Advances in Sediment Geochemistry and Chemostratigraphy

Energy Geoscience 2 (2021) 308e326
Contents lists available at ScienceDirect
Energy Geoscience
journal homepage: www.keaipublishing.com/en/journals/energy-geoscience
Advances in sediment geochemistry and chemostratigraphy for

reservoir characterization
Mu Ramkumar a, *, R. Nagarajan b, c, M. Santosh d, e
a
Department of Geology, Periyar University, Salem, 636011, India
b
Department of Applied Geology, Curtin University, Malaysia
c
Curtin Malaysia Research Institute, Curtin University, Malaysia
d
School of Earth Sciences and Resources, China University of Geosciences Beijing, Beijing, China
e
Department of Earth Sciences, University of Adelaide, Adelaide, SA, 5005, Australia
a r t i c l e i n f o a b s t r a c t
Article history: Sedimentary sequences preserve the records of changes in major controls of sedimentation namely,
Received 8 December 2020 tectonics, climate, relative sea level and sediment production and preservation. The potential to char-
Received in revised form acterize these changes in spatial and temporal scales has led to the development of the branch of che-
25 January 2021
mostratigraphy. Chemostratigraphic study of sedimentary sequences commenced from recognizing
Accepted 4 February 2021
identical/contrasting geochemical features across major geochronological boundaries, and evolved into
one of the essential tools in exploration, characterization, and well development strategies. Chemo-
Keywords:
stratigraphy incorporates applications on continuous, real-time geochemical mapping and direction of
Biomarker
Chemostratigraphy
lateral drilling, and machine learning, among others. As the sedimentary systems operate on a variety of
Geochemical fingerprinting temporal scales that range from few hours (tidal cycles) to few tens of millions of years, within which
Machine learning many perturbations such as catastrophic and diagenetic events take place, that lead to unique
Oil family geochemical signature which can be correlated at appropriate spatial and temporal scales. The appli-
Stratigraphic correlation cation of chemostratigraphic technique in hydrocarbon exploration and reservoir characterization has
gained momentum in recent years, particularly with the advent of developments in analytical instru-
mentation. This has also led to the integration of a variety of data from field sedimentary structures,
mineralogy, major, trace and isotopic chemical compositions of whole rock, selected components of
rocks, organic and inorganic components of oil and gas, etc., for reservoir characterization more accu-
rately than ever. The geochemical fingerprinting of oil and gas reservoir components plays a major role in
the identification of source rocks, discrimination of oil families, characterization of reservoir, source, and
seal segments in petroleum systems. Future trends indicate the relevance and growing applications of
machine learning techniques, artificial intelligence in real-time assessment, monitoring and planning of
hydrocarbon exploration and production.
© 2021 Sinopec Petroleum Exploration and Production Research Institute. Publishing services by Elsevier
B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction environments of deposition and diagenesis (Berger and Vincent,

1981; Das, 1997; Ramkumar, 1999; Sial et al., 2019). This trait is in
Geochemistry of the sediments is governed by many factors use to characterize sedimentary units and interpret the paleo-
including, but not limited to, the provenance, tectonic setting, climate, environment, etc. (e.g. Emiliani, 1955; Keith and Weber,
1964; Shackleton and Opdyke, 1973; Renard, 1986; Das, 1997; Roy
et al., 2019; Sial et al., 2019). Recognition, characterization and
* Corresponding author. distinction of individual depositional units based on geochemical
E-mail address: [email protected] (M. Ramkumar). composition either through bulk chemistry, or elemental percent-
ages or ratios of elements and/or isotopic composition, have
commenced in the 1980’s that led to the differentiation of a new
Production and Hosting by Elsevier on behalf of KeAi field of research known later as “chemostratigraphy” (e.g. Odin
et al., 1982; Kaminski and Malmgren, 1989; Das, 1997; Pearce
https://doi.org/10.1016/j.engeos.2021.02.001
2666-7592/© 2021 Sinopec Petroleum Exploration and Production Research Institute. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Ramkumar, R. Nagarajan and M. Santosh Energy Geoscience 2 (2021) 308e326
et al., 1999; Ramkumar, 1999; 2015; Ramkumar et al., 2019). Che- of choice, by the International Stratigraphic Commission, a call that
mostratigraphy or study of stratigraphic variations of selected has few takers such as Sial et al. (2019) and Scott et al. (2020).
elemental concentrations or isotopic composition was initially Ramkumar et al. (2019) presented various terminologies and their
utilized to document the changes across major chrono, litho and definitions used in this method of stratigraphic classification.
biostratigraphic boundaries or major catastrophic events (Keith
and Weber, 1964; Odin et al., 1982; Berger and Vincent, 1981; 3. Stratigraphic correlation
Renard, 1986; Kaminski and Malmgren, 1989; Svendsen and
Hartley, 2001; for an extensive review see, Ramkumar, 2015). This 3.1. The rationale
method/technique was later expanded into applying it for
addressing several geological problems (Ramkumar, 2015, Initially, chemostratigraphy was applied to recognize unique
Ramkumar et al., 2019; Roy et al., 2019; Sial et al., 2019 for detailed geochemical compositions for characterizing depositional units
review). In this review, we collate the published information on the and correlating them with coeval strata elsewhere and found its use
origin, development and applications of this branch of geosciences, in the stratigraphic location of boundaries and later expanded to
especially with reference to stratigraphic correlation and reservoir examine specific causes of the stratigraphic variations of
characterization. It is also to be noted that this paper is not intended geochemical compositions (Ramkumar et al., 2010, 2011). In addi-
to be a catalogue of all the published reports in this regard, rather, tion, the chemozones, calibrated with absolute time, are in use as
an attempt to take stock of the current understanding, trace the chemochrons (Ramkumar, 1999; Ramkumar et al., 2019; Sial et al.,
developmental stages that took place over time and present 2019). As each sedimentary environment is characterized by
pointers toward the future trends. unique physical, chemical, and biological milieu in a geomorphic
setup (Reineck and Singh, 1980; Ramkumar, 2014; Ramkumar et al.,
2. Chemostratigraphy 2010), the resultant sediments are subjected to varying spatio-
temporal scales and intensities of these processes, which produce
The sediments are faithful recorders of the changes in prove- spatiotemporal distinctness of chemical compositions of sedi-
nance, environment of deposition, and post-depositional history. mentary record (e.g. Pietras and Spiegel, 2018). An ability to
These pre-depositional, depositional and post-depositional recognize these differences in terms of geochemical fingerprints
changes show primary differences in either mineralogical grain (Ramkumar, 2015; Ramkumar et al., 2019) of specific tectonic
and/or in the chemistry of their constituent minerals and also in the setting, climate, provenance, prevalent depositional energy condi-
proportions of accessory phases such as heavy minerals and clays, tion, clay and or heavy mineral distribution, etc., in temporal scale
many of which have distinct chemical compositions (Das, 1997). In results in chemostratigraphic characterization of strata under study
a stratigraphic context, these differences result in a geochemical (Ramkumar, 2014) and in recognizing similar traits in sections
system consisting of information on geological setting, climate, and located elsewhere and linking coeval depositional surfaces and or
processes of sediment production (Berger and Vincent, 1981) and units results in chemostratigraphic correlation (Ramkumar et al.,
preservation (Ramkumar, 2015).Thus, the stratigraphic record 2010).
shows changes in the concentration of certain elements with time Theoretically, temporal scales of the sedimentary cycles vary
(Morante et al., 1994), as a function of geological conditions from few seconds (catastrophic events, mass wasting, avalanche,
including, but not limited to, tectonic, climatic, redox, oceano- etc.), through few hours (tidal cycles), diurnal variations, seasonal
graphic, biotic, and other processes. This trait had helped chemo- variations, annual climatic cycles, decadal cycles, Milankovitch cy-
stratigraphy to divide apparently uniform thick rock successions cles, and finally at the first order cycles (few tens of millions of
and correlate coeval strata located elsewhere (Ramkumar, 1999). years), all of which might have unique geochemical compositions at
From geochemical profiles of elemental concentrations, ratios of corresponding temporal scales. However, several causes, including
oxides and elements and isotopic values, linear, secular, cyclic and the stacking pattern of these cycles (cycle-in-cycle pattern), omis-
perturbed trends are recognized and utilized for chemostrati- sion surfaces, stratigraphic gaps, and diagenetic overprinting, etc.,
graphic classification and correlation (for detailed review, can alter the pristine signatures significantly. An ability to charac-
Ramkumar, 2015; Sial et al., 2019). There are several isotope sys- terize the depositional units in terms of unique geochemical sig-
tems such as carbon, oxygen, sulfur, nitrogen, calcium, boron, natures would help establish a robust chemostratigraphic model
chromium, molybdenum, lithium, strontium, neodymium, and correlation of widely separated strata with measurable confi-
osmium, iron, and zinc that have been successfully used in che- dence levels. As demonstrated more recently also by Dupont and
mostratigraphy. In order to apply the isotope record of any of these Grammer (2019) temporal accuracy of the chemostratigraphic
systems to chemostratigraphy of sedimentary sequences, it is correlation is dependent on the scale of sampling, which is quite
essential to have good knowledge of the secular and other varia- oblivious to any other stratigraphic method, which in turn places
tions of marine isotope ratios (Sial et al., 2019). Chemostratigraphic this method in a unique, unrivalled position. A combination of
data provide temporal and stratigraphic constraints even in rocks multivariate statistical analyses on textural, petrographic, facies,
where paleontological data are rare or absent (Caruthers et al., geochemical, mineralogical, and other data, distinction of deposi-
2018). Its effectiveness in comparing and contrasting geochemical tional units in terms of sequences, chemozones, lithostratigraphic
compositions of strata across major geochronological boundaries, formations that spanned a temporal resolution of about 1e18 Ma
such as PrecambrianeCambrian, PermianeTriassic, Triassice were applied to the Cauvery Basin in India (Ramkumar et al., 2010).
