Palaeoenvironmental variation of a sub ... -...

65st Annual Meeting of the ICCP’ 2013, Sosnowiec, Poland

55

Palaeoenvironmental variation of a sub-mountainous Holocene peat

in North Spain based on biomarkers and FTIR proxies

M. Arboleya, J. Pellegrini, J. Urbanczyk, V. López-Dias, C.G. Blanco, A.G. Borrego

Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain; [email protected]

The interest of peatlands as palaeoenvironmental records has increased in the recent years

because they may represent a continuous record of vegetation growth with a limited number

of species, peat profiles are in-land records close to populated areas and especially those fed

only by rainfall (ombrotrophic peats), are not affected by external supplies (Barber et al.,

2003). The North of Spain contains a number of peat bogs at littoral, submountainous and

mountainous locations, in which increasing height also correspond to increasing distance to

the coastline. Those at moderate height are known as cántabro-atlantic mires and

characterized by the association Erico mackaianae-Sphagnetum papillosi (Fernandez Prieto et

al., 1987). The Peat bog considered in this study is La Molina (UTM 29 T 716294 4806806,

height 648 m above sea level=m.a.s.l), whose profile reached a depth of 295 cm. The profile

consisted of ten top centimeters of living vegetation followed by brown-reddish bryophytic

peat from 10-230 cm, turning darker in the deepest 40 cm. This part of the profile has a

mineral matter content below 10%. The mineral matter content increases fast from 10 to 90 %

in the following 40 cm interval and it is higher than 90% from the cm 270 downwards

exhibiting an intermediate grey colour. The sample at 279 cm depth of the profile has yield an

AMS 14

C date of 9384 ± 45 cal. yr BP (Arboleya, 2011).

The biomarkers study by Gas Chromatography/Mass Spectrometry of the

dichloromethane/methanol peat extracts has allowed the establishment of humid/dry periods

on the assumption that herbs and heather dominate in dry periods with higher concentration of

n-C29 and n-C27 and Sphagnum dominate in humid periods with higher concentration of n-C23

and n-C25 (Bass et al., 2000; Bingham et al., 2010). High values of n-C23/n-C29, associated to

humid periods, have been recorded in two episodes in La Molina profile corresponding to

4200-4350 and 4500-5100 cal yr BP. These episodes have been also registered in other peats

of the region at slightly different ages (López-Dias et al., 2013). The combustion profiles of

the Sphagnum-rich intervals indicate a dominance of the first combustion peak in the profiles

(Borrego et al., 2011). This has been also observed during the humid episodes in La Molina

profile.

The Fourier Transformed Infrared (FTIR) spectra of peat provide an additional tool to find

out about organic matter input considering that different peat-forming plants slightly differ in

the relative intensity of their FTIR bands (Urbanczyk et al., 2012). The FTIR spectra exhibit

bands at 2920 and 2850 cm-1

corresponding to stretching of antisymmetric and asymmetric

CH2 groups in fats, wax and lipids; 1700 cm-1

band of carbonyl and carboxyl groups in

carboxylic acids, aromatic esters and free acids; 1600 cm-1

band of aromatic C=C stretching;

1265 cm-1

band of C–O stretching of phenolic groups and arylmethylethers; 1080-1030 cm-1

band of O–H deformation in polysaccharides (Fig. 1). The spectra of peat-forming plants


56

typically show bands at 1080-1030

cm-1

assigned to cellulose, and both

Ericaceae and Poaceae show two

distinct bands in the region 1700-

1600 cm-1

(Urbanczyk et al., 2012).

Typical spectra of peat from dry

periods, as derived from biomarker

analysis, show better resolved 1700

cm-1

band compared with peat from

humid periods, which could be

attributed to a higher proportion of

woody material in the former.

Acknowledgement: Financial support from

MICINN (CGL2009-13990-C02-01/02) is

gratefully acknowledged. J. Urbanczyk

thanks MEC for a FPU fellowship.

