BIOMARKER ANALYSIS OF COAL FOR PALEO-

VEGETATION
AND PALEOCLIMATE RECONSTRUCTION IN HANGU
FORMATION

Submitted by

Syed Fawad Hussain

Thesis Submitted to the National Center of Excellence in Geology,

University of Peshawar for Partial Fulfillment of Requirements for the Degree of
M.S. in Geology

NATIONAL CENTER OF EXCELLENCE IN GEOLOGY,

UNIVERSITY OF PESHAWAR Session (2021-22)

 BIOMARKER ANALYSIS OF COAL FOR PALEO-
VEGETATION
AND PALEOCLIMATE RECONSTRUCTION IN HANGU
FORMATION

Submitted by

Syed Fawad Hussain

Submitted to

Dr Samina Siddiqui

Thesis Submitted to the National Center of Excellence in Geology,

University of Peshawar for Partial Fulfillment of Requirements for the Degree of
M.S. in Geology

NATIONAL CENTER OF EXCELLENCE IN GEOLOGY,

UNIVERSITY OF PESHAWAR Session (2021-22)

 DEDICATION

To my beloved father for the understanding and

Encouragement provided throughout my life

&

To my respected supervisor for teaching me

That I should never surrender

i
 ACKNOWLEDGMENTS

I am highly thankful to Allah Almighty, the Merciful and the Beneficent, who

gave me health, thoughts and co-operative people to enable me achieveto achieve this

goal.

Deepest appreciation goes to Prof Dr Samina Siddiqui, supervisor of my

thesis, without whose consistent help, completion this project would not have been

possible. Her generosity, demonstrative guiding, compassionate attitude and

encouraging nature will always be appreciated.

I am also highly obliged to Dr. Samina Jahandad, my co-supervisor, for his

useful suggestions and assistance regarding the geochemical and Biomarkers studies

and tests of coal samples.

Heartfelt thanks are also extended to Dr. Saeed Abbas, Chief I/C (G&R Labs)

Chemist of Oil and Gas Development Company, Islamabad (OGDCL) for his help in

arrangements for mechanical tests of studied rocks.

My family members, especially my mother, also deserve deepest regards and

special thanks for their moral and financial support throughout my educational carrier,

without which I might not have been able to achieve my goals. May Allah sanctify

them all.

ii
Syed Fawad Hussain

LIST OF FIGURES

Figure No. Title Page No.

Figure 2.1 Showing Regional Tectonics of Pakistan ............................................. 8

Figure 2.2 Image showing the study area in the tectonic map of Pakistan ............ 12

Figure 3.1 Distribution of Coal mines in Pakistan (adapted from Warwick and
Wardlaw, 2003), some new coal field sectors are also
included……………..14

Figure 3.2 Geological Map of the Study area, showing lower Orakzai Agency

Coal deposits. (Mohammad et al., 1993) ............................................. 15

Figure 3.3 Accessibility map of the study area through Google maps................. 16

Figure 3.4 Examining coal mining process at site and collecting rock sample at

site mine ............................................................................................. 17

Figure 3.5 Collecting fresh coal and coal mine water samples from site.............. 17

Figure 3.6 Field photograph showing the Hangu Formation ................................. 18

Figure 3.7 Flow Chart of Methodology of Biomarker Analysis of Coal Sample. 21

Figure 3.8 Methodology used for Biomarker Analysis ........................................ 27

Figure 4.3 GC-FID Chromatogram of Coal Sample (Px-19815).......................... 37

Figure 4.4 M/z191 GCMS Chromatogram of Coal Sample (Px-19815).............. 38

Figure 4.5 M/z217 GMS Chromatogram of Coal Sample (Px-19815)................. 39

Figure 4.6 M/z218 GMS Chromatogram of Coal Sample (Px-19815)................. 39

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Figure 4.7 GC-FID Chromatogram of Mine Water Sample (Pw-19817) ............. 40

Figure 4.8 m/z 191 GCMS Chromatograms of Mine Water Sample

(Pw-19817) .......................................................................................... 42

Figure 4.9 m/z 217 GCMS Chromatograms of Mine Water Samples

(Pw-19817) .......................................................................................... 42

Figure 4.10 m/z 218 GCMS Chromatograms of Mine Water Sample

(Pw-19817) .......................................................................................... 43

Figure 4.11 m/z178, 192,184 (Phenanthrene, Methyl Phenanthrenes and

Dibenzothiophene) GMS Chromatogram of Coal Sample (Px-19815) 44

Figure 4.12 m/z198 (Methyl Dibenzothiophene) GMS Chromatogram of Coal

Sample (Px-19815) .............................................................................. 45

Figure 4.13 m/z128, 142,154 (Naphthalene, Methyl Naphthalene and Dimethyl ...

Naphthalene) GMS Chromatogram of Coal Sample (Px-19815) ....... 45

Figure 4.14 m/z170, 184 (Trimethyl Naphthalene and Dimethyl Dibenzothiophenes)

GMS Chromatogram of Coal Sample (Px-19815) .............................. 46

Figure 4.15 m/z TIC, 178,192,184 GMS Chromatogram of Coal Sample

(Pw-19817) .......................................................................................... 46

Figure 4.16 Figure showing collinite vein in coal sample...................................... 48

Figure 4.17 Figure showing semifusinite veins in coal sample .............................. 49

Figure 4.18 Figure showing inertodetrinite mineral in Coal sample ...................... 49

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Figure 4.19 Figure showing Funginite mineral in coal sample ..............................

50

LIST OF TABLES

Table No. Title Page No.

Table 3.1 The studied coal samples and sampling coordinates in the underground
coal mines (Carbonaceous)................................................................. 18
Showing the percentage values of TOC in Hangu Coal ......................
Table 4.2
33
Rock Eval pyrolysis and TOC test report detailed values ...................
Table 4.3
34

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Table 4.4 Biomarker Results of Saturated Hydrocarbons of NCEG Samples
(Px-19815 and Pw-19817) .................................................................. 36

Table 4.5 Results of Aromatic Hydrocarbons..................................................... 43

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 Table of Contents

DEDICATION............................................................................................................ II
ACKNOWLEDGMENTS..........................................................................................
II
LIST OF FIGURES................................................................................................... II
LIST OF TABLES..................................................................................................... V
ABSTRACT...............................................................................................................
VI
CHAPTER 1...................................................................................................................
INTRODUCTION.........................................................................................................
1.1 GENERAL STATEMENT............................................................................................1
1.2 PREVIOUS WORK....................................................................................................4
1.3 THE PRESENT INVESTIGATIONS.............................................................................5
1.5 AIM AND OBJECTIVES...........................................................................................6
1.6 SIGNIFICANCE OF RESEARCH WORK.....................................................................7
CHAPTER 2...................................................................................................................
REGIONAL TECTONICS...........................................................................................
2.1 OVERVIEW............................................................................................................8
2.2 KARAKORAM BLOCK.............................................................................................9
2.3 KOHISTAN ISLAND ARC.........................................................................................9
2.4 NORTH WEST DEFORMED FOLD-THRUST BELT....................................................10
2.5 SOUTHERN DEFORMED FOLD-THRUST BELT.......................................................11
2.6 POTWAR PLATEAU...............................................................................................11
2.7 KOHAT BASIN.......................................................................................................11
CHAPTER 3.................................................................................................................13
MATERIAL AND METHODOLOGY......................................................................13
3.1 STUDY AREA.........................................................................................................13
3.2 AIM AND OBJECTIVES...........................................................................................19
3.3 METHODOLOGY ADOPTED...................................................................................19
3.4 SAMPLE COLLECTION...........................................................................................21
3.5 LABORATORY ANALYSIS......................................................................................21
3.6 TOTAL ORGANIC CARBON...................................................................................22
3.7 ROCK EVAL PYROLYSIS.......................................................................................23
3.8 BIOMARKERS.......................................................................................................25
3.9 SOME INDICES CALCULATED FROM GCMS CHROMATOGRAM..............................27
3.9.1 Carbon preference index (CPI)....................................................................29
3.9.2 Average Chain Length (ACL).......................................................................29
3.9.3 Terrestrial to aquatic ratio (TAR)................................................................29
3.9.4 Odd Even Preference (OEP)........................................................................30