Jurassic, JurassiceCretaceous, CretaceouseTertiary, Petrographic and standard microfacies types of Maastrichtian car-
PaleoceneeEocene, etc. was utilized extensively and later its bonates (Ramkumar et al., 2002), lithostratigraphic members, for-
applicability was expanded to examine specific causes to the mations, petrographic types, standard microfacies types, and facies
stratigraphic variations of geochemical compositions (e.g. zones of Tertiary carbonates (Ramkumar and Guha, 2000), 21 types
Ramkumar et al., 2010) by integration of various types data from of sub-environments of modern delta (Ramkumar, 2001) and
other branches of geosciences. estuarine sediments deposited under flood and ebb tides
As this method meets all the criteria to be an independent (Ramkumar, 2004) are some other examples (Ramkumar and
stratigraphic classification, Ramkumar (2015) proposed it to be Sathish, 2007) that have demonstrated the ability of geochemical
recognized as one of the formal stratigraphic classificatory methods signatures to distinguish depositional units of various types. Based
309
on these, a scheme of discrimination and prediction of depositional chemostratigraphic hierarchical four-fold subdivision of the strata
units was presented (Ramkumar, 2014). It was also demonstrated that enabled correlation at required scales. Hildred et al. (2010)
statistically that the accuracy of the defined depositional units applied chemostratigraphy to discriminate between the three
could thwart human error or bias. informal lithostratigraphic units of the Basal Quartz of the Lower
Mannville Formation, namely the Horsefly, the Ban-
3.2. Historic-recent perspective tryeAldersoneTaber (BAT), and the Ellerslie units and demon-
strated that the technique can be utilized as a viable correlation tool
In one of the earliest studies, Emiliani (1955) applied chemo- in low-accommodation incised-valley settings and found that it is
stratigraphy (though the term was not available then) through most effective when the whole-rock geochemical data are placed in
documentation of oxygen isotopic composition of foraminifera a regional context by integration with a detailed stratigraphic
recovered from deep-sea cores to interpret and correlate global framework.
scale geological event. Later, Shackleton and Opdyke (1973) Based on a large dataset of spectral gamma-ray (SGR) log and
established the first 22 oxygen isotope stages. This was probably geochemical data of the Upper Jurassic Arab-D reservoir analog
the first formal application of chemostratigraphy. Williams et al. (central Saudi Arabia), Eltom et al. (2013) were able to distinguish
(1988) extended the oxygen isotope stage zonation to the Quater- four distinct lithofacies types, each with typical geochemical fea-
nary and Lisiecki and Raymo (2005) to the Pliocene. The success of tures namely, a) SiO2, Al3O2, Fe2O3, K2O, TiO2, Zr and Zn, b) U, K and
oxygen isotope chemostratigraphy encouraged researchers to use Th, c). CaO and Sr and d) MgO. These were helpful in developing a
stable isotope stratigraphy in ancient sedimentary successions. The method for predicting lithofacies from SGR log motifs within a
work of Roy et al. (2019) is a recent review of chemostratigraphy of high-resolution stratigraphic framework integrated with the
the Cenozoic. As carbon isotopes have higher resilience against geochemical data analysis. With these results, the authors have
post-depositional alteration, they are measured in carbonates and presented an exploration guide for subsurface reservoir zonation
organic matter that led to the establishment of a larger database and identification of formation tops. As the lithostratigraphic units
than other isotope systems. The C isotope stratigraphy can be even are diachronous, and also that the lithostratigraphic information
applied to diagenetically altered sedimentary rocks (Sial et al., are synthesized from wireline logs, well cuttings and cores, corre-
2019) or that have undergone up to amphibolite facies meta- lation at field-basin scale may be tenuous and may be misleading
morphism but that may have retained the original isotope signal and hence employing chemostratigraphic method, even in diage-
(Melezhik et al., 2005; Sial et al., 2019). Therefore, d13C on car- netically altered strata, was found to be successful by Metzger et al.
bonates are more widely used in chemostratigraphy, except in (2014). These authors used carbonate and total organic carbon
carbonate-poor successions characterized by black shales (e.g., percentages, and stable isotopic compositions of organic carbon
Johnston et al., 2010). Nevertheless, one can measure organic car- present in the sediments of Late Ordovician strata spanning the
bon isotopes or carbonate carbon isotopes on fossils such as bi- Black River Group, Trenton Group, and Utica Shale across the sub-
valves, ammonites, belemnites, ostracods, etc. if present in these surface of New York State to construct robust chemostratigraphic
successions, that can be of use to document the carbon isotope correlation across the basin. Koch et al. (2014) found that though
changes (Sial et al., 2019). Auer et al. (2015) used chemostratigraphy the Mississippian section of the Anadarko Basin, U.S.A. has been a
for correlating C and O isotope events in early to middle Miocene prolific hydrocarbon producer, regional correlation was non-
shallow marine carbonates with C isotope maxima observed during existent due to the heterogeneous nature of carbonate reservoirs.
Monterey Event. Huck et al. (2017) used bulk carbonate carbon Based on the carbon isotope trends, these authors found that the
isotope signature to differentiate the primary and diagenetic isotopic composition was independent of facies changes and re-
components by using chemostratigraphic approach and found that flected global changes in environmental factors. Using these as
the mid-Cretaceous shallow-water limestone succession from keys, a regional correlation was established by these authors.
Oman exhibited a noisy bulk carbon isotope pattern. The multi- Fairbanks et al. (2016) demonstrated based on rock-based studies of
stage diagenesis was evaluated by petrography and geochemistry, the Eagle Ford Group of Central Texas how comparison of total
and recognized the isotopic threshold signals for further strati- gamma-ray (GR) logs to computed GR logs is requisite, as GR alone
graphic and paleoenvironmental interpretations. Lau et al. (2017) provides misleading information on facies, TOC content, deposi-
studied the influence of seawater carbonate chemistry, miner- tional environment etc. These authors have also documented that
alogy and diagenesis on calcium isotope variations on Lower- use of geochemical proxies such as enrichment-depletion of
Middle Triassic carbonates from Turkey in order to reconstructing selected trace elements may help correlate a variety of facies types
first-order secular changes in seawater d44Ca/40Ca composition. In over a range of spatial scales. El Attar and Pranter (2016) stated that
which, the Ca isotope ratios have been compared with the previ- though the lithologic interpretations made from wireline logs of
ously reported d13C values and other measured or compiled pa- the Upper Cretaceous Niobrara Member of the Mancos Shale,
rameters such as Mg/Ca, Mn/Sr, Mn and Sr concentration etc. to Piceance Basin, Colorado, exposed in nine wells that are spaced at
check whether the Ca isotopic ratios are altered by diagenesis or about 32 km could identify only two major lithofacies types
not in order to reconstruct seawater Ca isotopic signatures. namely, interbedded calcareous shale and shaley limestone facies,
Cores from a series of seismically defined channel and overbank the elemental chemostratigraphy could identify six chemostrati-
deposits penetrated by three wells in the Upper Paleocene deep- graphic zones, exemplifying the efficacy of chemostratigraphy over
marine reservoir interval of the Foinaven Field, West of Shetland conventional methods of stratigraphic classification and correla-
were analyzed for trace element geochemistry and petrography by tion. Coleman and Jordan (2018) stated that technological advances
Hutchison et al. (2001). Based on similarities in geochemical and in handheld X-ray fluorescence (HHXRF) demonstrated the utility
petrographic data, these authors divided the succession into four of chemostratigraphic data to create higher-order sequence strati-
principal correlation zones with two additional sub-zones. Higher graphic interpretations. Pietras and Spiegel (2018) stated that a
variability of facies on spatial and temporal scales combined with wealth of elemental proxy information that can be readily accessed
lack of diagnostic fossil that thwarted local-field-regional-basinal by hand-held X-ray fluorescence (XRF) spectroscopy. Through the
scale stratigraphic correlation of major hydrocarbon reservoir of application of this technique on the mudstones of the Upper
Triassic Argilo-Gre seuxInfe rieur Formation of Algeria was over- Ordovician Trenton Group and Utica Shale, these authors demon-
come by Ratcliffe et al. (2006a) through application of strated its effectiveness in revealing more cryptic changes in
310
sediment provenance and bottom-water redox conditions. Wüst sediment provenances to reconstruct paleoflow pathways within
et al. (2018) reported high-resolution chemostratigraphy of the basins and model the history of sediment supply and basin fill.
Montney Formation across Alberta. They identified three unique Integration of systems tracts and diagenesis could provide a
and distinct chemostratigraphic units with several subunits (i.e. powerful tool for analysis and prediction of reservoir quality.
CS1a, 1b, 3a, 3b) based on stratigraphic variability of trace In a recent review, Tinnin and Darmaoen (2016) emphasized the
elemental concentrations and ratios such as Si/Ti, As/Zr. Based on application of major and trace elemental data to understand
stratigraphic variations of geochemical parameters such as SiO2/ geochemical variability within sedimentary sequences. The results
Al2O3, K2O/Al2O3, TiO2/Al2O3, Sr/Ca, and combining them with sharp and interpretations of this type of analysis can aid in the identifi-
vertical facies variations in Lower Cretaceous strata of the Kurnub cation of ideal acreage positions and/or defining horizontal well
Group (Jordan), Farouk et al. (2018) identified four sequence target zones when integrated with other datasets to determine
boundaries that are associated with 11 facies types and 9 system reservoir quality. Documentation of stratigraphic, sedimentological
tracts. This information was further linked to the Lower Cretaceous and geochemical relationships across buried Lower Cretaceous City
relative sea-level fluctuations and their eustatic origin, and enabled paleoreef-shelf margin in south Texas by Peters et al. (2018) has
correlation of the strata with local, regional and global counter- revealed basin ward decrease in calcite from 60% to 48% is
parts. Peng et al. (2020) interpreted significant changes in the trace- accompanied by an increase in clay minerals from 12% to 20%
element enrichment pattern, mineral composition, texture of suggestive of lateral facies variations as a result of changing
framboidal pyrite, and other bulk geochemical parameters in depositional setting and cyclic enrichments of molybdenum sug-
different lithofacies as results of high-amplitude and high- gestive of anoxic-euxinic water mass as a result of prevalent
frequency glacio-eustatic sea-level oscillations in the silled changes in depositional bathymetry. On the basis of outcrop
Midland Basin during the late Paleozoic ice age. These authors have reconnaissance and sample testing, high-quality source rocks of
also interpreted the depleted seawater Mo in the silled basin and black shales with total organic carbon contents of 3e6% and a
low sediment Mo/TOC as the results of glacio-eustatic falls that maximum of 17% were discovered by Zhu et al. (2018) within the
restricted the circulation and or separated the Midland Basin from lower Cambrian Yuertusi Formation, China. These authors have also
the Panthalasic Ocean. With this study, the authors have provided a characterized the source rock potential through vitrinite reflec-
geochemical key to correlate the studied strata with global coun- tance, d34S and recommended large-scale exploration of the basin
terparts. Zhang et al. (2020) reviewed the U isotopic signature in for hydrocarbon condensate and gas production. Vicea and
marine carbonates as a proxy for paleoredox conditions of global Hallecka (1999), Sechman and Dzieniewicz (2007), Azeez et al.
oceans and also discussed how the primary signatures of U-iso- (2011), Patil et al. (2013), Kumar et al. (2014), Sechman et al.
topes are affected by syn- and post-depositional diagenetic process (2015), Kalpana et al. (2016) and Twaro g et al. (2018) have
(i.e. meteoric diagenesis, dolomitization etc.). Milad et al. (2020) demonstrated methods of detecting hydrocarbon reserves in sub-
demonstrated how integration of information on field-scale sedi- surface through analysis and detection of biomarkers in surface soil
mentary structures, outcrop gamma-ray profile, and sequence and active tectonic structural features and microfractures. Shalaby
stratigraphic framework. The highlight of this study is the intro- et al. (2019) combined well log mathematical models and machine
duction of the machine learning concept, that too with appreciable learning methods to predict total organic carbon in Jurassic source
success. rocks in the Shams Field, Northwestern Desert, Egypt. The results
have shown that this method is applicable with confidence when
4. Reservoir characterization enough geochemical data are not available. Guo et al. (2020) opined
that though it is of general perception that the occurrences of hy-
4.1. Sedimentary facies and sequences drothermal dolomites in the Lower Paleozoic carbonate reservoirs
of the Tarim Basin may have a positive effect on reservoir devel-
Hydrocarbon exploration industry has been the beneficiary of opment, very high heterogeneity due to alteration by hydrothermal
the developments in chemostratigraphy as it has provided a reli- brine as well as various fault structures. These heterogeneities in
able tool where new reservoirs have to be identified, for applicable reservoir properties were documented by these authors through
analogues to be tracked in the vicinity of known reservoirs, and to integration of geophysical and geochemical data. Weibel et al.