References

Arboleya M., 2011 - Biomarcadores moleculares como indicadores paleoclimáticos en turberas asturianas de

ambiente submontano. MSc Thesis. University of Oviedo, Spain: 1-30.

Bass M., Pancost R., van Geel B., Sinninghe-Damsté J. 2000 - A comparative study of lipids in Sphagnum

species. Org. Geochem. 31: 535–541.

Barber K.E., Chambers F.M., Maddy D. 2003 - Holocene palaeoclimates from peat stratigraphy: macrofossil

proxy climate records from three oceanic raised bogs in England and Ireland. Quaternary Science Reviews

22: 521–539.

Bingham E.M., McClymont E.L., Väliranta M., Mauquoy D., Roberts Z., Chambers F.M., Pancost R.D.,

Evershed R.P. 2010 - Conservative composition of n-alkane biomarkers in Sphagnum species: Implications

for palaeoclimate reconstruction in ombrotrophic peat bogs. Org Geochem. 41: 214-220.

Borrego A.G., López-Dias V., Arboleya M., Urbanczyk J., de Luca V., Blanco C.G. 2011 - Variation of organic

matter input in peat as seen by combustion profiles. 63th ICCP Meeting, 10-16 September Porto, Portugal.

Fernández Prieto J.A., Fernández Ordóñez M.C., Collado Prieto M.A. 1987 - Datos sobre la vegetación de las

“turberas de esfagnos” galaico-asturianas y orocantábricas. Lazaroa7: 443-47.

Lopez-Dias, V., Urbanczyk J., Blanco, C.G., Borrego, A.G. 2013 - Biomarkers as palaeoclimate proxies in

peatlands from coastal high plains in Asturias, N Spain. Int J. Coal Geol.

dx.doi.org/10.1016/j.coal.2013.04.006.

Urbanczyk J., López Dias V., Borrego A.G. 2012 - Infrared Spectra: an additional tool to study organic matter

input in peat bogs. 64th

ICCP Meeting, 15-24 September, Beijing, China.

Fig. 1. FTIR spectra of representative samples of humid

and dry periods in La Molina. =stretching, =bending.


57

Differentiation of Ni, Co, Cr, Cu, Zn and Pb content in coal seams

from the Orzesze beds SW-part of Upper Silesia Coal Basin – Poland

B. Białecka1, J. Całusz-Moszko

1, Z. Adamczyk

2, J. Komorek

2, M. Lewandowska

2

1Central Mining Institute, Plac Gwarków 140-166 Katowice, Poland

2Silesian University of Technology, Faculty Of Mining And Geology, Institute of Applied Geology Akademicka 2,

44-100 Gliwice, Poland

The subject of the study were channel coal samples taken from the Orzesze beds of the coal

seams 360/1, 361, 362/1 from the southwest part of Upper Silesia Coal Basin (“Pniówek” coal

mine). The values of mean average reflectance of vitrinite was measured according to PN-

ISO 7404-5:2002 and maceral composition was analysed according to PN-ISO 7404-3:2001.

All measurement were carried out under reflected light (=546 nm) in immersion oil

(no=1.5176 at 23oC ) using an Axioscope Zeiss microscope. The coal samples were averaged,

then grinded to the grain below 0.2 mm. The high-temperature ashes (HTA) were prepared in

an electric furnace at 815oC. For all samples ash content (A

d) according to the PN-80/G-

04512, was determined. Inductively coupled plasma Fussion-ICP and ICP/MS analysis for Si,

Ti, Al, Fe, Mg, Ca, Na and K oxides and elements Ni, Co, Cr, Cu, Zn and Pb were performed

for a characterization of the bulk chemical composition of HTA. Chemical analysis were

performed with use Perkin Elmer SCIEX ELAN 6000 ICP/MS in the Activation Laboratories

Ltd. in Canada.

The total chemical composition of

coals and their ashes is important but

insufficient characteristic for a

reliable explanation of coal

properties. Most important are the

modes of element occurrence namely

whether a particular element is

present in minerals and other phases,

their origin and amount in coal, as

well as their behavior during

coalification process. The noted

characteristics may be a guide for

prediction of some properties,

benefits and behavior of coals and

their products during coal use

(Vassiliev 1998).