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 3.9.5 Pristane/Phytane Ratio................................................................................30
3.9.6 Gymnosperms/angiosperms parameters......................................................30
3.10 ORGANIC PETROGRAPHY...................................................................................31
3.10.1 Sample preparation...................................................................................31
3.10.2 Vitrinite Reflectance Measurement.............................................................32
CHAPTER 4.................................................................................................................33
RESULTS AND DISCUSSION..................................................................................33
4.1 GEOCHEMICAL ANALYSIS....................................................................................33
4.1.1 Total Organic Carbon and Rock Eval Analysis...........................................33
4.2 BIOMARKER ANALYSIS........................................................................................35
4.2.2 Biomarker Results........................................................................................35
4.3 SATURATED HYDROCARBONS ANALYSIS............................................................36
4.3.1 Biomarker Analysis of Coal Sample (Px-19815).........................................36
4.4 Biomarker Analysis of Mine Water Samples (Pw-19817)..........................39
4.5 Aromatic Hydrocarbon Analysis.................................................................43
4.5.1 Aromatic Hydrocarbon Analysis of Coal Sample (Px-19815).................44
4.5.2 Aromatic Hydrocarbon Analysis of Coal Sample (Pw-19817)...............46
4.3 ORGANIC PETROGRAPHY ANALYSIS.....................................................................47
4.3.1 Maceral study of Coal sample......................................................................47
4.3.1.1 Sample details........................................................................................47
CHAPTER 5…………………………………………………………………………..
CONCLUSION……………………………………………………………………..
REFERENCES:...........................................................................................................51

viii
 ABSTRACT

Information regarding the identification of paleo-vegetation biomarkers within the coal-

bearing Hangu Formation of the Paleocene era in Lower Orakzai, for the purpose of
reconstructing paleo-climate changes over geological timeframes, has been scarce. In this
study, we examined a 5-meter-thick coal-bearing section of the Paleocene Hangu Formation in
Lower Orakzai. Our objective was to reconstruct past climate conditions using aromatic
biomarkers as paleo-vegetative proxies. Additionally, we sought to determine the
environmental settings, thermal maturity, macerals, kerogen type, and source rock properties
through analyses such as Total Organic Carbon (TOC), Rock-Eval pyrolysis, organic
petrography, and various biomarker ratios. Both saturated and aromatic fractions were
quantitatively and qualitatively analyzed using Gas Chromatography-Mass Spectrometry (GC-
MS) and Gas Chromatography with Flame Ionization Detection (GC-FID) chromatography.
The coal sample's geochemical analysis SEM has given us a complete understanding of its
constituent makeup. As the dominating element, carbon emphasizes the coal's carbon-rich
nature. The likelihood of chemical activities connected to burning is suggested by the
comparatively high oxygen level. Iron and sulfur are also present, which emphasizes the need
to address any potential environmental and combustion-related hazards connected to these
specific materials.
Our findings indicated that the TOC content, being less than 1%, suggests that the coal is
derived from carbonaceous shale and is of low rank. Rock Eval data revealed S1, S2, and S3
values ranging from 0.4 to 0.24 mg/g, Tmax values spanning from -37 to 506°C, while PC and
RC varied from 0.01% to 0.2% and 0.05% to 0.28%, respectively. The source rock exhibited
PI, HI, and OI values within the ranges of 0.26-1, 0-40, and 0-400, respectively. Aromatic
biomarker analysis via GC-MS and GC-FID indicated significant biodegradation of steranes,
except for C29. Angiosperm input was observed in the organic matter, whereas steranes were
mostly absent. Petrographic analysis confirmed the presence of conspicuous, coarse-grained
organic matter, featuring vitrodertrinite and collinite, both crucial components of the vitrinite
maceral group. In conclusion, this study revealed that the coal had a low rank (lignite) but was
thermally mature, suggesting it may not be suitable for commercial electricity generation.
Understanding past vegetation and climate dynamics has implications for understanding how
ecosystems respond to environmental changes. This knowledge can be valuable for predicting
future environmental shifts.

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 CHAPTER 1

INTRODUCTION

1.1 Background

Important indications are biomarkers, which are complex chemical byproducts of the
biochemistry of once-living organisms. Coal, crude oil, and petroleum extracts extracted
from source rocks can all include these indicators. They provide useful information about a
number of things, including the amount of organic material in the source rock, the
environmental conditions during its formation and subsequent burial (diagenesis), the degree
of coal's heat exposure and maturation, the degree of biodegradation, and specifics about the
mineral composition (lithology) and age of the source rock.

Coals are formed from the decay of terrestrial trees and other vegetation trapped in
swamps over millions of years ago under high temperature and pressure. Coal
composition dependdepends on the presence of organic and inorganic compounds
released from the decay of terrestrial organic residues. Organic residues are composed
of heterogeneousa heterogeneous mixture of organic and inorganic compounds.
Organic compounds are commonly known as biomarkers further categorized in
saturate, aromatic, NSO compounds, asphaltenes, resins, waxes, carbohydrates, and
lignin (Miryam et al, 2020; Cheng et al., 2022). In-organic compounds are mainly trace
and major elements and rare earth elements (REE) present at various concentrations in
coal (Popov et al., 2022).

The importance of biomarker chemicals in reconstructing paleoclimate conditions is

highlighted by recent developments in the study of macromolecular organic matter
(CastaEda⠀and⠀Schouten. 2011). The carbon skeletal structures of biomarker
compounds continue to be surprisingly robust despite the organic matter being
susceptible to numerous modifications after its deposition, leading to changes in
carbon-hydrogen (C-H) bonds and functional groups in more recent advances. These
materials therefore persist for lengthy geological periods in the sedimentary record

1
 (Peterson et al., 2007). Inorganic geochemical parameters also provide important
insights aboutinto past environmental changes. As a result, many methods are used to
differentiate previous sedimentary ecosystems. One important factor that can provide
information on geodynamic and paleoclimate conditions is elemental composition (Fu
et al., 2018).⠀). ⠀

Coals biomarkers provide a deep insight about the climatic changes occurred in the
geological history (Strobl et al., 2014; Dai et al., 2020; Wang et al., 2022). To
reconstruct paleo climatic changes, vegetation type biomarkers are used as a proxy.

Saturate biomarkers or n-alkanes predominate coals. The higher carbon nalkanes (nC21
to nC37) of coals indicate that the source is organic matter derived from the decay of
terrestrial plantsplants, mainly angiosperms. The greater content of higher odd carbon
chain or straight carbon chain (nC25 --- nC35) indicates that these straight carbon chains
were originated from the decay of leaf wax of vascular plant. Whereas the greater
content of middle odd number nC19, nC21, nC23 and nC25 in coals samples show that
these straight carbon chains were derived from submerged and floating aquatic plants
under anoxic conditions in the geological past (Ficken et al., 2000). Odd straight carbon
chain from nC15, to nC19 usually indicate that the source was marine plants more likely
algaealgae, and the depositional environment was anoxic (Diefendorf et al., 2011).
Abundance of odd to even numbers of n-alkanes indicate that such odd straight chain
carbon in plant is either terrestrial or marine origin. Plants leaf wax is dominated by
odd carbon chain n-alkanes and indicate the type of vegetation of such high odd chain
carbon n-alkanes such as nC31 is derived from herbaceous plants whereas nC29 and nC27
at greater concentration indicate that these n-alkanes were derived from woody plants
or terrestrial plants (Simoneit.,1986 and Simoneit et al., 1989). Whereas the short
oddshort, odd carbon chain nC23 and nC25 shows that they are derived from Sphagnum
mosses in marshes (Van Beilen, 2003; Loez et al., 2013).

This preference of odd to even numbers of n-alkanes by plants is calculated

from carbon preference index (CPI), using a formula as described by Allan and
Douglas (1977).

CPI = (n-C 11 to n-C 27) / (n-C 10 to n-C 26).

2
Similar to CPI, the ratio of terrestrial to aquatic n-alkanes (nC27, nC29, nC31 to nC15,
nC17, and nC19) will be utilized to show the evolution of vegetation types during coals'
geological history. (Meyers, 1997; Peters et al., 2005; Jones and Hajek, 2007).

Gas chromatography mass spectrometry, more especially the Perkin Elmer 600 Clarus
Series, is used to analyze the saturated section of coal in order to find biomarkers. By
comparing the peak area of the sample to a standard, one can as certain the quantitative
and qualitative analysis of each carbon chain peak shown in the GC chromatogram. The
standard whereas mass to charge ratio (m/z) was used to identify the number of carbon
chain according to their emergence time. Straight chain carbon or n-alkanes mass to
charge m/z ratio is 57. This ratio indicates whether the carbon chains in organic matter
have a connection to terrestrial or marine plants as their source (Peters et al., 2005). In
order to evaluate the redox conditions of the deposition environment, the mass-to-
charge ratio (m/z) of 85 (m/z 85) is specifically used. For evaluating thermal maturity,
triterpanes and hopanes are examined at m/z 191, while steranes are studied at m/z
217(Powell and McKirdy et al., 1973). Furthermore, the m/z 218 is used to determine
the origin of the organic matter within steranes (Didyk et al., 1978). Non-steroid
pentacyclic triterpenoids are synthesized by C3 type-angiosperms vegetation and
indicate wet or humid climate whereas C4 type vegetation gymnosperms (conifers)
biomarkers mainly tricyclic diterpenoids indicate dry or warm climate (Diefendorf et
al., 2012). LithologicalThe lithological difference in the distribution of C3 type
angiosperms vegetation vs C4 type vegetation gymnosperms (conifers) in coal seams
may indicates the paleo-climate changes occurred in the geological past. Their
distribution is also influenced by temperature and precipitation (Soma et al. 1996;
Hautevelle et al. 2006; Xu et al. 2019).

N-C17/Pristane and nC18/Phytane ratio in coal will indicate the organic matter
composition as Kerogen Type I, II or III.

Paleo-vegetation type (C3/C4) aromatic biomarkers (di- to tri-terpenoid ratios)

in coal are used for reconstruction of floral and paleoclimatic changes occurred over a
geological timescale (Diefendorf 2014; Kirkels, 2022). Paleo-vegetation type
biomarkers such as non-steroid pentacyclic triterpenoids are synthesized by C3 type
angiosperms vegetation and indicate wet or humid climate whereas C4 type vegetation
3
 gymnosperms (conifers) biomarkers mainly tricyclic diterpenoids indicate dry or warm
climate (Erdtman, 1963; Pereira et al., 2009; Diefendorf, 2012; Song et al., 2022).