characterize the identified reservoirs for designing better exploi- (2010) used chemostratigraphy based on geochemical data from
tation strategies. Thus, chemostratigraphy became a potential tool 264 core samples from 8 wells on Upper Jurassic sandstones in the
for hydrocarbon exploration and reservoir characterization as it has northern Danish Central Graben. As per the study, two reservoir
proved its mettle even where other stratigraphic methods have sandstone units between the two offshore claystone were recog-
limitations. nized as a transgressive marginal marine to shoreface sandstone of
The chemostratigraphic technique is largely utilized to trace the Gert Member and the regressive to transgressive shoreface
individual beds as well as sequences over a large area sprawling sandstone of the Ravn Member (Weibal et al., 2010). By using
from interbasinal to global scale. The inter-well correlation of any different geochemical ratios and multivariate statistical analysis
strata can be achieved by recognition of similar geochemical with multiple data sets, the depositional differences between the
characteristics that is facilitated by close scrutiny of long-term geological members, diagenetic influences, differences in the
geochemical trends, geochemical fingerprinting of sedimentolog- sediment source area, and local volcanic sources are well
ical packages and individual beds. Geochemistry can also be used to established.
model sediment dispersal patterns to aid in characterization of Abell et al. (1989) used C and O isotopic signatures of dolostones
reservoir geometry; prediction of the extent of claystone perme- and plotted stratigraphically to see the variations in depositional
ability barriers in reservoirs, thus permitting assessment of po- and post-depositional conditions from the Carswell Formation,
tential reservoir partitioning; to eliminate ambiguities associated northern Saskatchewan, and found that the dolomites showed the
with gamma-ray responses of claystone barriers; to identify C and O isotopic concentrations close to the mainstream stromat-
diagenetic minerals and their distributions in a sequence in order to olites. However, they indicated some evaporative alterations during
establish depths, and lateral continuity. It is also useful for identi- the deposition. Ghazban et al. (1992) used C, O and Sr isotopic
fying the composition of major cementation zones which may signatures to characterize the multistage dolomitization in the
present permeability barriers in reservoirs and changes in Society Cliffs Formation, Canada. Tekün (2001) employed
311
stratigraphy and multiple geochemical approaches on celestine- The Al, Ti and Zr are considered as immobile elements due to their
bearing gypsifereous formations and stated that the celestine did low solubility in oxides and at low temperature in aqueous solu-
not develop through primary sedimentary processes, instead, high- tions (e.g. Stumm and Morgan, 1971; Wesolowski, 1992; Ayers and
temperature conditions prevailed during late-diagenetic celestine Watson, 1993; Ziemniak et al., 1993, Hayashi et al., 1997). Al is
formation. Amodio et al. (2008) used high-resolution carbon present mostly in feldspars of the felsic rocks; Ti is present in mafic
isotope stratigraphy of a shallow marine carbonate section from rocks associated with olivine, pyroxene and hornblende, and Zr in
Matese Mountains which were correlated with coeval sections zircon. The ratio of Al2O3/TiO2 is used to define the parent rock,
based on bio, cyclo and sequence stratigraphic criteria. where a weight ratio range of 3e8 is considered to represent mafic
Mohammadi et al. (2013) used chemostratigraphic approach based igneous rocks (45e52 wt% SiO2), a range of 8e21 represents in-
on major and minor elements and C and O isotope values of car- termediate igneous rocks (53e66 wt% SiO2), and a range of 21e70
bonates from the Kangan Formation, Iran to address the diagenesis, represents felsic igneous rocks (66e76 wt% SiO2) (Hayashi et al.,
paleo-temperature and sea-level changes. Four major transgressive 1997). The plots such as La/Sc versus Co/Th (Fig. 1c) and Cr/Th
and regressive events were established in 2 Ma duration. versus Sc/Th (Fig. 1d) ratios can discriminate the felsic and mafic
Svendsen and Hartley (2001) compared the high-resolution provenances (Condie and Wronkiewicz, 1990; McLennan et al.,
spectral gamma-ray (SGR) lot and whole-rock geochemistry in an 1990; McLennan and Taylor, 1991). Cullers et al. (1988) stated
analog reservoir scale outcrop from the Otter sandstone Formation that the geochemical ratios of immobile elements show distinct-
of the Sherwood Group, east Devon. Initially, three lithotypes were ness between the sediments derived from felsic and mafic source
discriminated based on Th/U and K2O data, then these data were rocks. Cullers et al. (1988) and Cullers and Podkovyrov (2002) have
applied to SGR log to find that SGR logs have a high potential for also proposed ranges of the geochemical ratios for the sand and fine
real-time lithotype prediction and thus useful to predict the fractions of sediments derived from mafic and felsic rocks. As the
reservoir quality, which can increase the confidence while inter- elements used in the calculation of these ratios are susceptible to
preting the sedimentary architecture (Svendsen and Hartley, 2001). fractionation during weathering and transport, these ratios should
Peters and Fowler (2002) reviewed the application of petroleum be used with caution. The input of sediments from ultramafic rocks
geochemistry for exploration and reservoir management as this can be distinguished by using Th/Sc versus Cr/Th plot (Condie and
tool offers a rapid, low-cost evaluation to understand the devel- Wrokiewicz, 1990; Totten et al., 2000) (Fig. 1d) and VeNieLa*4
opmental and production problems. Benzagouta and Amro (2009) ternary plot (Fig. 1e) proposed by Bracciali et al. (2007). In order to
used geochemistry for reservoir quality assessment to link them elucidate the original provenance signatures, the geochemical sig-
with petrophysical characteristics of the reservoir rocks in order to natures should be preserved well and should not be affected
delineate the net pay zones. Ito et al. (2017) evaluated the Gamma- significantly by geological processes (recycling, sorting, diagenesis,
ray (GR) log profile with radioactive elements to find out the source metamorphism, etc.). The effect of recycling can be identified by
of total GR and their significance for shale evaluation from Nagoka, using the discriminant plots of Roser and Korsch (1988), and Floyd
Japan. Thorium bearing minerals were mostly associated with the and Leveridge (1987) plot (La/Th versus Hf; Fig. 1b).
finer fractions of sediments while K-bearing minerals are associ- Sorting effects on primary geochemical signatures of the sedi-
ated with the coarser fractions of the sediments. The estimated mentary rocks can be identified using bivariate plot of McLennan
shale volume was agreeable with the measured values while et al. (1993) (Zr/Sc versus Th/Sc; Fig. 2a); and ternary plot (Zr-
selecting end members at each depositional sequence. Thus their 15*Al2O3-300*TiO2; Fig. 2c) of Garcia et al. (1994) based on the
study had recommended the combined use of GR logging and enrichment of elements associated with the heavy minerals.
detailed core analysis with sedimentology and geochemistry to Ancient clastic sedimentary rocks might have undergone mul-
assess the shale volume in the targeted sequences. Zhu et al. (2020) tiple sedimentary cycles and their mineralogical and geochemical
used integrated datasets such as sedimentological, petrography, signatures reflect the present and previous weathering and diage-
and geochemical analysis and reconstructed the depositional netic histories and thus it is a challenging task to separate the cli-
setting and diagenetic history to assess their impacts on reservoir matic signal from them as they carry more composite records
quality of a giant condensate heterogeneous reservoir (Zhanazhol (Garzanti et al., 2014). To overcome this issue, recently, Garzanti
reservoir, Pre-Caspian Basin, Kazakhstan). Accordingly, 12 microf- et al. (2014) and Garzanti and Resentini (2016) used a technique
acies types were identified based on vertical and lateral distribution and have successfully distinguished the effect of recycling from
and a depositional model was proposed with the different depo- weathering by plotting the WIP (Weathering Index or Parker;
sitional sequences such as tidal flat, inner ramp, and middle ramp. Parker, 1970) values against CIA values (Fig. 2b). Where, the WIP
The depositional environment and diagenetic evaluation had an decreases linearly with the addition of quartz into the system.
impact on the formation types of vertical distribution patterns of However, CIA values are not unaffected and thus, this plot distin-
porosity and concluded that the impact of depositional and guishes the effect of extensive recycling (Garzanti et al., 2014).
diagenetic interaction on the reservoir quality can be a reliable Besides, Zr/Sc versus Th/Sc biplot (McLennan et al., 1993, Fig. 2a)
predictor of the reservoir properties and also comparable to the and the ternary plot (Zr-15*Al2O3-300*TiO2; Fig. 2c) of Garcia et al.
adjacent fields and the reservoir has similar settings. (1994) also can be used to establish the heavy mineral enrichments
by the sorting and recycling effects. These examples demonstrate
4.2. Provenance and tectonic setting the importance of integrating bulk chemistry of sedimentary rocks
with additional other datasets such as heavy mineral analysis,
A classic provenance discriminant diagram was proposed by mineral chemistry, petrography, mineralogy (bulk and clay miner-
Roser and Korsh (1988) using major oxides, which can discriminate alogy), zircon geochronology and other isotopic ratios in accurate
four important provenance source regions as a) felsic igneous rocks, delineation of provenance and tectonic setting.
b) intermediate igneous rocks, c) mafic igneous rocks and d) Scheffler et al. (2003) utilized geochemical proxies such as CIA
quartzose sedimentary/quartzose igneous rocks (Fig. 1a). This (chemical index of alteration), Zr/Ti, Rb/K, V/Cr to interpret changes
discriminant function diagram can be used to trace the provenance in provenance, climate and paleoenvironments of the Karoo Basin.
signature of sandstone and mudstone suites using major oxides. Martínez-Monasterio et al. (2006) combined chemical character-
The elemental concentrations of Al, Ti and Zr are often used to ization of titanomagnetite grains with magnetic parameters and
differentiate the felsic and mafic provenances (Hayashi et al., 1997). applied Discriminant function analysis to accurately differentiate
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Fig. 1. Geochemical fingerprinting of provenance. (a) Discriminant function diagram of Roser and Korsch (1988) showing the major provenance field for the clastic rocks. (b) La/Th
versus Hf diagram (after Floyd and Leveridge, 1987) showing the provenance field. (c) Co/Th versus La/Sc shows major source rocks composition. (d) Mixing values are shown in %
on the mixing curve representing the mafic end member contribution to the mixing products (after Condie and Wronkiewitcz, 1990; Totten et al., 2000). The mixing of ultramafic
end member is also shown on the plot. (e) NieVeLa*4 ternary plot shows the major provenance fields (after Bracciali et al., 2007).
sediment provenances. Using whole-rock chemistry were Mahantango Formation. As the whole-rock chemistry clubs
employed to infer relative changes in clay and heavy mineral together the detrital input as well as authigenic input, the inter-
occurrence and finally to constrain on provenance and reservoir pretation of provenance may be exercised with caution, especially
characteristics of the Bowser and Sustut basins by Ratcliffe et al. based on whole-rock geochemical data. Weltje and Von Eynatten
(2007) through application of chemostratigraphic principles. (2004) have documented the influence of texture over whole-
Hupp and Weislogel (2018) interpreted a felsic igneous, granodio- rock chemistry. These limitations could be alleviated by the docu-
ritic, upper-continental crustal source with additional influx from a mentation of TiO2/Al2O3 as detrital indicator (Chen et al., 2013), Zr/
recycled quartzose sedimentary source for the Hamilton Group, Sc as an indicator of intensity of recycling (McLennan, 1993;
Middle Devonian Acadian foreland basin based on geochemistry. Mongelli et al., 2006) and TiO2/K2O to determine the input of
These authors have also documented subtle changes in clay prov- weathered material to the basin over time (Playter et al., 2018). The
enance throughout deposition of the Marcellus Shale and the Si/Al ratio (proxy for quartz content in clay) is considered to
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Fig. 2. Binary and ternary plots which distinguish the effect of sorting and recycling from the primary geochemical signatures of the sedimentary rocks (a. Zr/SceTh/Sc
diagram showing the effect of weathering and recycling with the possible source rocks (after McLennan et al., 1993) b. CIA/WIP biplot shows the effect of recycling by increasing
quartz content which affects the WIP values rather than CIA values (after Garzanti et al., 2014). and c. the Zr-15*Al2O3-300*TiO2 ternary plot shows the sorting trend of sandstones
due to enrichment of heavy minerals in clastic rocks (after Garcia et al., 1994)).