It was found that examined coal

samples represent high grade (Ad<10%), medium- rank metabituminous coal – B (ECE

Geneva 1994) with high vitrinite content (>60%). The normalized chemical composition of

HTA samples and an ash classification system based on the quantities of main five oxides

Fig. 1 Chemical classification system for the main

composition of HTA Samples [wt.%]

(Vassilev, 1998)

M9

M1

M3

M14

M7

M8

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

SiO2 + Al2O3

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

CaO + MgO

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

Fe2O3

M9

M1

M3

M14

M7

M8

http://maps.google.pl/maps/ms?ie=UTF8&hl=pl&msa=0&msid=100380917387059618639.00046a3ede8c1ff8d6bcd&ll=50.343708,18.853226&spn=0.259417,0.624847&z=11

http://maps.google.pl/maps/ms?ie=UTF8&hl=pl&msa=0&msid=100380917387059618639.00046a3ede8c1ff8d6bcd&ll=50.343708,18.853226&spn=0.259417,0.624847&z=11


58

(Vassiliev 1998) show that the specimens belong to, ferrisialic and ferricalsialic HTA types

(Fig. 1.). Maximum concentration Cr, Co, Ni, Cu and Zn was found in the HTA sample from

362/1 seam (sample 6). Minimum concentration of examined elements was found in HTA

from stratigraphically younger seams 360 and 361. The research showed differences in

contents of analyzed elements within a single seam (Fig 2.)

Adjusted to organic matter content of examined elements has value from the range

determined for most coals (Taylor 1998). Coal clark (Ketris and Yudovich 2009) for Cr, Co

and Cu has lager value than observed in analyzed samples. Coal clark Ni has lower value than

in coal samples (Fig 3).

References

Ketris M.P., Yodovich Ya.E. 2009 - Estimation of Clarkes for Carbonaceous biolithes: world averages for trace

element contents in black shales and coals. International Journal of Coal Geology, 78: 135-148.

Taylor G.H., Teichmüller M., Davis A., Diessel C.K.F., Littke R., Robert T. 1998 - Organic Petrology. Gebr.

Borntraeger, Berlin-Stuttgart.

Vassilev S.V., Vassileva C. G. 1998 - Comparative chemical and mineral characterization of some Bulgarian

coals. Fuel Processing Technology, 55: 55-69.

Wang X. 2009 - Geochemistry of Late Triassic coals in the Changhe Mine, Sichuan Basin, southwestern China:

Evidence for authigenic lanthanide enrichment. International Journal of Coal Geology, 80: 167-174.

Cr Co Ni Cu Zn Pb0

200

400

600

800

1000

1200

1800

2000

Conte

nt

[ppm

]

- 360/1 seam, sample M9- 361 seam, sample M1- 361 seam, sample M3- 361 seam, sample M14- 362/1 seam, sample M7- 362/1 seam, sample M8

Fig. 2. Content of Cr, Co, Ni, Cu, Zn and Pb

in HTA samples

Cr Co Ni Cu Zn Pb0

20

40

60

80280

300

Conte

nt

[ppm

]

- content of trace element in coals (G.H.Taylor et.al. 1998) with coal clark (X. Wang 2009)

- range of element content in examined coals

Fig. 3. Content of Cr, Co, Ni, Cu, Zn and Pb

in coal samples against a background of content of

trace element in coals (G.H. Taylor et.al., 1998) with

coal clark (Wang, 2009; Ketris and Yodovich, 2009)


59

The possibility of underground gasification of lignite from Polish deposits

B. Bielowicz, K. Matl

AGH University of Science and Technology, Mickiewicza 30, 30-059 Kraków, Poland;

+48 12 617 23 75; [email protected]

Polish economic reserves of lignite occur in the Miocene formations in numerous deposits

within the Polish-German Lowland. Aforementioned reserves can be used for heating

purposes, mainly in power plants, for chemical processing, in order to obtain gaseous and

liquid products in chemical plants, and for underground gasification processes.