1.2 Literature Review

Abdin et al. (2022) found that the dominant biomarkers in Mukah coals of
Malaysia were n-alkane, pristane/phytane (1.0/3.67) derived from higher plants
deposited under oxic to suboxic environment under fresh water to water-saturated
environment. They reported that the presence of dipterans biomarkers in the coal
indicated that the paleo-vegetation type was angiosperms (C3 paleo-vegetation type).
Paleo-vegetation type C3 was further confirmed by the higher concentration of
tetracyclic terpanes in the coal. They concluded that the coal was formed as a result of
fluctuating water tables under increasingly humid climate changes during the Neogene.

Table 1.0 Showing Aromatic hydrocarbons

Compounds Carbon Sedimentation type Organic matter source Dominant

chain alkanes

n-alkanes C0-C21 Marine/Lacustrine Algal (C3)-lipids and C15, C17

nitrogenous compounds and C19

C25-C37 Terrestrial plant Plant wax (C4)- C27, C29

cellulose and lignin and C31

C12-C24 Marine/Lacustrine Bacteria

Carbonates/evaporites C20-C24

Acyclic C19,C19, Marine Prokaryotes/chlorophyll

isoprenoids C20 phytyl side-chain
Pristane, Phytane and/or α-tocopherol

4
 (vitamin E)

Zhang et al. (2022) used biomarkers as proxies to reconstruct the paleo-climate

change of Zhangjialiang coal from the Middle Jurassic Yan'an Formation in the Ordos
Basin of China. They reported presence of a higher concentration of nalkanes, a
pristane/phytane ratio (2.03-10.6) and nC29 versus nC27 steranes supported the claim
that the depositional environment was oxidized freshwater and that the organic matter
was predominantly derived from C4 vegetation type of terrestrial environment.
Biomarkers of paleo-vegetation type were labdan, norpimarane, isopimaran,
phyllocladane indicating that C4 conifers (gymnosperm) was the plant.

Numerous previous information was focused on the coal lithology and

stratigraphy and suitability of the coal deposits sites to be explore (Landis et al., 1973;
Warwick, 1990; Thomas et al., 1993; Ahmad and Zaigham, 1993; Rehman et al., 2016;
Sajid et al., 2022), geochemical characteristics, organic petrography and depositional
environment (Ahmed et al., 2015), palynofacies and age of the coal bearing seams
(Faiqa, 2001; Iram, 2001),

1.3 The Present investigations

Nonetheless information about identification of various paleo-vegetation

biomarkers in coals bearing succession to reconstruct the paleo-climate change over a
geological timescale is in scarcity. Numerous terrestrial plants are intimately related to
the temperature and moisture levels of their particular environments, therefore changes
in plant life are commonly attributed to changes in climate (Takahara et al., 2010; Lim
et al., 2013; Popv et al., 2022). Research has repeatedly shown a connection between
changes in vegetation and changes in local climatic patterns (Litwin et al., 2013). The
intricate relationship between climate and vegetation changes has the potential to have
an impact on human existence on a global scale (Alley et al., 2003). More specifically,
utilizing organic proxies like n-alkanes across different habitats, historical variations in
vegetation have been detected and examined as markers of past climatic oscillations
(Yamamoto et al., 2010; Zhang et al., 2022, 2023; Zech et al., 2012).This). This study
5
 will be the first to use paleo-vegetation biomarkers as proxies to reconstruct the
paleoclimate of coalbeds over geological timescales. Coals are among the finest grained
sediments deposited in continental environments and are sensitive natural archives of
high-resolution paleo climatic and paleo environmental information (Meng et al., 2012,
2013, Song et al., 2020).

Coal biomarkers are the indicator of past and present coal deposition,
anddeposition and are used to help identify and characterize coal deposits. These
biomarkers can include various types of organic molecules that are specific to the type
of coal being studied. They can be used for a variety of applications, ranging from
exploring potential coal reservereserves, to assessing the environmentenvironmental
impact of coal mining and combustion. AdditionallyAdditionally, coal biomarkers can
provide insight into the origin of coal and the geological process that have influenced
its formation over time.

1.5 Aim and Objectives

The aim of this study will be to reconstruct paleo-climatic changes using

paleovegetation biomarkers (C3-C4 types) and organic petrography as a proxy for the
coal of paleEocene age-Hangu Formation. To achieve this aim followingthe following
objectives will be carried out.
• To identify the geochemical parameter, total organic carbon and vegetation type
biomarkers in coals of Hangu formation of Eocene age.
• To reconstruct the paleo-climatic changes using n-alkanes, pristane/phytane, and
diterpenoids and triterpenoids biomarkers ratio as a proxy.
• To conduct organic petrography of coal samples collected from study area.

1.6 Significance of Research Work

This study will provide an insight to reconstruct the paleo climatic changes occurred underneath the
surface during coal formation at a range of geological timescale. Vegetation type biomarkers are used
as a proxy for better understanding of the paleo environment and paleoclimate underneath the earth
surface. Recent advancements in the analysis of large organic molecules underscore the
significance of biomarker compounds in the reconstruction of paleoclimate conditions.

6
(Castañeda and Schouten, 2011). For a better understanding of how ecosystems react to
environmental changes, it is important to study previous vegetation and climate dynamics.
This information can be useful for forecasting upcoming environmental change

7
 CHAPTER 2

REGIONAL TECTONICS

2.1 Overview

The striking Himalaya Mountains is the result of an active continent-continent

collision of Indian and Eurasian plates. Pakistan lies on the prominent seismic belt and
is an aggregation of various plates. The Himalayan ranges are composed of amalgam of
various rocks of the Indian and Eurasian plates, squeezing the Kohistan islandKohistan
Island arc.

It is believed that Indian plate departed from Gondwana Continent around 120
million years ago, (Johnson et al., 1976) and is thought to have moved northward more
than 4000 km, collided in Paleogene, closing the Tethys (Molnar and Taponnier, 1975)
((Michae G. Petterson and Treloar, 2004).

0
 Figure 2.1 Showing Study area in Regional Tectonics map of Pakistan, adopted
after Kazmi and Rana (1982)

Thus, two major sutures formed, one from the closure of Tethys and another
from formation of KIA, Shyok suture in the north (MKT) and Indus suture (MMT) in
the south. Also, two other fault system i.e. MBT and Trans Indus Ranges thrust have
emerged in the aftermath of this collision and subdivided the Himalayas into five
lithotectonic terrains, each one has typical stratigraphy and physiography.

The Karakorum block, the Kohistan islandKohistan Island arc, the northern
deformed fold-thrust belt, the southern deformed fold-thrust belt, and the Punjab fore
deep make up the geological zones, which run from the northernmost region to the
southernmost region.

2.2 Karakoram Block

Karakoram block, also called as Asian plate sequence lies in the north of mainmain.

1
 Karakoram thrust and contains Pre-Ordovician crystalline basement. It has an area of
70 to 120 km wide and 1400 km long. Both Kohistan and Karakoram are believed to be
intruded by early subduction related to 102-95 million year (M. P. Searle and R.
Tirrule, 1991). This particular block was joined to Eurasia as a byproduct of the
Cimmerian amalgamations of Gondwanaland. Sedimentary and igneous rock
formations that have undergone extensive alteration can be found throughout this block.
The Main Karakorum thrust, which was formed during the Cretaceous period
(Tahirkheli, 1982) (Coward et al, 1986), serves as the main border to the south of the
Karakorum block. The South Pamir fault separates it from the Southern Pamir block to
the north (A Desio, 1979).

2.3 Kohistan Island ARC

Kohistan island arc is one of the younger crusts resulting by magmatism due to
interoceanic convergent margin in the Neo-Tethys Ocean (Jean Pierre Bard, 1983)
(Tahirkheli R., 1979).

Kohistan island arc has been sandwiched between Indian and Eurasian plateplate.

(Tahirkheli R., 1979) (Chris T. Klootwijk Jeff S. Gee John W. Peirce Guy M. Smith
Phil L. McFadden, 1992) (Rehman et al, 2011).

This arc, which is oriented from east to west, is made up of a variety of secondary
sedimentary, volcanic, and plutonic rock formations that have undergone various degrees
of metamorphism and deformation. The Nanga Parbat Harmosh massif, which spans in a
north-south direction and separates the island arc into the Kohistan and Ladakh arcs, is a
notable structure that divides this island arc into two pieces(pieces (Seeber. L. &
Armbruster, 1979). Toward the north of the arc lies MKT and in south there is MMT.

2.4 North West Deformed Fold-Thrust Belt

This belt covers an area which is 250km wide and about 560 km long, this belt
lies to the south of MMT and make a curve shape geometry. The rocks are highly
deformed including sedimentary, metasedimentary and igneous rocks. The area of this

2
belt is from Pak-Afghan border in the proximity of Parachinar up to Kashmir basin. The
territory in between MMT and SRT/MFT comes in North WestNorthwest deformed
fold and
thrust belt.

Mountain ranges of southern Kohistan, Nanga Parbat, swat Hazara, Margalla

hills, Kalachitta, Kohat, Sufaid koh, Salt range and Trans Indus ranges occur in this
belt.

The Northwestern Himalayan sequence is divided into two well identifiable regions by
the Panjal-Khairabad push. The deformed southern zone is one of these regions; it is
also known as the external or foreland zone. The hinterland zone is the other, and it is
characterized by processes of metamorphism and deformation.(deformation. (Dieptro et
al 1996, Pivinik et al 1996).