represent the detrital quartz relative to aluminosilicate compo- in the shale normalized plot. Similarly, the shales from passive
nents derived from the source area (Hofmann et al., 2001). The margin are similar to post-Archean shales with a flat trend. By
relative variations of clay minerals such as illite and I/S mixed-layer plotting the geochemical ratios to the stratigraphic profile the
minerals are represented by K/Al ratios (proxy for illite content). variations of minerals, provenance area, weathering pattern and
Similarly, Al2O3/SiO2 (molar ratio) ratio is used as a grain size index. depositional environment have been successfully identified
Other elemental ratios used in the provenance study are Sc/Th, (Hoffman et al., 2001). The effect of recycling and felsic provenance
Al2O3/TiO2, Ni/Al, Cr/Al, Th/Sc, Ti/Zr, MgO/Al2O3 and Ti/Nb; signature can be evaluated by the stratigraphic variation of Zr and
(Amorosi et al., 2007; Dinelli et al., 2007; Taylor and McLennan, Hf which are mainly controlled by zircon minerals and similarly Ti,
1985; Hayashi et al., 1997; Vital and Stattegger, 2000; Chetelat Nb are controlled by ilmenite or anatase and Cr by chromite etc.
et al., 2013). (Pe-Piper et al., 2008, Nagarajan et al., 2017a,b; 2019; 2020). The
Most of the elements in sediments and sedimentary rocks are enrichments of selected elements (V, Ni, Co, Cr, and Sc) at certain
primarily controlled by the host minerals and their abundance in stratigraphic positions represent mafic rock input (Pe-Piper et al.,
the sediments. Thus, variations of the elements (i.e. Sr, Rb, Y, Ni, Co, 2005; Ryan and Williams, 2007). The variations of Sc and V
Sc, Th, Th, U, Ti and REEs etc.) in sediments represent the source together Zr, Hf, Cr and Ti suggest that the elements are mainly
rock composition (Totten et al., 2000). Stratigraphic profiles of controlled by heavy minerals. Many studies have used to detect the
these elements may show the changes in the source rock compo- heavy minerals by using geochemical ratios such as Zr/Sc
sition (Bhatia and Crook 1986; McLennan et al., 1990; Pe-Piper et al., (McLennan et al., 1993; Mongelli et al., 2006) and clay content/type
2008) on a temporal scale. Winchester and Max (1989) found that by Cr/Sc, Zr/La, Zn/Sc, SiO2/Al2O3, Ga/Rb, K2O/Al2O3, K2O/Rb, Na2O/
the concentrations of elements are showing significant variation Al2O3 and Rb/Al (Plank and Langmuir, 1998; Preston et al., 1998;
when normalized against the shales. Accordingly, shales deposited Pearce et al., 1999, 2010; Hofmann et al., 2001; Hofer et al., 2013;
in Ocean arc settings show a depletion of many elements than that Clift et al., 2014; Ratcliffe et al., 2015; Playter et al., 2018). SmeNd
of Post-Archean continental shale, while the shales deposited in isotopic analysis of selected samples revealed extrabasinal
continental arc and active continental margin are characterized by detritus of the Hamilton Group that originated from a mixed
high large ion lithophile elements and show broad curving profile sediment source, with clay influx from both rocks associated with
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the Superior Craton to the north and northwest (tDM > 2.7 Ga) and dolomitization, and meteoric cementation and stabilization during
Grenville-sourced sediments derived from the adjacent Acadian sea level lowstands and identified these through documentation of
foldethrust belt to the east (tDM~ 1.4e1.6 Ga). In addition, older trends in carbon and oxygen stable isotopic compositions of
SmeNd model ages, felsic composition, and evidence of sediment texturally well-preserved calcites of marine cements, brachiopods,
recycling suggest little to no contribution from the Acadian volcanic bulk carbonate, micritic matrix and the first generation of meteoric
arc, indicating that volcanic tuff of the Tioga ash beds represents spars. The numerical models have affirmed the interpretation of
isolated episodes of volcanic input into the basin. Predominant diagenetic alteration in a partially closed system. Relative abun-
influx of sediments from Grenvillian granite-gneissic rocks and dances of the elements such as Ca, Mg, Sr, Fe, Mn and Sr in the
subordinate sediments from Taconic igneous rocks were inter- marine limestones are being widely used to study carbonate
preted by Hattori et al. (2019) as provenance for the organic-rich diagenesis (Brand and Veizer, 1981; Veizer, 1983a,b; Banner and
Macasty shale in the Gulf of St. Lawrence during the Late Ordovi- Hanson, 1990). The classic works by Brand and Veizer (1980) and
cian. Zhao and Zheng (2015) used various detrital element con- Veizer (1983a, b) explained the theory and application of trace
centrations and isotopic ratios of detrital sediments from lower elemental abundances for understanding chemical diagenesis of
Yangtze basin South China to address the variations of the intensity carbonates. They proposed diagenetic stabilization fields for
of weathering and provenance of Permian to Triassic sediments. aragonite, high-Mg calcite and low-Mg calcite in meteoric water
Dickinson and Suzek (1979) and Dickinson et al. (1983) observed (after Brand and Veizer, 1980, Fig. 4a). In addition to C and O iso-
that sandstones can be linked to a specific tectonic setting of their topes, trace elements such as Sr, Ba, Mg, Mn, Fe, Zn and radiogenic
provenance based on detrital modes which in turn was affirmed by isotope (87Sr/86Sr) also can be used for studying chemical diagen-
related studies by other workers (for example, Bhatia, 1983; Bhatia esis of carbonates (Veizer, 1983a, b) (Fig. 4aeh). The Sr/Ca ratio of
and Crook, 1986; Roser and Korsch, 1986, 1988) who in turn have the carbonates decreases with repetitive dissolution and precipi-
proposed different geochemical parameters for tectonic discrimi- tation due to low partition coefficient of Sr (Banner and Hanson,
nation of clastic sedimentary rocks. As each tectonic environment 1990). Diagenesis in marine carbonates decreases Sr/Ca ratio with
has distinctive characters of provenance and is controlled by an increase in Mn and Fe concentration (Veizer, 1983a, b; Fig. 4f and
distinctive sedimentary processes, Bhatia and Crook (1986) pro- g). The Mn/Sr and Rb/Sr ratios were found to be useful in identifying
posed the existences of different tectonic environments, such as post-depositional alterations (Derry et al., 1992; Kaufman et al.,
oceanic island arc, continental island arc, active continental margin, 1991, 1992 and Kaufman and Knoll, 1995; Knoll et al., 1995) and
passive continental margin, collisional setting and rift setting have been widely used to study diagenesis (Fig. 4e, h) of the car-
(Fig. 3a) that could be recognized from sedimentary geochemistry. bonate rock components (Ramkumar et al. 2014,2015) and rocks
Based on major oxides chemistry, Bhatia (1983) proposed three (Nagarajan et al., 2008, 2011, 2013). Unaltered limestones typically
different discriminant diagrams for sandstones (DF plot, display low Mn/Sr (<1.5 Folling and Frimmel, 2002; <2, Jacobsen
(Fe2O3þMgO versus TiO2) and (Fe2O3þMgO versus Al2O3/SiO2), and Kaufman, 1999), Fe/Sr < 50, and d18O values > 10‰. Similarly,
which can discriminate tectonic environments. Later, Roser and the d18O values between -1‰ and 14‰ are considered as slightly
Korsch (1986) proposed a discriminant diagram for sandstone altered and values < -14‰ are considered as highly altered by
and mudstone based on K2O/Na2O and SiO2 (dry wt% basis), which diagenesis (Folling and Frimmel, 2002) (Fig. 4b, h). Sr isotopic
can discriminate three major tectonic settings such as passive concentrations in carbonates are highly susceptible to diagenetic
continental margin (PM), active continental margin (ACM) and alteration and thus increase the Sr isotopic ratios (Fig. 4c) in car-
oceanic island arc (ARC) (Fig. 3b). Evaluation of the tectonic bonates (Knoll, 2000). Carbonates affected by diagenesis show
discriminant function diagrams proposed by Bhatia (1983) and covariance and show more negative values (Fig. 4b) of O and C
Roser and Korsch (1986) using major elements indicated the diffi- isotopes. The O isotopic signatures of carbonate are easily reset
culties in using geochemistry to interpret the tectonic setting (e.g., (Frank and Bernet, 2000) when compared to d13C signatures
Van de Kamp and Leake, 1985; Nesbitt and Young, 1989; (Banner and Hanson, 1990). Nelson and Smith (1996) proposed a
Milodowski and Zalasiewicz, 1991; Armstrong-Altrin and Verma, discrimination plot based on d13C and d18O compositions, which
2005; Ryan and Williams, 2007). These validations concluded discriminates different depositional and diagenetic environments.
that the overprinting of original depositional signatures by intense Nelson and Smith (1996) reviewed O and C isotope compositional
diagenesis and metamorphism might be the reason for the inac- fields for skeletal and diagenetic components in non-tropical car-
curacies in tectonic discrimination diagrams. Verma and bonate sediment and limestones. Many studies have documented
Armstrong-Altrin (2013) proposed two new discriminant tectonic the combined use of trace elemental geochemistry, stable isotope
setting diagrams using silica content in sediments such as high- and radiogenic isotopic compositions to document various types of
silica [(SiO2)adj; 63e95%] and low silica diagrams [(SiO2)adj; diagenetic transformations in carbonates (for example, Knoll et al.,
35e63%)] (Fig. 3c and d). Discriminant-function multi-dimensional 1995; Kaufman and Knoll, 1995; Derry, 2010; Nagarajan et al., 2008,
diagram (Verma and Armstrong-Altrin, 2013) involves ten major 2013; Mahboubi et al., 2015; Huck et al., 2017; Jiang et al., 2018).
oxides with an adjustment of their proportions to 100 wt% and Kuleshov and Sedaeva (2009) and Pokrovsky and Bbujakaite
calculated on a volatile free basis. This diagram is considered to be (2016) used C, O isotope signatures and constructed stratigraphic
stable (Ghaznavi et al., 2018). Later, Verma and Armstrong-Altrin profiles to study the depositional environment and stratigraphic
(2016) created new discrimination diagrams (Fig. 3e and f) to correlations and also found that the studied carbonate has under-
differentiate the active and passive margin settings using isometric gone post-sedimentary transformations. Himmler et al. (2010)
log-ratio transformation. studied rare earth elements in authigenic methane seep carbon-
ates as a tracer for fluid composition during early diagenesis
4.3. Diagenesis together with C and O isotope signatures and elemental concen-
trations and concluded that pore fluid composition is not only
Bishop et al. (2014) noted that common criteria such as textural evolved during formation of different phases, but has changed
preservation, staining, luminescence, and depletion near sequence during the precipitation of individual phases of the seep carbonates
boundaries are inadequate to record diagenetic alterations. They from Makran accretionary prism.