The annual production of lignite in Polish open cast mines amounts to 65.0 million tons per

year, while it is primarily used by power plants. However, chemical processing of lignite is

not yet developed. It is planned to develop pilot plants for underground lignite gasification in

the near future.

Currently studied conditions of this process are resulting from the geology of Neogene and

Paleogene coal formations, coal quality, chemical and technological parameters of coal and

from the limitations related to environmental protection and land development.

Lignite from the Polish deposits coal has the characteristics of low rank coal (mean Rr 0.2

- 0.35), an average carbon content at around 62 - 65% C, high moisture content (> 50%) and

net calorific value (NCV ) 6 - 20 MJ/kg (mean 8.0 MJ / kg). Petrographic composition of

lignite (> 80% humic components) makes it a preferred material for chemical processing.

Geological parameters, deposit parameters, chemical and technological properties of coal

are all very important for the proper course of the underground gasification process (Table 1).

The process of underground lignite gasification will face significant technological barriers

associated with high humidity of coal and water accumulation.

Even though a large number of reserves meet the aforementioned criteria, only a small part

is planned to be subjected to underground gasification process.

Work performed under task of research No. 3 funded under the Agreement NCBiR No.

SP/E/3/7708/10".


60

Table 1 Criteria for lignite deposits for underground gasification processes.

No. Criterion Range of variability

1 Type of coal and physicochemical

parameters:

calorific value

volatile matter

ash content

natural moisture

sulfur content

Minimum amount not specified (from 6.5 MJ/kg)

below 50%

below 20% optionally 25%

below 55%

below 4.0%

2 Deposit thickness:

minimal

maximum

2 m up to 4 m (optimal)

dependent on hydraulic insulation, overall conservation and the conservation

of the boreholes (controlling overburden collapse)

3 Depth:

minimal

over 150 m* - below erosion washouts and glacitectonic channels. In case of

the deposits not associated with glacial activity, the depth may be lower

4 Deposit type:

single-seam deposit

multi-seam deposit,

preferred

possible when using advanced technology (e.g. using backfill), the distance

between. seams >20m

5 Overburden ratio: > 12 (10) roof of the deposit at a depth of up to 350 m**

6 Inclination angle of the deposit horizontal or slightly inclined

7 Thermal insulation of the

surrounding rocks

Roof rocks are clays and silts of very low permeability (k ≤ 9 10-8m/s) with a

thickness of≥10-20m; 2,8 of deposit thickness **

8 The hydrogeological conditions:

position in relation to aquifer

volume of water flow to the

seam

below the usable aquifers and outside the Major Groundwater Reservoirs, the

minimum distance is 40m.

Below 2 m3 / Mg of lignite without additional draining

9 Tectonics No cracks and faults, no significant tectonic disturbances within the mining

fields

10 The porosity of the surrounding

rocks

Roof rocks and the floor rocks should have lower gas permeability than

lignite seam, while the thickness of poorly permeable rocks surrounding the

seam should be 1-2 meters or 2-4 meters for 2 meters and 3-10 meters of

seam thickness, respectively **

11 The amount of reserves Reserves required for pilot plant are around 75 - 450 thousand. Mg, while

commercial project will need a minimum of 3,5 Mt**

12 Filtration properties of the rock The ratio of porosity of lignite seam to that of surrounding rocks should not

be less than mD 18:20**

Depending on location

13 The area of required for

underground lignite gasification

plant

minimal area for the pilot plant is 50 - 100 ha (0.5 - 1 km 2

), while for the

commercial installation it is over 100 hectares **

Safety conditions minimum distance from: residential areas (1-3km), rivers and lakes (1-3km),

protected areas (5km), currently exploited mines / mining areas (5km),

abandoned mines / workings (3km), transmission lines and railways (1-3km)

**

* in specific cases - including no glacial activity - conditions may be less restrictive