3
2.5 Southern Deformed Fold-Thrust Belt

The Himalayan mountainThe Himalayan Mountain range is encircled by the southern

fold and thrust band, which stretches from the Ganga delta in India to the South
Waziristan agency in Pakistan. This belt can be further separated into the Potwar Plateau
to the east of the Indus River and the Kohat basin to the west of the same river within the
Trans Indus mountains, which are two separate tectonic regions.

2.6 Potwar Plateau

The Indus River to the west, the Jhelum River to the east, the Kalachitta-Margalla hill
ranges to the north, and the Salt Range to the south all serve as physical boundaries for
the Potwar Plateau. Siwalik sediments make up the majority of this plateau's surface, with
limestone and Eocene shales sprinkled here and there. The North Potwar Deformed Zone
(NDPZ), in the north of the plateau, exhibits a greater degree of geological deformation.

2.7 Kohat Basin

Sedimentary rock deposits from the Eocene and subsequent periods can be
found in the Kohat basin. It is located somewhat away from the collision zone within
the southern fold and thrust belt. Between its northern and southern sections, there are
different structural characteristics. We see tightly folded formations, mostly overturned
folds, and strongly thrust fault systems in the north. In contrast, the southern portion of
the basin has north-south inclined reverse faults and east-west trending folds. In certain
places, lower Eocene strata have also been forced over the Miocene molasses. (Pivniks,
1993).

Surghar Ranges is the south-east frontier of the basin and downward south the
divide line can be drawn with Banu unreformed basin. To the north, the plateau is
surrounded by main boundary thrust (MBT).

4
Figure 2.2 Image showing the study area in the tectonic map of Pakistan
(google.com)

5
 CHAPTER 3

MATERIALS AND METHODS

3.1 Study area

CoalThe coal assets of Khyber Pakhtunkhwa and FATA with new coalfields are shown
in Figure 3.1. The Old Paleocene Hangu Formation, which can be found in places like
Karak, Hangu-Orakzai, and Cherat, is a part of these coalfields. Notably, Gula Khel is a
prime illustration of how the Makerwal (Surhar Coalfields) are subsurfacely continued in
the Karak Coalfields. The Khyber Pakhtunkhwa (KPK) coalfields are proven in table 1
The KPK coalfields host the Old Paleocene Hangu Formation in Karak, Hangu-Orakzai
and Cherat (Ahmed et al., 1986, Warwick et al., 1995, Malkani 2012). The Karak
Coalfields are a subsurface extension of Makerwal (Surhar Coalfields). Gula Khel is one
such example. A new addition is the Bagnotar-Kala Pani coal deposits around
Abbottabad (Hazara).

Hangu Coalfields: Hangu Coalfields are located in Kohat and Hangu Districts and
Orakzai Tribal Corporation. Most of the mines are in tribal organizationorganizations
while some are in other populated areas. Hangu is connected to Peshawar via Kohat and
Dara Adam Khel. The Hangu Formation is predominantly made up of well-consolidated,
reddish-brown, terrestrial sandstones that have undergone bioturbation. These sandstones
are interspersed with carbonaceous clays, limestone deposits, coal seams, and bluish-
gray shale. According to appearances, clay and coal are frequently found together. The
clay layer is thickest (8–10 meters) and coal deposits are thicker than 1 meter in places
like Darwazai and Dauli. In contrast, the southern part of the region has significantly
thinner layers of both clay and coal. Similarly, clays and coal are absent in the south of
Uch Bazar, indicating that the Kasha and Shahu areas became the southern limit of the
swamp, while the eastern limit seems to be around Kachai .Due to the existence of a
thrust fault, the southern boundary is not clearly defined, and our knowledge of the
western boundary is frequently lacking. A stagnant or paralyzed environment is also
suggested by allusions to coal at the Toravai site, which is characterized by high amounts
of ash and surplus sulfur. It denotes an environment with too much sulfur and ash, which
6
is paralyzing. When compared to the northern member, which has a lower and less
consistent bituminous rank, the southern member has a lower rank for coal quality
(subbituminous B). A coastal or shoreline environment is strongly implied by the
sedimentary structures (paralic) (Shah, 2001). The thickness of a coal seam can range
from 30 centimeters to three meters, with 0.6 to 1 metersmeter being the most typical
thickness recorded. According to estimations, there are 81 million tons of coal reserves
with 1 million tons being measured, 4 million tons indicated, and 76 million tons
inferred.

7
 Figure 3.1 Distribution of Coal mines in Pakistan (adapted adopted from Warwick and
Wardlaw, 2003).some). Some new coal fields are also included.

Coal is found in Kohat and Hangu districts as well as in the Orakzai tribal organization.
Most of the coal mines are in the tribal area, according to a survey of Pakistan topo sheets.
The coal reserves owned by the Hangu-Orakzai Trading Company are found in the upper
part of the early Paleocene Hangu Formation. With sporadic occurrences of carbonaceous
clays and siltstones, this geological formation is predominantly composed of sandstone.
There is only one coal seam known to exist in this area. Proximate analyzes showanalysis
shows that this coal has excessive ash and sulfur content. The high ash appears to be due to
the presence of coal near the edge of the bogs, and in all likelihood the paralytic nature of
these bogs provides an upward pull for excess Sulphur, consistent with the heating costs of
the order of these coal grades for sub-bituminous B to medium volatile. Bituminous,
maximum rank in Pakistan coal. Petrographically, these coals are rich in vitrinite and
remarkably poor in liptinite macerals. The average intertinite content is eleven.2%.
Estimated reserves of this area are eighty million lots.

Figure 3.2 Geological Map of the Study area, showing lower Orakzai Agency coal
deposits. (Mohammad et al., 1993)

8
Figure 3.3 Accessibility map of the study area through Google maps

This area's weather is similar to the Peshawar Valley's, with cold winters and
temperate summers. The monsoon season is when there is the most rain, and December,
January, and February are the coldest months with the most snowfall. Maximum
temperatures in the summer rarely rise beyond 30 degrees Celsius. A cooling effect
during the summer is produced by the neighboring mountains, which are protected by
thick woods. Geographically, Dolly Village is bounded by the Kurram district to the
west, the Kohat district to the east and south, and the Khyber district to the north. Rocks
exposed within the study area are at Middle Jurassic to Eocene levels, commonly
consisting of limestone, sandstone, shale, and some recent alluvium. The vicinity is
effortlessly on hand from Peshawar via N-fifty five (Indus dual carriageway). it is
positioned one hundred twenty km south west of Peshawar and reached by using a
metaled road from Kohat to Dolly village, district Orakzai (See Fig;3.3). Traverses
have been pretty hard with notable phase exposures because of seasonal flow/river
activities.

9
 Figure 3.4 Examining coal mining process at site and collecting rock sample at site
mine

Figure 3.5 Collecting fresh coal and coal mine water samples from site

10
Figure 3.6 Field photograph showing the Hangu Formation

Table 3.1 The studied coal samples and sampling coordinates in the
underground coal mines (Carbonaceous)

Coal field Seam Sample No Lithology Y(East) X (North) Z(Elevation)

Lower Dowlly area 01 Hangu 710454 334105 85.5m

Orakzai Coal mine A coal

Lower Coal mine B 02 Hangu 710452 334106 42.3m

Orakzai coal

Lower Coal mine C 03 Hangu 710451 334110 171m

Orakzai coal

11
3.2 Aim and Objectives

The aim of this study will be to reconstruct paleo-climatic changes using paleo
vegetation biomarkers (C3-C4 types) and organic petrography as a proxy for the coal of
Eocene age-Hangu Formation. To achieve this aim following objectives will be carried
out.

1. To identify the geochemical parameter, total organic carbon and vegetation

type biomarkers in coals of Hangu formation of Eocene age.
2. To reconstruct the paleo-climatic changes using n-alkanes, pristane/phytane,
and diterpenoids and triterpenoids biomarkers ratio as a proxy.

3. To conduct organic petrography of coal samples collected from study area.

3.3 Methodology Adopted

The methodology of the current work will include field work and laboratory
research from designated locations.

The sample analysis followed the study plan outlined below.

12
 SCHEME OF ANALYTICAL WORK
Rock Samples

Sample
Preparation
(Washing / Crushing /
Pulverisation /

Screening

Pyrolysis Total
By Rock Eval 6
(S1, S2, S3, Tmax,
Organic
HI*, OI*, GP*) Carbon
C15+ Extractable Organic
Matter
By Soxhlet extraction technique

Liquid Column
Chromatography

GC-MS for
C15+
Biomarker

Figure 3.7 Flow Chart of Methodology of Biomarker Analysis of Coal Sample

3.4 Sample Collection

Coal samples will be collected from the Hangu Formation in Dolly area of
Lower Orakzai. All samples will be placed in plastic containers and moved to the
NCEG laboratory for further analysis.