further demonstrated the domination of early diagenesis during Zhao and Zheng (2013) studied origin of post-depositional fluids
sea level highstands by marine cementation and reflux in Ediacaran carbonates from South China using stable isotopes and
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Fig. 3. Different tectonic setting discriminant plots for the clastic sedimentary rocks. (a)The discriminant function diagram for sandstone proposed by Bhatia (1983) and Bhatia
and Crook (1986) which discriminates four tectonic environments as passive margin, active continental margin, continental and oceanic island arcs. (b) The log (K2O/Na2O) versus
SiO2 plot discriminates three tectonic environments of sandstone-mudstone suites (Roser and Korsh, 1986). (c) A new discriminant function diagram (after Verma and Armstrong-
Altrin, 2013) for high silica clastic sediments which discriminates arc, continental rift and collision tectonic settings. (d) A new discriminant function diagram (after Verma and
Armstrong-Altrin, 2013) for low silica clastic sediments which discriminates arc, continental rift and collision tectonic settings. (e) A new major element based multidimen-
sional discriminant function diagram (after Verma and Armstrong-Altrin, 2016), discriminates active and passive tectonic settings of the clastic sediments. (f) A new major and trace
elements based multidimensional discriminant function diagram (after Verma and Armstrong-Altrin, 2013), discriminates active and passive tectonic settings of the clastic
sediments.
petrography. They found that the wall rock carbonates experienced tracing (Zhao and Zheng, 2013). Barbier et al. (2015) studied the
very-limited recrystallization. Based on the similarity of factors controlling the nature and distribution of the diagenetic
geochemical pattern (REE þ Y and C and O isotopes) between the phases that gave rise to carbonate reservoirs.
wall rock carbonates and the veins, the authors interpreted com- Jiang et al. (2018) studied petrography, isotopic, fluid inclusion
mon depositional fluids for both. Further, they have documented and quantitative porosity data to predict and study the diagenetic
significant differences in geochemical pattern of the lower unit of processes, which exercised significant control on the reservoir
the same succession and suggested different origins of their quality of dolostones and limestones from the Sichuan Basin, China.
depositional fluid. This study had concluded that the origin of post- Similarly, the diagenetic constraints on the heterogeneity of tight
depositional fluids can be distinguished from the depositional sandstone reservoir from the Sichuan Basin, China, were addressed
fluids by the integrated use of trace elements and stable isotope by Liu et al. (2017) based on C and O isotopic data of carbonate
316
Fig. 4. Geochemical fingerprinting of diagenesis. (a) Mn versus Sr/Ca bi-plot shows the Diagenetic “stabilization for aragonite (A: wavy), high-Mg calcite (HMC: inclined ruling),
and low-Mg calcite (LMC: vertical ruling) in meteoric water (after Brand and Veizer, 1980). The ranges inside the boxes mark the theoretical ranges of inorganic A, HMC, and LMC
precipitated in equilibrium with present-day average surface seawater. (beh) Bi-plots showing various diagenetic trends of the carbonates.
cements along with data on porosity, petrography, fluid inclusion some similarities. These authors have also stated that fluid-
and elemental chemistry. Khan et al. (2019) used stable isotope inclusion, d18O, and paragenetic evidence point to the formation
geochemistry on carbonates of Kachchh, India, to study microfacies, of ankerite during deep burial after the onset of over-pressuring,
diagenesis and their implication for depositional environment and but before hydrocarbon emplacement in the reservoirs, implying
reservoir quality and have stated that the observed diagenetic indirectly that scattered ankerite formation has not affected the
features were developed in marine phreatic, fresh water phreatic, reservoir quality. Localized calcite cementation was identified
mixed marine-fresh water phreatic and burial diagenetic through stable isotopic and strontium isotopic data of the gas res-
environments. ervoirs of the upper Miocene Abu Madi Formation, Nile Delta Basin,
Hendry et al. (2000) reported distinct ranges of isotopic com- Egypt, and the occurrences of kaolin in the lowstand systems tract
positions between disseminated ankerite cement and ankerite fluvial sandstones and pyrite in the transgressive systems tract
concretions in the Franklin and Elgin Fields of Upper Jurassic estuarine sandstone and a model of diagenetic origin was proposed
Fulmar Formation, South Central Graben, North Sea, in spite of by Salem et al. (2005). However, the authors reported that owing to
317
their localized occurrences, they were not able to significantly identify clay dominated facies of a sedimentary basin. For example,
affect the reservoir quality. The relationships between diagenetic Ga/Rb reflects the kaolinite content related to illite (Ratcliffe et al.,
transformation of carbonates into dolomites of various morphol- 2010, 2015). Low values of K/Rb and high values of K2O/Al2O3
ogies and types, ranging from low-temperature to hydrothermal indicate high illite content (Ratcliffe et al., 2006b, 2015; Hofmann
origins and their impacts on reservoir properties were recently et al., 2001; Hofer et al., 2013; Playter et al., 2018) and Na/Al ratio
examined by Xin Hui et al. (2020) with the help of petrography, is a proxy for smectite content in the sediments (Hofmann et al.,
mineralogy and geochemistry of the Paleozoic carbonates of the 2001; Hofer et al., 2013; Playter et al., 2018).
Kinta valley, Malaysia. These authors have concluded that, among Fustic et al. (2011) suggested that integration of sedimentolog-
the seven facies/morphological types, the sucrosic dolomites ical and bitumen geochemical data is essential for the identification
exhibit appreciable porosity development. Based on documenta- of barriers and baffles to fluid flow in oil sand reservoirs, especially
tion and analysis of spatial variations of selected geochemical when vertical permeability has to be modeled before attempting
characteristics, Wüst et al. (2018) inferred diagenetic trans- thermally-mediated recovery. O’Neal and Sonnelberg (2018) inte-
formation of in-situ porous biogenic debris (metastable aragonite, grated core description, high-resolution chemostratigraphy, and
high Mg-calcite, biogenic silica and rare detrital and organic mat- petrophysical logs to characterize well-length scale lateral hetero-
ter) during burial to “pseudo-laminated dolomitic siltstones” and geneity to ease horizontal steering, well-completion, and assess-
occur as isolated carbonate concretions which in turn significantly ment of well -performance. Through combining trace elemental
alter the reservoir properties. Hattori et al. (2019) interpreted low- and organic carbon data with these acquired data the authors could
temperature diagenesis based on the preservation of abundant infer lateral bentonite discontinuity and distinct changes in sedi-
organic matter and occurrence of calcite in pore spaces of the mentary structures that have implications on unconventional oil
organic-rich Macasty shale in the Gulf of St. Lawrence. The Ordo- and gas development. Though known to have existed in practice
vician marine carbonates are found to be reservoir rocks in Tahe previously, Wilhelms et al. (2001) were one among the first who
Oilfield, Tarim Basin, NW China; however, prevalent multistage documented the use of geochemistry for detecting sealing of faults,
structural uplifts and subsequent paleo-exposure, weathering and identification of reservoir compartments and well path.
erosion have impacted the reservoir properties significantly. In Recently, Worden et al. (2020) reviewed the character, quanti-
order to characterize them, integrated petrographic studies, fication, integration of signals from downhole logs, origins, and
elemental and C, O, Sr isotopes geochemistry and fluid inclusions sources of chlorite in sandstones. The positive and negative effects
study were attempted that revealed the origin and types of of chlorite on sandstone reservoir quality were also discussed in the
diagenetic fluids, with which the dissolution and development of review as chlorites commonly occur in sandstones by grain coating
secondary porosity enhancements were documented by Han et al. and pore filling. Quite oblivious to the commonly held view that
(2019). clean sandstones are expected to have better reservoir quality than
Jones et al. (2019) documented lateral gradients in d44Ca and clay cemented sandstones, recent studies such as Bloch et al. (2002)
13
d C that reflect variations in the extent of early marine diagenesis and Worden et al. (2020) suggested that a small amount of clay in
across the platform. Xie et al. (2020) examined data on d13C of the the form of grain coated chlorite can lead to superior quality than
sandstones in the Upper Triassic Yanchang Formation of the Ordos the clean sandstones. These observations imply that though not all
Basin, China that indicated precipitation of diagenetic calcite under chlorites have a negative impact on the sandstone reservoir quality,
the influence of thermodynamic decarboxylation of organic matter. the physical position and volume in the pore network are para-
Supply of Ca2þ, Mn2þ, Fe2þ, and Mg2þ for calcite precipitation mount factors for the reservoir quality. The presence of chlorite is
through interaction with feldspar and other silicates, such as primarily controlled by the source of Fe. As most of the chlorite
dissolution and replacement together with transformation of cemented sandstones are deposited in a relatively Fe-rich marginal
smectite to illite were also recognized. These geochemical proxies marine environment and the main sources of Fe are from the hin-
have identified the calcite-cemented zones which in turn signifi- terland, which is important to generate chlorite-rich sandstones.
cantly affected the reservoir quality. Weibel et al. (2020) studied distribution and morphology of illite to
characterize the reservoir properties as the growth of fibrous illite
4.4. Clay mineral and other barriers may destroy the promising reservoir properties. Based on the study,
it was suggested that microquartz coating can help to preserve the
The chemical index of alteration, AeCNeK porosity and permeability and when it occurs with fibrous illite, the
(Al2O3eCaO þ Na2OeK2O) relations, index of compositional vari- permeability is reduced (Weibel et al., 2020). It was illustrated that
ability, and Th/Sc versus Zr/Sc ratios are routinely used to interpret geochemistry is an effective tool for reservoir characterization
the intensity of chemical weathering in source areas, compositional when combined with petrography, mineralogy, and Gamma-ray
maturity of sediments and to evaluate the sorting and recycling log.
effect (Nesbitt and Young, 1982, 1984; McLennan et al., 1993;
Nesbitt et al., 1996; Nagarajan et al., 2014, 2015, 2017a, b, 2019, 5. Geochemical fingerprinting
2020) which in turn have implications on the spatial heterogeneity
of the reservoir-seal facies types. The Al normalized trace element 5.1. Physical properties of the reservoir
concentrations are used to document enrichment of trace element
concentrations with reference to average shale (Wedepohl, 1971; Through a combination of detailed core description, high-
Taylor and McLennan, 1985) to determine the detrital input, clay resolution chemostratigraphy and petrophysical logs, O’Neal and
mineral variation, maturity etc. Playter et al. (2018) used multiple Sonnenberg (2018) were able to identify lateral discontinuities of
geochemical indicators i.e. mineralogical, clay, provenance and bentonite occurrences, trace element and organic carbon variations
detrital proxies, categorised the Montney Formation into different and distinct changes in sedimentary structures that affect reservoir
chemofacies (n ¼ 13) and identified mineralogical and geochemical properties of the Late Cretaceous Niobrara Formation, Julesberg
variations., The SiO2/Al2O3 ratio is also used as a clay indicator Basin, U.S.A. The role of increasing depth of burial over increasing
(Playter et al., 2018) and analysis of its temporal variability can maturity was demonstrated through geochemical proxies by the
indicate the chemofacies variations (e.g. Playter et al., 2018). In study of Bolandi et al. (2015) who have analyzed 45 cutting samples
addition, there are other indicators of clay, which can be used to from 9 wells located in the Azadegan oilfield Lower Cretaceous
318
Kazhdumi Formation, SW Iran. While documenting the matrix bulk dolomite abundance also exhibit a short-scale correlation length of
rock permeability, with the use of documenting stratigraphic 3.7 m and a long-range oscillatory pattern (hole-effect) at ~ 16 m,
variability of a few selected elemental concentrations and ratios, El both of which are also periodic. Trace elements (Mn, Sr) and
Attar and Pranter (2016) have estimated the relative-rock brittle- permeability exhibit a short-range correlation to 5.8 m, but no
ness. They stated that the relative-rock brittleness estimates from long-range pattern. This indicates that the lateral patterns in
element and TOC data show the stratigraphic variability of alter- dolomite abundance, porosity, permeability, Sr, and Mn contents
nating ductile (TOC rich, Ca and Si/Al poor) and brittle (TOC poor, Ca were not inherited from the limestone precursor and thus un-
and Si/Al rich) intervals for the Niobrara Member, Piceance Basin, equivocally diagenetic in origin. Hasiuk et al. (2016) suggested that
Colorado. Major elements are used to calculate the brittle mineral micron-size pores are common in limestones, and they host sig-
fraction while redox-sensitive trace elements are used as paleo- nificant hydrocarbon reserves in conventional and unconventional
depositional proxies to recognize where organic carbon-rich in- plays represented by all depositional environments and burial
tervals occur as a result of organic matter deposition and preser- depths worldwide. A geochemical study undertaken by these au-
vation. Well performance positively correlates with an increase in thors to investigate a global dataset collected from seven new
brittle minerals and an oxygen-poor (anoxic) paleo-environment. subsurface microporous reservoirs as well as data from 21 previous
Romero-Sarmiento et al. (2017) identified a positive relationship studies revealed that the microcrystals are composed of low-Mg
between quantity of organic matter and permeability and calcite (average 14 mmol/mol, range 1.6e90, Mg/Ca). Microcrystal
concluded that TOC values play the main control on poromechan- Sr/Mg ratios are consistent with abiotic calcite cements, though
ical characteristics. Mathur et al. (2001) stated that distinguishing overall Mg/Ca and Sr/Ca are lower than modern abiotic calcite ce-
low, intermediate and normal-gravity oil-bearing zones, resolving ments reported in the literature. Higher Sr/Ca observed in deposi-
the problem of density-neutron porosity crossover for gas and oil- tional chalks implies a biotic, though probably not aragonitic,
bearing reservoirs are major impediments in characterizing precursor. Most calcite microcrystals have oxygen isotope compo-
hydrocarbon-producing horizons of a reservoir. These authors have sitions that are 0e4‰ more negative, and carbon isotope compo-
demonstrated that through the use of geochemical analyses of sitions just slightly more negative (<1‰), than contemporaneous
sidewall core extracts by thin-layer chromatography with flame abiotic marine calcite.
