their high random reflectance.
6. The study of the their structural order and degree of crystallinity
carried out by micro-Raman spectroscopy and X-ray diffraction has
confirmed these materials as being disordered with a low degree of
crystallinity.
7. The issue of how disordered they are, has been solved by comparing
the FWHM values for the D1 and G bands obtained by micro-Raman
spectroscopy with data from high-rank coals and graphites. This
comparison indicates a degree of structural order/disorder in the SB
equivalent to that of high-rank coals, specifically anthracites B (in­
termediate between anthracites A with random reflectances be­
tween 4.0 and 6.0% and anthracites C with random reflectances
between 2.0 and 3.0). This has also been confirmed by the values of
d002, and the Lc and La parameters obtained by X-ray diffraction
analysis.
8. The use of solid bitumens with a very high reflectance but with a
low structural order or disorder may have implications for em­
ploying the reflectance of solid bitumens to obtain the equivalent
reflectance of vitrinite and might explain why some equations pro­
posed in the literature are not universally applicable.
9. Assuming that these solid bitumens are materials with a structural
order similar to that of the anthracites B, the different equations
reported in the literature to obtain the equivalent vitrinite re­
flectance were applied to determine which reflectance values pro­
vided by the transformation equations would be most consistent
with the described structural order of these solid bitumens. The
equation proposed by Jacob (1989) was found to be the only one
whose equivalent vitrinite reflectance values, in the range of
~3.0–4.0% of reflectance, fit the structural order determined for the
SB investigated in this work. This suggests the possibility of ex­
tending the range of application of this equation to include cata-
impsonites in order to allow all types of solid bitumen to be covered,
particularly solid bitumens that have a high random reflectance and
a low structural order probably due to their thermal evolution in the
reservoir rock in the absence of pressure.

16
I. Suárez-Ruiz, et al.
Fig. 17. Location of the high reflectance solid bitumens investigated in this work in the Jacob's diagram (Jacob, 1989) after the conversion of the solid bitumen
reflectance to vitrinite equivalent reflectance by using the equation: Ro eq. Vitrinite = 0.618 RB + 0.40.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
The authors are grateful to INCAR-CSIC (Oviedo, Spain) for offering
the use of their laboratories and to the personnel in charge, particularly
Dionisio Luis (in sample preparation), for carrying out the analyses.
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