13
3.5 Laboratory Analysis

The samples collected during the fieldwork were subjected to a number of

laboratory tests. To start, water was used to rinse all of the samples to remove any
contaminants. These samples were then put in an oven and heated to 40 C overnight to
complete the drying process. To enable screening examination, which included tests for
Total Organic Carbon (TOC) and Rock Eval pyrolysis, the samples were crushed and
powdered into a fine powder after being thoroughly dried.
3.6 Geochemical analysis (SEM)

Sample preparation and collection are the first steps in the process for geochemical study
of coal using scanning electron microscopy (SEM), which is then followed by sample
mounting and, if desired, conductive coating. For imaging and analysis, the SEM
instrument has been configured, calibrated, and optimized. Surface morphology, mineral
phases, and microstructures are all captured by SEM imaging, and elemental analysis
were done by using Energy-Dispersive X-ray Spectroscopy (EDS) at SEM laboratory
National Center of Excellence in Geology, Peshawar. If necessary, quantitative analysis,
maceral observation, and mineral identification should carried out .The data are compiled
in an extensive report, and the results are evaluated to comprehend the composition,
mineralogy, and microstructure of coal in order to support geological and quality
assessments.

3.7 Total Organic Carbon

The method described in the study by Peters and Simoneit (1982) will be used to
determine the coal's total organic content. The analysis will be carried out at the Oil and
Gas Training Instituete, IslamabadNCEG Petroleum Geology Laboratory, University of
Peshawar, utilizing an ELTRA CW-800 analyzer. Generally speaking, a fine-grained
rock with the ability to create hydrocarbons under particular temperature and pressure
circumstances is known as a hydrocarbon reservoir rock (Lashin and Mogren, 2012. An
outstanding source rock should have a Total Organic Carbon (TOC) concentration that
is greater than 1% by weight, which means that there should be at least 1 gram of
organic carbon in a sample of 100 grams. The main technique for quantitatively

14
 evaluating source rocks is the measurement of Total Organic Carbon (TOC). The
sample is initially pulverized in this process to create a fine powder. Acids are then
used to remove any carbon that may be connected to carbonate lithologies. One gram of
the pulverized sample is then subjected to combustion at temperatures as high as
1200°C, utilizing a high-frequency induction furnace. This process converts the carbon
within the kerogen into CO and CO2. Utilizing infrared cells, carbon values are
detected and converted into Total Organic Carbon (TOC), which is expressed as a mass
weight percentage of the rock. A ceramic crucible containing 100 to 150 mg of the
sample is used to decarbonize it using 5% HCl in order to remove inorganic carbon
before doing the TOC analysis. The sample is then dried on a hot plate at 40°C and
subjected to a TOC analysis with a Leco CS-300 equipment. Combustion converts the
sample's organic carbon into the gases CO and CO2, which are then used in the
analysis.

In TOC analyzer, carbon content material is decided by means of IR detectors. To

improve the accuracy of evaluation, Leco widespread become used for calibration.

The accuracy of evaluation became improved with the aid of studying the samples
in replica and using lab stand being repeated after every 10th analysis. The outcomes of
TOC analysis are presented in Table no 4.2.

3.8 Rock Eval Pyrolysis

The most extensively used technique for determining the thermal maturity and
potential for petroleum generation in carbonaceous rock formations is rock-eval
pyrolysis. This method has the benefits of being quick, affordable, requiring few
samples, and often producing reliable data. Anhydrous, open system pyrolysis is
performed by the Rock-Eval apparatus, which was created by the Institut Français du
Pétrole (IFP) in 1977(Espitalie´ et al., 1977). The next section goes into further detail
about the instrument, how it works, and the parameters it measures. Both the rank and
the kind of organic material present naturally affect all Rock-Eval parameters. In the
case of coal, the relationships between some important Rock-Eval characteristics, such
BI and HI, and rank are more complex than is generally recognized. It is crucial to first
identify the natural coalification or maturation pathways for the various categories and

15
subtypes of coal in order to properly use Rock-Eval criteria for determining the type of
kerogen, generative potential, or maturity of coal formations. Furthermore, there is no
consistent rate of advancement indicated by these pathways (Espitalie et al., 1987;
Suggate, 1998).

The Rock Eval Pyrolysis will be carried out using the procedure described by Peters
(1986). The procedure entails gradually raising the sample's temperature (25°C/min),
starting at 25°C and going up to 650°C, while also measuring the hydrocarbons
released as a result of this heating. Using a Flame Ionization Detector (FID), the
hydrocarbons emitted are monitored, forming the peaks S1 and S2. Additionally, the
S3 peak signifies the presence of oxygen-containing molecules within the kerogen,
and it quantifies the levels of CO and CO2 through Infrared (IR) detectors. The Rock
Eval (RE) results are presented in Table 4.1.

The following are the parameters that RE pyrolysis directly measures and those that are
deduced from the ratios:

S1 - This particular peak represents the quantity of unbound hydrocarbons, such as oil
and gas that are present inside the rock and evaporate at temperatures lower than 300
°C (measured in milligrams of hydrocarbon per gram of rock).

S2 - This peak offers information about the amount of hydrocarbon compounds

produced by the cracking of the kerogen as the temperature rises from 300 to 650°C
(measured in milligrams of hydrocarbon per gram of rock). It also shows how much
hydrocarbons might be produced from the source rock if it goes through more
maturation and burial processes.

S3 - This specific peak corresponds to the quantity of CO2 produced during the
pyrolysis of the organic content contained inside the source rock, which took place up
to a temperature of 390°C, and is expressed in milligrams of CO2 per gram of rock.

PI- S1 is divided by the total of S1 and S2 to determine the Production Index (PI). The
level of maturity of the biological substance is indicated by PI. In general, PI tends to
climb with depth and can be used to locate regions with unusually high or low
hydrocarbon contents.

16
 GP- Genetic Potential (GP) is determined by adding the values S1 and S2 together. It
provides information about the hydrocarbon production potential of the source rock.

S2/S3 = S2/S3 This method is utilized to ascertain the nature of organic materials
within the rock.

HI- Hydrogen Index = (100 x S2)/TOC. HI evaluates the hydrogen-to-carbon ratio in an

indirect manner. It functions as a parameter for determining the thermal maturity and
type of organic matter intake.

OI- Oxygen Index = (100 x S3)/TOC. OI measures the oxygen-to-carbon ratio

inferentially. It is used to evaluate the thermal maturity and kind of organic matter
input, and it can also shed light on the depositional environment.

Tmax- The temperature at which the greatest amount of S2 hydrocarbon production

takes place is referred to as Tmax.

3.9 Biomarkers

Biomarkers will be determined by the fractionation method using GCMS as des

cribbed by Murphy (2006) and Asif et al. (2011) conducted in NCEG at University of
Peshawar. Four coal samples will be collected from studythe study area for laboratory
analysis to reconstruct paleo climatic change. Coal biomarkers will be analyzed in the
lower, middle, and upper parts of the Lower Orakzai coal to investigate macroscopic
and molecular changes in the coal seam.

We provided 02 samples for Biomarker Analysis that includes 01 (Px-19815)

coal sample and 01 mine water (Pw-19817). Detailed biomarker study of these two
samples has been carried out at HDIP Islamabad.

The study's main goal was to analyze biomarkers for both aromatic and saturated
fractions. The strategy used to achieve this goal included the following:

• Extraction of Organic Matter (EOM) by Soxhelt extractor of coal sample.

• Extraction of hydrocarbons from water samples using an organic solvent in a

liquid-liquid process.
17
 • Liquid column chromatography is employed to segregate saturated and
aromatic hydrocarbons within the extracted organic material from the
samples.
• Gas chromatography (GC-FID) is used to do thorough analysis and
fingerprinting of hydrocarbons in the saturated and aromatic fractions.

• GCMS, also known as gas chromatography-mass spectrometry, is used

to analyze biomarkers.

The provided samples are of 02 different types (coal and mine water). Hence
methodology varies depending on nature of sample to extract the organic matter for
column chromatography to separate saturated, aromatic and NSO (polar
compounds), and further C15+ hydrocarbon fingerprinting by GC-FID and
biomarker analysis by GCMS. Detailed methodology is given in Figure.

18
 Figure 3.8 Methodology used for Biomarker Analysis

3.9 Some indices calculated from GCMS chromatogram

Four samples from the Hangu coal mine were subjected to biomarker analysis. A
dichloromethane: methanol solution (9:1, v: v) was used, and the samples were
subjected to an ultrasonic treatment for 30 minutes. Asphaltenes were then eliminated
by precipitating them with too much n-hexane. A column chromatography method
using activated silica gel was used to separate the various components. Elution was
performed sequentially using hexane and a dichloromethane-hexane mixture (1:4) to
saturate the aromatic fractions. The analysis was conducted using an Agilent 7890A
gas chromatograph (GC) coupled with a mass spectrometer (5975C).

The equipment used for detailed hydrocarbon analysis comprised of Shimadzu

2010 GC (Gas Chromatograph) and Shimadzu QP2010 mass spectrometer (MS). The
components from mixture are separated by GC based on the molecular size and its
affinity for stationary phase of column. The separated compounds (class of
hydrocarbons) when enter mass spectrometer are bombarded by high energy electrons
(70eV) that results in specific fragmentation of molecules having particular shape, and
these molecules carry charge and are identified by MS in terms of mass/charge ratio
(m/z). Each class of hydrocarbon is characterized by that specific m/z value like n-
alkanes and iso-alkanes (isoprenoids) are characterized by m/z 57 or 85.