ionization detection and gas chromatography the parameters Yuan et al. (2019) reviewed feldspar alteration and its geological
needed to identify the nature and composition of the reservoir significance of sedimentary basins from a shallow aquifer to deep
fluids can be precisely estimated and the impediments can be hydrocarbon reservoirs. A verity of controlled mechanisms are
alleviated. Martin et al. (2019) have demonstrated the utility of a involved in alteration feldspars such as surface reaction controlled
combination of immobile elemental concentration and statistical dissolution, preferential leaching-diffusion, diffusion-precipitation,
discrimination to precisely locate and predict micro-fracture zones and interfacial dissolution-reprecipitation, which are mainly
in mudstone reservoirs. Mahmoudi et al. (2017) documented responsible for the dissolution of feldspars. Such processes can
identical geochemical signatures of oil samples from widely generate the secondary porosity and permeability in open
geographically spaced as well as at different depths of oil- geochemical systems at the shallow depth or at a moderate to a
producing wells in the Ghadames Basin, Southern Tunisia and deep depth where faults develop widely. However, under closed
concluded that these oils have single source and the reservoirs are systems at moderate to deep depth, this process may generate
interconnected laterally as well as vertically. On a related context, redistributed secondary porosity which can impact on the rock
Ekpo et al. (2018) used gas chromatography (GC), gas permeability. The authigenic clay minerals formed due to feldspar
chromatography-mass spectrometry (GC-MS) and carbon isotopic dissolution can alter the rock wettability and affect the charge and
data to fingerprint oil samples collected from different wells in the entrapment of hydrocarbon in a reservoir. Besides, alteration of
western offshore Niger Delta of Nigeria in order to check existence feldspar may promote CO2 sequestration by consuming Hþ ions,
of reservoir continuity. generation of HCO3, and water pH buffering in the formation (Yuan
The study of Cantrell et al. (2001) linked the porosity- et al., 2019). Similar studies are essential for better understanding
permeability characteristics of various dolomite textures and and precise characterization of the reservoirs in the sedimentary
their affinity with oxygen isotope values. According to these au- basins.
thors, among the four types of distinct texture-isotope-reservoir
quality zones, documentation of two types namely, a medium to 5.2. Petroleum system and its components
coarsely-crystalline non-fabric preserving dolomite with low oxy-
gen isotopic values and very good reservoir quality and a medium- Baskin et al. (1995) applied oil fingerprinting of sidewall core
crystalline non-fabric preserving dolomite with high oxygen extracts to find oil-saturated sands with topped (C15þ) whole oils
isotope values and very poor reservoir quality are important. and abbreviated hydrocarbons in gas-dominated sands. This
Vandeginste et al. (2014) documented a weak geochemical trend method has also helped re-evaluation of older wells that lack
with more depleted 18O, Fe, and Mn concentrations in the core than modern wireline measurements, but have sidewall or conventional
at the rim of the dolomite bodies of Ediacaran limestones, northern core material available and also in modern wells wherein thin or
Oman and interpreted these to be minor heterogeneities within the low permeability sands that may not yield definitive wireline log
dolomite bodies and thus, variations in reservoir properties. Pet- responses. Obermajer et al. (1998) used biomarker characteristics of
rophysical and geochemical properties of dolomites may exhibit a southwestern Ontario to identify three different oil families and
nested set of lateral patterns, typically at the scales of a few meters further inferred a carbonate/evaporite source rock deposited under
to ~ 20 m. Based on this premise, Budd and Mathias (2015) exam- hypersaline conditions in a strongly reducing environment for the
ined a preserved limestone-to-dolomite reaction front in grain- Silurian oils, and a clastic source formed under dysoxic to anoxic
stones of the Miocene Seroe Domi Formation, Bonaire, Netherlands conditions for the Devonian and Cambro-Ordovician oils.
Antilles. Porosity, permeability, and geochemical (d18O, d13C, Mn, Sr, Geochemical study of oil samples to understand the types and
and Na) analyses were performed on all 287 recovered samples, distributions of effective source rocks were attempted by Guthrie
and 287 thin sections were point-counted for petrographic attri- and Pratt (1995) and Milkov et al. (2019). Evaluation of the
butes. The results indicated that the dolomite abundance and geographic extent of the petroleum systems in the Barents Sea and
porosity contain three scales of lateral variability. Porosity and northern Timan-Pechora Basin through geochemical traits was
319
attempted by He et al. (2012). This study had discriminated five from different source rocks or different organofacies of the same
major source rocks in the Barents Sea and the northern Timan- source rock were recognized using multivariate statistical analysis
Pechora Basin based on taxon-specific, age-related, and source- of source-related biomarker and isotopic ratios for 73 crude oil
related biomarkers and isotope data. Geochemical fingerprinting samples from the Middle Magdalena Valley (MMV), Colombia by
of stray fluids, (i.e., formation water or hydrocarbon occurring at Thompson-Butler et al. (2019). The geochemical fingerprinting has
surface and subsurface away from their points of origin pose permitted Kotarba et al. (2019) to recognize prevalent secondary
considerable risks to exploration as well as public health) using 18O, processes namely biodegradation and occasional water-washing.
2
H, 13C, Sr isotopic signatures are becoming a routine exercise According to Song et al. (2019), the gas chromatography, gas
(Rostron and Akadakskiy, 2014). chromatographyemass spectrometry, and stable carbon isotope
While the traditional geochemical methods such as high- data of hydrocarbons in the Bashituo oil field of the Tarim Basin
performance liquid chromatography, carbon isotope, gas chroma- indicated similar C15þ molecular marker compositions of marine
tography and biomarker analysis are useful in identification of oil organic matter origin for the crude oils in the Devonian and
types, ReeOs geochronology is being applied to fingerprint the oils Carboniferous reservoirs, whereas their light hydrocarbon com-
precisely (Finlay et al., 2011). There are many previous publications positions showed distinct differences. Light hydrocarbon indicators
in this regard. For example, Clark and Philip (1989) stated that suggested a relatively high maturity beyond peak oil generation for
biomarker and geochemical data of crude oils and potential source the late fresh oil, whereas C15þ molecular marker parameters
rocks from the Black Creek Basin in northwestern Alberta indicate a indicated a maturity equivalent to early peak oil generation for the
local source for the oil consisting of bituminous carbonate units in early-charged biodegraded oil. Spaak et al. (2020) conducted a
the Muskeg Formation and bituminous mud-mound and deeper geochemical study using data on aromatic hydrocarbons, saturated
water units in the Lower Keg River Member. Obermajer et al. (1998) biomarker ratios and stable carbon isotopes to establish oil-oil
used open column liquid chromatography, gas chromatography correlations and evaluate potential source rocks within the latest
(GC) and gas chromatography-mass spectrometry (GCMS) tech- Devonianeearliest Carboniferous succession of the onshore Can-
niques for characterizing the studied oil and gas samples from ning Basin, Western Australia. The results demonstrated that the
southwestern Ontario based on variability in gross composition and recently discovered Ungani oilfield located on the southern margin
the gasoline range characteristics into three oil families viz., the of the Fitzroy Trough are similar, but not identical, to the early
Cambro-Ordovician, Silurian and Devonian families. These authors Carboniferous oil family present to the north of the Fitzroy Trough
have also recognized subtle compositional irregularities of Devo- on the Lennard Shelf. Identification of reservoir oilegasewater
nian oils and attributed them to geographical variabilities in the layers is a fundamental task in petroleum exploration and exploi-
maturity and composition of source kerogen. Depending on their tation, but is difficult, especially in cases of complex hydrocarbon
geographical proximity, Devonian oils may be genetically related to migration and accumulation. Wu et al. (2014), attempted allevi-
source rocks deposited in either Michigan or Appalachian basins or ating this difficulty through analyzing organic geochemistry and
both. Based on geochemical characteristics of the rock and oil with which estimating the ratio of mineral grains containing oil
samples of the North Yellow Sea Basin, Ping et al. (2015), inter- inclusions to the total number of mineral grains to find this method
preted derivation of organic matter for the Middle Jurassic black successful.
mudstone source rocks from terrigenous higher plants whereas the
Upper Jurassic source rocks have received mixture of terrigenous 5.3. Origin and migration of hydrocarbon
higher plants and aquatic lower organisms. They have further
constrained on the oil and gas generation potentials of different Generation of porosity in organic matter during oil generation
source rocks of the study area. Geochemical fingerprinting is the was documented in the Upper Cretaceous Tuscaloosa marine shale
only tool of choice when the origin and source rock of oil and gas through an integrated study of log resistivity, Rock-Eval pyrolysis,
are in question, such as the controversy over origin of oil in the Field-emission scanning electron microscopy, petrography, miner-
CretaceouseTertiary reservoirs of northern Iraq, which was disen- alogy and geochemistry by Lu et al. (2015). Occurrence of mixed
tangled finally through the application of a detailed geochemical marine and terrestrial organic matter and it’s over maturity with
study (Diasty et al., 2016), including Rock-Eval pyrolysis, gas reference to oil-gas generation potential were interpreted by Geel
chromatographyemass spectrometry, and carbon isotope analysis et al. (2015) based on geochemistry, TOC and d13C and d15N iso-
conducted on 65 source rock core and cuttings samples from the topic analyses of the shales from the Prince Albert, Whitehill and
Najmah, Chia Gara, and Balambo formations, northern Iraq. Similar Collingham Formations of the Lower Karoo Supergroup in the
source rock identification and stages of hydrocarbon charging were Eastern Cape. Based on a large dataset containing molecular com-
identified by Abbassi et al. (2014) through geochemical methods on positions of thousands of gas samples, CO2 carbon isotope values of
the Jurassic and Cretaceous rocks in the Vulcan Sub-basin, Bona- hundreds of samples, Jin-Xing et al. (1996) were able to identify the
parte Basin, North West Shelf of Australia. occurrences of exclusively organic CO2 in tectonically stable oil and
Huang et al. (2017) analyzed 225 rock samples and 37 oil sam- gas-bearing basins, and significant amounts of inorganic CO2 in
ples from the Beibuwan Basin, South China Sea for geochemistry basins wherein active faults and magmatism and or modern vol-
and organic petrography to evaluate the Eocene lacustrine source canic activity are reported. Though not exactly the same, but a more
rocks for documenting the distribution of different oil families in or less related experiment was conducted by Prinzhofer et al.