Shimadzu GC-2010 was coupled with QP-2010 mass spectrometer. A DB-5-

MS fused silica column with dimensions of 30 meters, 0.32 millimeters in diameter,
and 0.25 micrometers in thickness was installed in the gas chromatograph. The oven's
temperature was initially set at 40°C and held there for around 1.5 minutes before
being raised to 300°C at a rate of 4°C per minute and kept there for 5 minutes.
Temperatures for the ion source and injector were kept at 200°C and 300°C,
respectively. 1.5 milliliters of helium gas were used as the carrier gas, and the transfer
line temperature was maintained at 250 °C. Full scan mode was used to analyze the
composition of hydrocarbons, covering a mass range of 50 to 550 atomic mass units
(a.m.u.). In order to do this, an 11 μl volume of the diluted sample was injected into
the split/splitless injector.

19
 Several standards were used; for identification of hydrocarbons Norwegian
Standard, North Sea Oil (NSO-1), and mixture of n-alkanes and iso-alkanes for
quality control biomarker standards of terpanes (Ts, Tm), steranes (ββ C 29, ββ C27)
were used before analysis.

3.9.1 Carbon preference index (CPI)

This preference of straight odd or even chain carbon by plants will be calculated
from carbon preference index (CPI), using a formula as described by Allan and
Douglas (1977).

CPI = (n-C 11 to n-C 27)/ (n-C 10 to n-C 26).

The lower CPI the greater the anthropogenic input the higher the CPI the greater
the biogenic input.

3.9.2 Average Chain Length (ACL)

Changes occurred in straight chain carbon distribution in coal samples will be

calculated using average chain length (ACL) of straight chain carbon using a formula as
described by Eglinton and Hamilton (1967):

ACL= (25n-C25+27n-C27+29n-C29+31n-C31+33n-C33+35n-C35)/(n-C25+n-C27+n-

C29+n-C31+n-C33+n-C35)

ACL value ranged between 26 to 34 indicates that the source of such n-alkanes
are terrestrial plants.

3.9.3 Terrestrial to aquatic ratio (TAR)

This ratio was calculated from the ratio of terrestrial plant n-alkanes (nC 27, nC29,
nC31) to aquatic plant n-alkanes (nC15, nC17, nC19) using the formula as described by
20
 Bourbonniere and Meyers (1996):

3.9.4 Odd Even Preference (OEP)

Further information about odd-even predominance (OEP) of n-alkanes in coals

will be calculated using the equation as described by Scalan and Smith (1970). This
OEP characterizecharacterizes the n-alkanes separated in coals.

OEP = C i+6C i+2 + C i+4/4C i+1 + 4C i+3] (-1) i+1

Ci represents the percentage by weight of n-alkanes with i carbon atoms per molecule.

3.9.5 Pristane/Phytane Ratio

Pristane and phytane m/z ratio will be calculated from the GC chromatogram.
Their ratio indicates the difference between an oxic and anoxic conditions prevails
during the decomposition and formation of coals over the geological timescale. They
also represent the presence or absence of salts in the water during the decay process of
organic matter from the plants. This ratio will help to understand the depositional
environment of coal formation (Montero-Serrano et al., 2010).

3.9.6 Gymnosperms/angiosperms parameters

Di-terpenoids/ (Di +Tri-terpenoids) ratio will be used to reconstruct

paleoclimatic changes occurred over a geological timescale. The ratio will be calculated
using a formula as mentioned below (Bechtel et al., 2003)

Di-/ (Di-+Tri-terpenoids)

High ratio indicates a variable contribution of angiosperms of the plant

community whereas,

21
 3.10 Organic petrography

Organic petrology provides a complete understanding about the thermal

maturity and organic matter types or Kerogen I, II or III and determines the quality of
coal. Organic petrography will be performed by the method by Sykorova et al. (2005).

One coal sample from Orakzai area provided for the Maceral study to HDIP,
Islamabad. Araldite was used to implant the roughly 1mm-sized samples, and polished
portions were painstakingly manufactured. These sections were then inspected with the
Spectrometer system coupled to an MCS CCD Z1M Zeiss microscope in both white
and blue light. It's important to remember that the sample consists mostly of organic
stuff. The study of organic material that is scattered finely within sedimentary rocks is
the main objective of the field of organic petrography. This analytical method is
frequently used to assess two important parameters:

Type of Organic Matter: It helps identify the various organic constituents present within the
sample.
Maturity Assessment: It aids in assessing the thermal maturity or degree of thermal alteration
experienced by the organic material in the rock.
Macerals are a term used to describe microscopic organic components. The remains of
plants from lacustrine, terrestrial, and marine settings are the source of these macerals.
The origin of the organic material, the stage of diagenesis or catagenesis, and its initial
condition of decomposition are all described using the features of macerals. Based on
their physico-optical characteristics, minerals are divided into three groups: liptinite,
vitrinite, and inertinite. (Tissot and Welte, 1984).

3.10.1 Sample preparation

The crushed materials underwent a sifting process using a 0.8-2 sized sieve to
create particle sections or pellets. In order to firmly attach the particles, a suitable
volume of the crushed sample was then added to a plastic mold along with epoxy resin.
Overnight, the sample was left undisturbed to finish drying.

22
Different grit sizes of silicon carbide papers were sequentially attached to a disc that was
moving at around 200 revolutions per minute during the grinding operation. The sample
pellets were then manually ground using silicon carbide papers with grit numbers of 120,
320, 400, and 600 over four further phases, all the while using flowing water.

Following the grinding procedure, a polishing machine (TF-250, Jeanwirtz) was used to
polish the samples. Sonax oil was utilized as a lubricant to improve the surface
reflectivity of the samples, and diamond powders with varied grain sizes (0-5, 2-5, 4-6,
and 6-8 from Electroschmelzwerk Kempten GmbH) were used as the polishing agents.

3.10.2 Vitrinite Reflectance Measurement

Incident light microscopes, notably the Zeiss Microscope, outfitted with both
tungsten halogen and xenon gas discharge light sources, were used to examine the
material. Using a mechanical stage and a point-counting technique, it was possible to
determine the samples' organic content. A photometer and peak detection software were
used to measure the sample's reflectance in order to perform a thermal maturation
investigation.

23
 CHAPTER 4

RESULTS AND DISCUSSION

4.1 Geochemical Analysis

Figure 4.1 Showing coal samples from the study areaarea.

The coal sample's constituent composition was determined by geochemical analysis, Table 4.1
shows coal analysis of REEs with carbon (C) dominating at 77.05 mass% and 84.62 atom%.
Other elements, such as aluminum (Al) and silicon (Si), provided tiny fractions at 0.43% and
0.45% in terms of mass, respectively. Oxygen (O) accounted for 16.12 mass% and 13.15 atom
%. The presence of sulfur (S) at substantial concentrations of 3.51 mass% and 1.43 atom%
suggests the possibility of sulfur-related problems during combustion or use. 1.65 mass% and
0.39 atom% of iron (Fe) were discovered. For each element, the K ratio, which stands for the
net-to-gross ratio, was computed. Carbon had the highest K ratio at 0.04, followed by sulfur at
0.02. This information offers useful insights into the elements that make up coal and can help
0
determine whether or not it is suitable for use in a variety of applications, especially when it
comes to energy production and environmental concerns.

Figure 4.2 Graph of geochemical analysis showing peaks of REEs in coal

Table 4.1 Showing REEs from geochemical analysis results of coal

FORMULA MASS% ATOM% NET K RATIO LINE LINE

C 77.05 84.62 0.04 147432 0.0185960 K

O 16.12 13.15 0.13 9152 0.0052752 K

AL 0.43 0.21 0.02 4566 0.0008213 K

SI 0.45 0.21 0.02 4877 0.0008475 K

S 3.51 1.43 0.02 39220 0.0080535 K

FE 1.65 0.39 0.03 5946 0.0035343 K

TOTAL 100.00 100.00

1
The geochemical analysis of the coal sample has provided a comprehensive understanding of
its elemental composition. Carbon was found to be the dominant element, indicating the
carbonaceous nature of the coal. The relatively high oxygen content suggests a potential for
combustion-related reactions. The presence of sulfur and iron highlights the importance of
addressing potential environmental and combustion challenges associated with these elements.
The calculated K ratios offer insights into the net-to-gross ratios of these elements within the
coal, with carbon having the highest value, indicating its prominence. This elemental
information is crucial for evaluating the coal'scoal’s suitability for various applications,
including energy generation, industrial processes, and environmental impact assessments.

4.1.1 Total Organic Carbon and Rock Eval Pyrolysis

According to Hunt (1996, p. 635), coals are commonly described as rocks that contain more
than 50% by weight of organic matter, which includes components like C, H, N, O, P, and S.
The total organic carbon content (TOC) of low-rank coals, such as lignite, can, however, be as
low as 20% by weight. The TOC values in the source rock samples taken from the Hangu coal
mines were found to be between 0.03 and 0.06% (as shown in Table 4.1). With one exception
(HC 1.ROO, which has a TOC of 0.6% by weight), rock samples that are visually identified as
carbonaceous shale typically have TOC levels of less than 16%.
Table 4.2 showing the percentage values of TOC in Hangu Coal

Analysis Date Depth TOC

(%)
Sample- 02-13- 1m 0.06

1.R00 2023
Sample- 02-13- 1m 0.3

2.R00 2023

The source rock of the coal may have a lithology related to carbonaceous shale if the Total
Organic Carbon (TOC) level is less than 1%. A type of sedimentary rock known as
carbonaceous shale is a significant source rock for the creation of coal because it contains a
significant quantity of organic carbon. In this situation, the low TOC level suggests that the
2
source rock for the coal contains less organic matter, which may have an effect on the coal's
quality and rank.
The procedure specified by Peters (1986) was followed when performing Rock Eval Pyrolysis.
The kind, quantity, and thermal maturity of the organic matter in the samples were all
insightfully revealed by this examination. The OGDCL's Petro Research and Training Institute
(PRTI) laboratory in Islamabad is where the analytical work was done. The Rock-Eval method
was used to pyrolyze a range of materials, including coal, carbonaceous shale, and silty
sandstone cores, for detailed investigation.
Table 4.3 Rock Eval pyrolysis and TOC test report detailed valuesvalues.

Analysis Sample-1.ROO Sample-2.ROO

Date 02-13-2023 02-13-2023

Depth 1 1

TOC (%) 0.06 0.03

S1(mg/g) 96.55 0

S2(mg/g) 72.91 0

S3(mg/g 0.26 0.24

Tmax(°C) 414 -37

PI 0.57 1

HI 438 0

OI 2 400

PC (%) 14.25 0.01

RC (%) 2.38 0.05

MINC (%) 3.25 0.26

PyroMINC (%) 1.16 0.07

OxiMINC (%) 2.09 0.18

OICO 7 33

S3CO(mg/g) 1.2 0.02

3
 S3'CO(mg/g 5.7 0

S3'(mg/g) 38.1 2.7

S5(s) 582532 472301

Qty(mg) 7.6 70.8

Table 4.2 shows analysis of Sample-1.ROO and Sample-2.ROO, both collected at a depth of 1
meter, revealsrevealing significant differences in their composition. Sample-1.ROO exhibits a
higher Total Organic Carbon (TOC) content of 0.06% compared to Sample-2.ROO, which has
a TOC of 0.03%. Moreover, Sample-1.ROO shows substantial S1 (mg/g) and S2 (mg/g)
values of 96.55 and 72.91, respectively, indicating higher hydrocarbon generation potential. In
contrast, Sample-2.ROO has negligible S1 and S2 values. The Tmax (°C) for Sample-1.ROO
is 414°C, suggesting significant thermal maturity, while Sample-2.ROO exhibits a negative
Tmax (-37°C), indicating immaturity. Production Index (PI) and Hydrogen Index (HI) values
also differ, with Sample-1.ROO having a lower PI of 0.57 and a higher HI of 438, while
Sample-2.ROO has a PI of 1 and a HI of 0. The Oxygen Index (OI) values highlight a
substantial contrast, with Sample-1.ROO at 2 and Sample-2.ROO at 400. Reflectance Carbon
(RC), Mineral Carbon (MINC), and other parameters further underscore the dissimilarity
between these samples. The Quantity (mg) of Sample-1.ROO is 7.6, whereas Sample-2.ROO
has a significantly higher quantity of 70.8 mg. These variations in parameters indicate
differences in organic matter type, maturity, and source between the two samples, making
them valuable for further geological investigations.
4.2 Biomarker analysis

4.2.2 Biomarker Results

Saturated and aromatic fractions both are analyzed by GCMS for biomarker
analysis and detailed aromatic hydrocarbons Analysis, the saturated fractions are
subjected to get the chromatograms of fingerprints and biomarkers of GC-FID
chromatograms, m/z 191 (Terpanes), m/z 217 (Steranes) and m/z 218 (Steranes) and
aromatic fraction is subjected to get chromatograms of Phenanthrenes,
Dibenzothiophenes, Naphthalene etc.

4
 Table 4.4 Biomarker Results of Saturated Hydrocarbons of NCEG Samples Samples
(Px-19815 and Pw-19817)

S. No Parameters Px-19815 Pw-19817

(Mine Water)
(Coal)

1 Isoalkanes (Pr/ph) 2.19 0.49

2 Iso Alkanes (Pr/nC17) 0.47 0.43

3 Isoalkanes (Ph/nC18) 0.21 0.39

4 OEP 0.90 -

5 Triterpanes (Ts/Ts+Tm) 0.41 0.57

6 Triterpanes (C19/C19+C23) Only C19 is present 0.15

7 Triterpanes (C29/C30) C30 is biodegraded 1.27

8 Gammacerane / H30 - 0.13

9 Moretane (M30/H30) - 0.10

10 Oleanane (O/H30) Prominent peak -

12 Homohopanes (H32S/ H32S+ H32R) Not clear peaks 0.60

13 Steranes (C27/C27+C29) Only C29 is present 0.39

14 Steranes (C29S/C29S+C29R) - 0.51

15 Steranes (C29ββ/C29ββ+C29αα) - 0.53

4.3 Saturated Hydrocarbons Analysis

4.3.1 Biomarker Analysis of Coal Sample (Px-19815)

GC-FID chromatogram (Px-19815) is showingshows the fingerprints of C15+

hydrocarbons in which nC14-nC28 normal Alkanes are present and pattern of
fingerprints is showing that sample is thermally mature and also contains light
5
 hydrocarbons in high concentration. Pr/Ph ratio is 2.19 indicate the sub-oxic
depositional environment of the organic matter and may also indicate the terrestrial
source of organic matter. OEP value is 0.90 that is almost≈1 it also indicates the
thermal maturity of the sample.

Figure 4.3 GC-FID Chromatogram of Coal Sample (Px-19815)

Ion chromatogram of m/z 191 of Px19815 shows that low concentration of

terpanes is present and mainly the terrestrial organic matter input because marine
biomarker C23 is almost absent and prominent peaks of terrestrial organic matter
biomarkers C19, C20 are present in the chromatogram. C24 tetracyclic terpanes is in high
concentration indicating the high terrestrial input in organic matter. C 30 hopane peak is
in negligible amount as comparecompared to C29. Oleanane is present in high
concentration and indicateindicates the angiosperm input in the organic matter.
Ts/Ts+Tm ratio is almost 0.41 which is indicating that organic matter is at peak
maturity stage but on the other hand H 32S/ H32S+ H32R homohopanes are not clearly
visible it seems like that the sample is thermally mature.

6
 Figure 4.4 m/z191 GCMS Chromatogram of Coal Sample (Px-19815)

Ion chromatograms of m/z 217 (Fig.3) of Px-19815 shows that Sterane

biomarkers are absent in sample is so C 29ββ/C29ββ+C29αα and C29S/C29S+C29R
ratiosratios.
Cannot be calculated.

Ion chromatograms of m/z 218 (Fig.4) of Px-19815 indicate that the sample has
only terrestrial organic matter input because only C 29 (ββR and ββS) steranes are
appearing in the chromatogram, the marine biomarker C 27 steranes and fluvial/deltaic
C28 biomarkers are almost absent. So organic matter is mainly generated from the
Terrestrial source.

7
 Figure 4.5 m/z217 GMS Chromatogram of Coal Sample (Px-19815)

Figure 4.6 m/z218 GMS Chromatogram of Coal Sample (Px-19815)

4.4 Biomarker Analysis of Mine Water Samples (Pw-19817)

Saturated and aromatic fractions both are analyzed by GCMS for biomarker
analysis, the saturated fractions are subjected to get the chromatograms of fingerprints
and biomarkers of GC-FID chromatograms, m/z 191, m/z 217 and m/z 218.

GC-FID chromatogram of mine water sample Pw-19817 is showing the

fingerprints of C15+ hydrocarbons in which n-C17 – n-C33 normal Alkanes are present,
and pattern of fingerprints is showing that sample is biodegraded because UCM
(unresolved complex mixture) is present and on the other hand low concentration of n-
Alkanes (n-C14 – n-C22), pristane and phytane are also present. As a result, the gas
chromatogram displays a uniquely sharp rising baseline, which is a feature frequently
connected to oils that have undergone significant biodegradation. The molecules in this
unresolved complex mixture (UCM) have displayed extraordinary biodegradation
resistance. Although pristane and phytane appear to be undamaged, the existence of
lesser n-alkanes (such as nC14-n-C20) suggests the presence of a secondary oil charge
that interacted with the extensively biodegraded oil and then experienced minor
biodegradation(biodegradation (Peters et al., 1999b; Peter et al., 2005, pg. 668)..

8
 Notably, the ratios of pristane and phytane to n-C17 and n-C18 are quite low,
measuring 0.47 and 0.39, respectively (both below the cutoff of 0.5), indicating that
they are present in lower amounts than these two carbon atoms. This shows that
biodegradation hasn't had a significant impact on the blended oil. Furthermore, a Pr/Ph
ratio of 0.49 denotes an anoxic depositional environment.

Figure 4.7 GC-FID Chromatogram of Mine Water Sample (Pw-19817)

It is clear that there is a little larger concentration of marine organic matter input
in the chromatogram at m/z 191 for Px19817. This is clear from the fact that the marine
biomarker C23 has a higher concentration than the biomarkers for terrestrial organic
matter, C19 and C20. C24 tetracyclic triterpenes is also in high concentration indicating
the high terrestrial input in organic matter. C29/C30 ratio is >1 which indicating the
carbonate lithology of source rock, low C 24 biomarker is also indicating the low clastic
content in the source rock. The G/H30 ratio is 0.13, indicating a marine environment
that is somewhat salinized. It also shows that there are no hypersaline carbonate
evaporates in the region.Ts/Ts+Tm ratio is almost 0.57 which indicates that organic
matter is at peak maturity stage, H 32S/ H32S+ H32R ratio is also 0.60 which reinforces
the evidence of peak oil window of the organic matter. Moretane (M 30) is in low
concentration (0.10) which indicates the thermal maturity of the sample or organic
matter.