the basin. Organic geochemical investigations including TOC, C/N, (2000) who reported gas migration to the Reco^ncavo Basin,
and lipid biomarkers indicate the organic matter in the central Brazil from subsurface-offshore source which was facilitated by
Karoo Basin was primarily of algal origin (Scheffler et al., 2003). He Mata Catu fault. Hu et al. (2020) suggested that internal oil
et al. (2018) utilized geochemical fingerprinting of crude oil migration within shale systems is of significance and indicates the
recovered from Baiyun Sag, South China Sea to constrain on as- retention, expulsion, and accumulation. However, conventional
sessments on maturity of the oil, possible source(s), depositional geochemical proxies to study this internal oil migration are
environments of the source rocks and the rates of organic matter commonly overlapped, and thus the migration is well understood.
input to the depositional setting. Though a plethora of studies are available on geochemical charac-
Six distinct oil families that showed a systematic distribution in teristics of shale gas, studies on the numerical relationship between
terms of basin location and reservoir rock age and which originated the quantity of the gas and the gas geochemistry are rare. Chen
320
et al. (2020) presented a novel study to make reliable estimate of homogenization temperature (Th) and salinity of hydrocarbon-
the same, taking elemental geochemical and isotopic compositions bearing brine inclusions, determined the phase, direction, and
of shale gas samples, and the gas content of the Lower Silurian pathway of natural gas migration to evaluate the migration pro-
Longmaxi marine shale in the Huangjinba area, southern Sichuan cesses and mechanisms of the Jurassic hydrocarbon in western
Basin, China. Abubakar et al. (2020) documented geochemistry of Sichuan. This study demonstrates the utility of geochemical proxies
reservoir core material from Bridport Sandstone and Inferior Oolite, in reservoir characterization. Kotarba et al. (2019) documented the
Wessex Basin, using gas chromatography-mass spectrometry (GC- generation and migration processes as well as the influence of
MS), and found that the oil in the Wessex Basins from a single secondary processes of hydrocarbons accumulated in Lower
source, and those small variations in environmentally sensitive Cretaceous-Oligocene strata of the western part of the Ukrainian
biomarkers are likely due to small differences in maturity or Outer Carpathians. Based on trace elemental and isotopic
depositional conditions during the formation. geochemical characteristics (Yamamoto et al., 2018) the stages of
Peters et al. (2013) performed chemometric analyses of dolomitization and the control of depositional fabric and porosity
geochemical data for 165 crude oil samples from the San Joaquin over intensity of dolomitization were identified, which in turn
Basin to identify 22 oil families within the basin that were gener- affected the later stage oil migration.
ated from four major source rocks viz., the Kreyenhagen Formation,
the Tumey Formation, the Monterey Formation (Buttonwillow 6. Conclusions
depocenter), and the Monterey Formation. These authors have also
identified five oil families that originated from the Kreyenhagen Chemostratigraphic techniques have witnessed a systematic,
Formation, three families from the overlying Tumey Formation, and but rapid development in the use, sophistication and accuracy
fourteen oil families that migrated from the upper and the lower over the past few decades. This paper provides an in-depth re-
Monterey Formation. Based on high-resolution gas chromatog- view of classic as well as most recent publications on this
raphy of the C7 compounds, and compositional differences, Wever growing branch of geosciences.
(2000) proposed a method to characterize hydrocarbons for source The technique has commenced from a humble beginning of
rock discrimination, identification of prevalent evaporative frac- recognizing identical/contrasting geochemical features across
tionation, water washing, and biodegradation. Hydrocarbon major geochronological boundaries. It has evolved into one of
exploration efforts in the Qi-nan Slope belt located in the south- the most indispensable tools in exploration, characterization,
western Qikou Sag in the Bohai Bay Basin suffer from paucity of well development strategies, including continuous, real-time
data and understanding on oil-oil relationship, oil migration geochemical mapping and direction of lateral drilling, and ma-
pathway and source rock type In order to alleviate this lacunae, Zhu chine learning, among other aspects.
et al. (2020) attempted hierarchical cluster analysis of available oil While the advancements in the sophistication of analytical
geochemical data, and integrated them with oil-gas test results techniques and equipments have provided initial impetus to
from major wells on the seismic profiles to model preferential wider application of the chemostratigraphic method, integrated
migration pathways for hydrocarbon accumulation. Ge et al. (2020) analyses of geochemical elemental abundances with other types
documented organic geochemistry of the hydrocarbons of newly of data such as petrography, mineralogy, fossil occurrence and
discovered oil reserves from Halahatang oil field in the northern abundance, geophysical log data, etc., have enhanced the
Tarim Basin. Analysis of coeval aqueous and hydrocarbon-bearing applicability of this method in real-time analysis of reservoir
inclusion data with previously published data on ReeOs age and characteristics, well progress, etc. Future directions may include
reservoir illite KeAr suggested oil belonging to single family, origin application of machine learning concepts and artificial intelli-
of from Paleozoic marine source, migration of oil during middle- gence in chemostratigraphic methods. Already a beginning has
late Permian and fluid trapping temperatures and pressures of been made in this regard.
100e110 C and approximately 39e59 MPa (~5656e8557 psi), Improved understanding of the reservoirs have also been
respectively. This information and methods explain how effectively benefitted from precise interpretation of provenance and tec-
and precisely the geochemical characterization methods serve to tonic setting, enumeration of paleoclimatic models and accurate
the hydrocarbon exploration and production strategies. On the inter-well correlation which in turn are being facilitated through
other hand, based on stable carbon isotope ratios of individual integration of geochemical elemental data with elemental ra-
gasoline range (C5eC10) compounds, Harris et al. (2003) discrimi- tios, stable and radiogenic isotopic compositions, etc. Multivar-
nated generation of six types or families of oil from a common iate statistical analyses of these data have proved to be an
source rock and opined that systematic isotope distributions in indispensable tool for accurate characterization, prediction of
straight chain and branched alkanes can help to delineate a com- applicable analogues and removal of human error or bias.
mon source rock along with the influence of secondary alteration Geochemical fingerprinting of identified source-reservoir-seal
processes such as biodegradation, evaporation, and thermochem- facies, gas and oil families, occurrence and distribution of clay
ical sulfate reduction. These two examples demonstrate the intri- and other mineral barriers, types, modes and processes of
cate and complex nature of hydrocarbon generation, migration and diagenetic events has been a regular application in the explo-
storage that can be untangled only through concerted efforts of ration strategy and also during production stage as the finger
applying techniques and methods as appropriate to individual printing method is being increasingly integrated into real-time
cases. assessment and monitoring. The review has also brought to
Sujuan et al. (2017) used integrated geochemical and isotopic light the efficiency of integrated analyses and applications of
analysis of natural gases, formation waters, authigenic minerals, multiple analytical techniques for precise characterization of the
and fluid inclusions, based on which a set of organic and inorganic reservoirs and to design the exploration/production strategies.
geochemical tracing parameters were delineated. These include
methane/ethane ratio (C1/C2), N2 content, arene/alkane ratio, car-
bon isotope of methane (d13C1), total dissolved solids (TDS) and Conflict of interest statement
chemistry of formation water, oxygen and carbon isotopic compo-
sition of authigenic calcite cement (d18Ocalcite and d13Ccalcite), and Authors declare that there is no conflict of interest whatsoever.
321
Acknowledgements Perspectives from Petrography and Geochemistry. Geological Society of Amer-

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Ramkumar, M., 2004. Dynamics of moderately well mixed tropical estuarine sys- for determining the tectonic depositional environment of ancient sedimentary
tem, Krishna estuary, India: part IV Zones of active exchange of physico- basins. Chem. Geol. 242, 103e125.
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Ramkumar, M., 2014. Characterization of depositional units for stratigraphic cor- Reservoir-Quality Evolution of Incised-Valley Sandstones: Evidence from the
relation, petroleum exploration and reservoir characterization. In: Sinha, S. Abu Madi Gas Reservoirs (Upper Miocene), the Nile Delta Basin, Egypt.
(Ed.), Advances in Petroleum Engineering. Studium Press L.L.C., U.S.A, pp. 1e13. J. Sediment. Res. 75, 572e584.
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chemostratigraphy as a formal stratigraphic method. In: Ramkumar, M. (Ed.), CarboniferousePermian glaciation of Gondwana: Linking polar and equatorial
Chemostratigraphy: Concepts, Techniques and Applications. Elsevier, pp. 1e21. climate evolution by geochemical proxies. Geology 31, 605e608.
https://doi.org/10.1016/B978-0-12-419968-2.00001-7. Scott, R.W., Brett, C.E., Fluegeman, R.H., Pratt, B.R., 2020. North American Com-
Ramkumar, M., Guha, A.K., 2000. Multivariate statistical verification of petrographic mission on Stratigraphic Nomenclature: Note 71 e Application for addition of
and standard microfacies types and lithostratigraphy of Tertiary carbonates of chemostratigraphic units to the North American Stratigraphic Code: A case for
western Kutch, Gujarat, India: implications on global stratigraphic correlation formalizing chemostratigraphic units. Stratigraphy 17, 135e139.
and hydrocarbon exploration. Indian J. Petrol Geol. 9, 52e74. Sechman, H., Dzieniewicz, M., 2007. Influence of soil moisture on the results of
Ramkumar, M., Sathish, G., 2007. Integrated sequence and chemostratigraphic surface geochemical survey applied to petroleum exploration. J. Petrol. Sci. Eng.
modelling: a sure-fire technique for stratigraphic correlation, petroleum 56, 267e282.
exploration and reservoir characterization. In: Rajendran, S., Sechman, H., Izydor, G., Guzy, P., Dzieniewiczz, M., 2015. Surface geochemical
Srinivasamoorty, K., Aravindan, S. (Eds.), Mineral Exploration: Recent Strategies. exploration for hydrocarbons in the area of prospective structures of the Lublin
New India Publishers, New Delhi, pp. 21e40. Trough (Eastern Poland). Mar. Petrol. Geol. 61, 22e38.
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selected carbonate petrographic classifications: implications on applicability of raphy of Equatorial Pacific core V28-238: Oxygen isotope temperatures and ice
classification systems and predictability of petrographic types. Geochemistry volumes on a 105 year and 106 year scale. Quat. Res. 3, 39e55.
62, 145e159. Shalaby, M.R., Jumat, N., Lai, D., Malik, O., 2019. Integrated TOC prediction and
Ramkumar, M., Stuben, D., Berner, Z., 2010. Hierarchical delineation and multivar- source rock characterization using machine learning, well logs and geochemical
iate statistical discrimination of chemozones of the Cauvery Basin, South India: analysis: Case study from the Jurassic source rocks in Shams Field, NW Desert,
Implications on Spatio-temporal scales of stratigraphic correlation. Petrol. Sci. 7, Egypt. J. Petrol. Sci. Eng. 176, 369e380.