9
Figure 4.8: m/z 191 GCMS Chromatograms of Mine Water Sample (Pw-19817)

In chromatograms of m/z 217 of Pw-19817 indicates that sample is thermally mature

because C29ββ/C29ββ+C29αα and C29S/C29S+C29R ratios are in the range of 0.51-0.56, so
sample falls in the thermally mature oil window.

10
 Figure 4.9: m/z 217 GCMS Chromatograms of Mine Water Samples (Pw-19817)

In chromatograms of m/z 218 of Pw-19817 indicate that sample has terrestrial/mixed

organic matter input because C27/C27+C29 ratio is 0.39, indicating that marine biomarker
C27 steranes is little bit low in concentration as compared to the terrestrial biomarker C 29
steranes. So, it seems like the organic matter is mainly generated from the mixed
(terrestrial and marine) source.

Figure 4.10: m/z 218 GCMS Chromatograms of Mine Water Sample (Pw-19817)

4.5 Aromatic Hydrocarbon Analysis

DBT/P; Dibenzothiophene/Phenanthrene, MPI (Methyl Phenanthrene Index; (1.5(2MP+3MP)/

(PHEN+1MP+9MP), RC calculated equivalent vitrinite reflectancereflectance.
(0.6 x MPI + 0.4), MDR=4MDBT/1MDBT, Rc (MDR) = 0.51+0.73 x MDR, DNR1:
Dimethyl Naphthalene ratio= (2, 6 DMN+2, 7 DMN)/1, 5-DMN), TNR-1: Trimethyl
Naphthalene ratio= (2, 3, 6 TMN)/1, 4, 6-TMN+1, 3, 5-TMN),
11
Table 4.5: Results of Aromatic Hydrocarbons

Sr. No Parameters Px-19815 Coal Px-19817 Mine Water

1 DBT/P 1.04 -

2 MPI-1 1.27 -

3 Rc (MPI) 1.16 -

4 MDR 0.03 -

5 Rc (MDR) 0.53 -

6 DNR-1 5.03 -

7 TNR-1 3.35 -

4.5.1 Aromatic Hydrocarbon Analysis of Coal Sample (Px-19815)

Aromatic fractions are analyzed by GCMS detailed aromatic

hydrocarbonshydrocarbons.

Analysis, the aromatic fraction is subjected to get chromatograms of Phenanthrenes,

Dibenzothiophenes, Naphthalene and their isomers etc.

MPI-1 and Rc values are 1.27 and 1.16 respectively indicate the late oil
window, MDR value is 0.03 also leading towards the thermal maturity of the organic
matter because 4MDBT is in quiet high concentration as comparecompared to the
1MDBT. DNR-1 and TNR-1 values are high (5.03 and 3.35) because they show
pronounced increase above 0.9% Rm (Radke et at, 1982a; 1984b). DBT/P ratio is >1
indicate marine carbonate zone of deposition (Interpretation scheme according to
Hughes et al., 1995)

12
Figure 4.11: m/z178, 192,184 (Phenanthrene, Methyl Phenanthrenes and
Dibenzothiophene) GMS Chromatogram of Coal Sample (Px-19815)

Figure 4.12 m/z198 (Methyl Dibenzothiophene) GMS Chromatogram of Coal

Sample (Px-19815)

13
 Figure 4.13: m/z12, 142,154 (Naphthalene, Methyl Naphthalene and Dimethyl Dimethyl
Naphthalene) GMS Chromatogram of Coal Sample (Px-19815)

Figure 4.14 m/z170, 184 (Trimethyl Naphthalene and Dimethyl Dimethyl

Dibenzothiophenes) GMS Chromatogram of Coal Sample (Px-19815)
4.5.2 Aromatic Hydrocarbon Analysis of Coal Sample (Pw-19817)
Aromatic Hydrocarbons are absent in the aromatic fraction of the mine water
(Px-19817)

14
 Figure 4.15: m/z TIC, 178,192,184 GMS Chromatogram of Coal Sample (Pw
19817)

4.3 Organic Petrography analysis

4.3.1 Maceral study of Coal sample

A coal sample from the Hangu Formation in the Orakzai district was selected for maceral
study. These samples, which were approximately 1mm in size, were embedded in araldite, and
sections were carefully polished. The analysis involved examining the sample under both
white and blue light using the Spectrometer system MCS CCD Z1M Zeiss microscope.
Notably, the sample predominantly consists of organic matter. A brief overview of the study is
provided below.4.3.1.1 Sample detailsdetails.
4.3.1.1 Sample details

Pr-No: 19816

15
 Sample No: V-2313

Sender Number/Depth: No-2 Organic Matter Type: The sample is distinguished by the
predominance of organic materials, which has observably larger grains. When evaluating
the macerals present, vitrinite, which appears as collinite and vitrodetrinite, takes the
lead. Inertinite, which comprises components like funginite, inertodetrinite, and
semifusinite, is the second most prevalent maceral after vitrinite. This composition offers
insightful information on the sample's organic composition. Maturity was not
requestedrequested.

Pr - 19816/No
Collinite

16
 Pr - 19816/No

Collinite

Figure 4.16 Figure showing collinite vein in coal sample

Pr - 19816 /No

Semifusinite

Figure 4.17 Figure showing semifusinite veins in coal sample

17
 Pr - 19816 /No
Inertodetrinite

Figure 4.18 Figure showing inertodetrinite mineral in Coal sample

Pr - 19816/No

Funginite

18
Figure 4.19 Figure showing Funginite mineral in coal samplesample.

4.3.2 Elementary and microscopic constituent of coal.

Some important conclusions about the sample's composition are drawn from the analysis of
the sample. The sample is primarily distinguished by the predominance of organic matter,
which makes up a sizeable component of its content. The larger particle size of this organic
material reveals details about its genesis and origin. Intriguing information can be found by
looking closer at the macerals in the sample. The main maceral found is vitrinite (WOODTY
PLANT MATERIALS, CEDARS, CONFIERS, PINE, YEW, AND MANY MORE) THEY
GROW UNDER DIFFERTN CLIMATIC REGIME-SUBHUMID TO HUMID CLIMATE-
CONDITION LACK OXYGEN RESINS ARE DERIVED FROM CHIR TREE AND
WAXES THIS CONFIRMS OUR PALEVEGETATION BIOMARKERS THAT THE
BIOMARKERS ARE TERPENES AND DERIVED FROM THE TERRESTRIAL PLANTS
WITH OXIC ENVIRONMENT, WARM, DRY CONDITIONS AND PRESENCE OF
DBT/P, GREATER THAN 1 MEANS THAT THE LITHOLOGY OR SOURCE ROCK IS
CARBONATE AND IN BRINE OR WATER PRESENCE OF C30 AND C23
BIOMAARKERS PF TETRCYCLIC TERPNES SHOWS THAT THE SOURCE ROCK OF
BRINE IS CARBONATE AND LESS C24 SHOWS THAT CLASTIC INPUT IS LOW
THIS IS FROM VEGETATIVE BIOMARKERS WHEREAS ALL THE AROMATIC
BIOMARKERS WERE COMPLETLEY ABSENT IN BRINE BUT PRESENT IN COAL
AND SUGGESTED BY THE OBSERVAION THAT COAL AND RINE DERIVED
FROM THE SAME SOURCE OF CARBONATES which also exists as vitrodetrinite and
collinite. Being a significant component, vitrinite sheds light on the origin and nature of the
organic material. Another important maceral included in the sample is inertinite, of which
three distinct types funginite, inertodetrinite, and semifusinite have been identified. These
macerals provide insight into the diagenetic processes and plant sources that contributed to
the development of the organicorganic materials. The assessment of maturity was not a part
of the investigation, which focused primarily on the maceral composition and characteristics
of the organic matter, even if the analysis has disclosed these facts.

19
 CHAPTER 5

Conclusion

In conclusion, the genetic analysis of the coal samples revealed that they all came from
carbonaceous shale, indicating a terrestrial depositional environment heavily influenced by
C4 vegetation. The Paleocene-aged Hangu Formation's comparatively low organic matter
abundance shows that in an oxic to suboxic environment, organic matter decomposes
quickly. Terpanes had a significant amount of biodegradation, and angiosperms had
contributed to the organic matter, according to biomarker tests. Except for C29, there are no
steranes in the chromatogram, highlighting the dominance of terrestrial organic compounds.
The mine water sample's composition consists of a mixture of minimally and severely
biodegraded organic matter, indicating thermal maturity and a variety of organic matter
sources within a depositional environment distinguished by carbonate lithology, moderate
salinity, and anoxia. All samples reached thermal maturity before entering the oil/gas
window, according to steranes.

Overall, the research indicates that low-rank coal is inappropriate for industrialindustrial, or
power generation uses. It is advised to do systematic outcrop and mine sampling in order to
further investigate the variations in coal rank between the mines in the Lower Orakzai coal
mining site. Due to resource limitations, the study was only able to examine a small number
of mines; nonetheless, it is advised to do a thorough analysis of coal quality across all mines
and involve stakeholder groups in seminars and workshops. For a more thorough grasp of
paleoclimate reconstruction, comparative investigations between low-grade and high-grade
coal mines should also be carried out, as well as more extensive research employing
vegetative biomarkers.

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