435e447. Sial, A.N., Gaucher, C., Ramkumar, M., Fereira, V., 2019. Introduction: Chemo-
Ramkumar, M., Stuben, D., Berner, Z., 2011. BarremianeDanian chemostratigraphic stratigraphy as a formal stratigraphic method. In: Sial, A.N., Gaucher, C.,
sequences of the Cauvery Basin, South India: Implications on scales of strati- Ramkumar, M., Fereira, V. (Eds.), Chemostratigraphy across Major Chronological
graphic correlation. Gondwana Res. 19, 291e309. Boundaries, AGU Geophysical Monograph Series. Wiley, U.S.A, pp. 3e25.
Ramkumar, M., Alberti, M., Fürsich, F.T., 2014. Interpretation of Palaeoclimate, Song, D., Li, M., Shi, S., Han, Z., Meng, B., 2019. Geochemistry and possible origin of
relative sealevel and scale of stratigraphic correlation through Spatio-temporal crude oils from Bashituo oil field, Tarim Basin. AAPG (Am. Assoc. Pet. Geol.) Bull.
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pp. 284e307. Geochemical characteristics of early Carboniferous petroleum systems in
Ramkumar, M., Alberti, M., Fürsich, F.T., 2015. Chemostratigraphy of the Dhosa Western Australia. Mar. Petrol. Geol. 113 https://doi.org/10.1016/
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Bowser and Sustut basins, British Columbia, Canada. Bull. Can. Petrol. Geol. 55, Identification of genetically distinct petroleum tribes in the Middle Magdalena
320e336. Valley, Colombia. AAPG (Am. Assoc. Pet. Geol.) Bull. 103, 3003e3034.
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325
Twaro g, A., Stefaniuk, M., Sechman, H., Guzy, P., 2018. Integrated analysis of geo- 27e49.
electric and surface geochemical data for exploration of subsurface hydrocar- Zhao, Y.Y., Zheng, Y.F., 2013. Geochemical constraints on the origin of post-
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Vandeginste, V., John, C.M., Cosgrove, J.W., Manning, C., 2014. Dimensions, texture Zhu, G., Chen, F., Wang, M., Zhang, Z., Ren, R., Wu, L., 2018. Discovery of the lower
distribution, and geochemical heterogeneities of fractureerelated dolomite Cambrian high-quality source rocks and deep oil and gas exploration potential
geobodies hosted in Ediacaran limestones, northern Oman. AAPG (Am. Assoc. in the Tarim Basin, China. American Association of Petroleum Geologists 102,
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Verma, S.P., Armstrong-Altrin, J.S., 2013. New multi-dimensional diagrams for tec- ment, diagenetic evolution, and their impact on the reservoir quality of the
tonic discrimination of siliciclastic sediments and their application to Precam- carboniferous KT-II carbonate in the Zhanazhol reservoir, Pre-Caspian Basin,
brian basins. Chem. Geol. 355, 117e133. Kazakhstan. Mar. Petrol. Geol. 117 https://doi.org/10.1016/
Verma, S.P., Armstrong-Altrin, J.S., 2016. Geochemical discrimination of siliciclastic j.marpetgeo.2020.104411.
sediments from active and passive margin settings. Sediment. Geol. 332, 1e12. Ziemniak, S.E., Jones, M.E., Combs, K.E.S., 1993. Solubility behaviour of titanium (IV)
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surface geochemical surveys to detect underlying hydrocarbon traps.
J. Geochem. Explor. 66, 457e468.
Vital, H., Stattegger, K., 2000. Major and trace elements of stream sediments from Mu.Ramkumar, is Associate Professor in the Department
the lowermost Amazon River. Chem. Geol. 168, 151e168. of Geology, Periyar University, India. He had completed his
Wedepohl, K.H., 1971. Environmental influences on the chemical composition of B.Sc. (Geology) from the National College, Bharathidasan
shales and clays. In: Ahrens, L.H., Press, F., Runcorn, S.K., Urey, H.C. (Eds.), University, Tiruchirapalli, M.Sc. (Geology) from the Anna-
Physics and Chemistry of the Earth, vol. 8. Pergamon, Oxford, pp. 307e333. malai University, Chidambaram, and Ph.D. (Earth Sciences)
Weibel, R., Johannessen, P.N., Dybkjær, K., Rosenberg, P., Knudsen, C., 2010. Che- from the Bharathidasan University. He was the recipient of
mostratigraphy of upper Jurassic reservoir sandstones, Danish Central Graben, the Best paper award (Geoscience Frontiers, Elsevier,
North Sea. Mar. Petrol. Geol. 27, 1572e1594. 2017), Alexander Von Humboldt Fellowship, and was
Weibel, R., Nielsen, M.T., Therkelsen, J., Jakobsen, F.C., Bjerager, M., Mork, F., Visiting Scientist (thrice), Germany, Visiting Professor
Mathiesen, A., Hovikoski, J., Pedersen, S.S., Johannessen, P.N., Dybkjar, K., 2020. (France), Visiting Scientist (Malaysia) and Young Scientist
Illite distribution and morphology explaining basinal variations in reservoir (twice), Government of India. His recent book on chemo-
properties of Upper Jurassic sandstones, Danish North Sea. Mar. Petrol. Geol. 116 stratigraphy of geochronological boundaries has won the
https://doi.org/10.1016/j.marpetgeo.2020.104290. Prose Award. His research interest is on documenting dy-
Weltje, G.J., Von Eynatten, H., 2004. Quantitative Provenance Analysis of Sediments: namics of spatial-temporal controls of sedimentary sys-
Review and Outlook. Sediment. Geol. 171, 1e11. tems for applications in landscape evolution,
Wesolowski, D.J., 1992. Aluminum speciation and equilibria in aqueous solution: I. environmental modeling, petroleum exploration and geo-
The solubility of gibbsite in the system Na-K-Cl-OH-Al(OH)4 from 0-100 C. archaeology. He is recognized M.Sc. and Ph.D. research su-
Geochem. Cosmochim. Acta 56, 1065e1092. pervisor in the Periyar University, Curtin University, and
Wever, H.E., 2000. Petroleum and Source Rock Characterization Based on C7 Star Universiti Teknologi Petronas. He is also serving as Execu-
Plot Results: Examples from Egypt. AAPG (Am. Assoc. Pet. Geol.) Bull. 84, tive Editor of the Geological Journal (Wiley), Associate Ed-
1041e1054. itor of the Energy Geoscience (Elsevier) and Member of
Wilhelms, A., Rein, E., Zwach, C., Steen, A.S., 2001. Application and implication of Council of Geoscience Frontiers (Elsevier).
horizontal well geochemistry. Petrol. Geosci. 7, 75e79.
Williams, D.F., Thunell, R.C., Tappa, E., Rio, D., Raffi, I., 1988. Chronology of the
Pleistocene oxygen isotope record: 0e1.88 my BP. Palaeogeogr. Palaeoclimatol.
Palaeoecol. 64, 221e240. R. Nagarajan is Professor in the Department of Applied
Winchester, J.A., Max, M.D., 1989. Tectonic setting discrimination in clastic se- Geology, Dean R&D and Director of Curtin Malaysia
quences: an example from the Late Proterozoic Erris Group, NW Ireland. Pre- Research Institute. He had graduated B.Sc. (Geology) from
cambrian Res. 45, 191e201. the VOC College, Tuticorin, M.Sc., (Geology) from the
Worden, R.H., Griffiths, J., Wooldridge, L.J., Utley, J.E.P., Lawan, A.Y., University of Madras and Ph.D., (Geochemistry) from the
Muhammed, D.D., Simon, N., Armitage, P.J., 2020. Chlorite in sandstones. Earth Anna University, Chennai. His research interests include
Sci. Rev. 204 https://doi.org/10.1016/j.earscirev.2020.103105. applications of geochemistry to various evolution of sedi-
Wu, M., Cao, J., Wang, X., Tanag, Y., Xianag, B., Wang, B., 2014. Organic geochemical mentary systems, petroleum geology, environmental geo-
identification of reservoir oilegasewater layers in the Junggar Basin, NW China. sciences and biogeochemistry. He has published over 85
Mar. Petrol. Geol. 57, 594e602. indexed publications (Journal papers, conference pro-
Wüst, R.A.J., Tu, S., Nassichuk, B., Bozarth, T., Tucker, J., Cui, A., 2018. Chemo- ceedings and book chapters). His current research focuses
stratigraphy, petrography, and SEM investigations of the Lower Triassic Mon- on geochemistry of Oligocene to Neogene sedimentary/
tney Formation in Alberta: Implications for a new and revised diagenetic and metasedimentary rocks and Recent sediments of Borneo.
depositional model. Bull. Can. Petrol. Geol. 66, 436e471.
Xie, D., Yao, S., Cao, J., Hu, W., Qin, Y., 2020. Origin of calcite cements and their
impact on reservoir heterogeneity in the Triassic Yanchang Formation, Ordos M. Santosh is Professor at the China University of Geo-
Basin, China: A combined petrological and geochemical study. Mar. Petrol. Geol. sciences Beijing (China), Specially Appointed Foreign
117 https://doi.org/10.1016/j.marpetgeo.2020.104376. Expert of China, Professor at the University of Adelaide,
Xin Hui, P., Ramkumar, M., Nagarajan, R., Mathew, M.J., Ng, T.F., 2020. Episodic Australia and Emeritus Professor at the Faculty of Science,
dolomitization of Paleozoic limestones in the Kinta Valley, Malaysia: Implica- Kochi University, Japan. PhD (Cochin University of Science
tions on porosity evolution and reservoir properties. Energy Geoscience. and Technology, India), D.Sc. (Osaka City University, Japan)
https://doi.org/10.1016/j.engeos. 2020.11.003. and D.Sc. (University of Pretoria, South Africa). He is the
Yamamoto, K., Ottinger, G., Al Zinati, O., Takayanagi, H., Yamamoto, K., Iryu, Y., 2018. Founding Editor of Gondwana Research as well as the
Geochemical, petrographical, and petrophysical evaluations of a heterogeneous, Editorial Advisor of Geoscience Frontiers. Research fields
stratiform dolomite from a Barremian oil field, offshore Abu Dhabi (United Arab include petrology, fluid inclusions, geochemistry,
Emirates). AAPG (Am. Assoc. Pet. Geol.) Bull. 102, 129e152. geochronology, metallogeny and supercontinent tectonics.
Yuan, G., Cao, Y., Schulz, H.-M., Hao, F., Gluyas, J., Liu, K., Yang, T., Wang, Y., Xi, K., Published over 1500 research papers, edited several
Li, F., 2019. A review of feldspar alteration and its geological significance in memoir volumes and journal special issues, and co-author
sedimentary basins: From shallow aquifers to deep hydrocarbon reservoirs. of the book ‘Continents and Supercontinents’ (Oxford Uni-
Earth Sci. Rev. 191, 114e140. versity Press, 2004). Recipient of National Mineral Award,
Zhang, F., Lenton, T.M., del Rey, A., Romaniello, S.J., Chen, X., Planavsky, N.J., Outstanding Geologist Award, Thomson Reuters 2012
Clarkson, M.O., Dahl, T.W., Lau, K.V., Wang, W., Li, Z., Zhao, M., Isson, T., Research Front Award, Thomson Reuters/Clarivate High
Algeo, T.J., Anbar, A.D., 2020. Uranium isotopes in marine carbonates as a global Cited Researcher recognition during the last five years
ocean paleoredox proxy: A critical review. Geochem. Cosmochim. Acta 287, and the top most cited Researcher for the year 2019.
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Contents lists available at ScienceDirect

Advances in sediment geochemistry and chemostratigraphy for

1. Introduction environments of deposition and diagenesis (Berger and Vincent,

Acknowledgements Perspectives from Petrography and Geochemistry. Geological Society of Amer-

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