** criteria according to Cupprum


61

Oligocene bituminous marls of Eastern Carpathians –

geochemical appraisal using Rock-Eval and vitrinite reflectance data

M.D. Ghiran1, S. Gheorghe

1, I. Maris

2

1 OMV Petrom S.A., E&P Development Business Unit – ICPT Campina, 29 Culturii Bulevard;

[email protected]; [email protected] 2 OMV Petrom S.A., E&P, Easter Carpathians Department, 22 Coralilor St., Bucharest;

[email protected]

The study area is located on the Teleajen Valley (Romania), in the Southern-East side of

Eastern Carpathian Belt, in the Tarcau Nappe. The outcrop is represented by Oligocene

marine sedimentary deposits. Based on geological setting, this structure is a part of the over

thrust system, which evolution started in the Middle Cretaceous – Pleistocene. The

sedimentary formations from this area are part of a single sedimentary cycle of the Cretaceous

– Miocene. The characteristic lithofacies are siliciclastic and sometimes mixed siliciclastic –

carbonated. The most important petroleum system is being found in the Oligocene level, and

contains source rocks, reservoir rocks and protector rocks.

The outcrop researched is located on the right side of the Teleajen River, next to the

Valenii de Munte City. The formation is approximately 120 m long and 20 m high. The

sedimentary succession from the outcrop is built up on the vertical. The profile to be

researched is part of an synclinal overthrust. The facies is represented by intercalation of

quartzose sandstone and bituminous marls. The bituminous marls look like a tabular body

with sedimentary structure - parallel laminated. The colour of the bituminous marls is dark –

brown, bright, due to the presence of high quantity of organic material. There is also present

strong smell of hydrocarbon. On the strata face pyrite can be seen. Eight outcrop samples

were collected from the Teleajen Valley and these rock samples were crushed and grinded

before analysis. The samples were then pyrolized using Rock-Eval 6 in order to determinate

the following parameters: S1 (free hydrocarbon), S2 (oil potential), S3 (CO2 organic source),

Tmax (maximum temperature), TOC% (Total Organic Carbon), HI (Hydrogen Index) and OI

(Oxygen Index). These parameters indicate the maturation conditions of the source rocks and

detect the petroleum potential of sediments. Interpretation of these results leads to

determination of kerogen type, maturity level, generated hydrocarbons and generation

potential. All the samples with higher TOC content were selected for vitrinite reflectance

measurements. The samples for vitrinite reflectance were cut perpendicularly to the bedding

plane, mounted in epoxy resin and polished. Using a J& MMSP 200 software the results were

plotted as histograms and interpreted based on different maceral population occurrence

modes.

The samples have not reached maturity since Tmax individual values are less than 435°C

but it must be considered that they were collected from outcrops which are subjected to

surface environmental conditions and due to this fact the maturity level resulted cannot be

interpreted as accurate. The pseudo-Van Krevelen diagram indicates that organic matter

belongs to kerogen type II and III.

mailto:[email protected]




62

Source potential is interpreted according to TOC% values which range between 2.33% and

12.87% and S2 with very good values (32.42%, 39.96%, 42.57% and 71.01%), indicating

that the samples have very good to excellent source rock generation potential.

a b c

d e f

Fig. 1. Photomicrographs of different types of macerals, reflected light, oil immersion, 50X;

a, b, d, f: vitrinite; c, e: inertinite.

The samples collected from Oligocene sedimentary formation located in the Teleajen

Valley, indicate a very good to excellent source rocks formation for generating oil and gas,

and kerogen types II and III.

Acknowledgments: The authors sincerely thank Prof. Dr. Cornelia Panaitescu and Dr. Georgeta Predeanu from

the University Politehnica Bucharest for their assistance and kind support when learning coal petrology.

References

Peters K.E., Cassa M.R. 1994 - The Petroleum System – From Source to Trap. Chapter 5: Applied Source Rock

Geochemistry: 93-120.

Panaitescu C. 1991 - Coal Petrography, Cokes and Carbon Products. Ed. Enciclopedica: 1-323.

Panaitescu C., Predeanu G. 1999 - Atlas Carbopetrografic. Ed. Academiei Romane, (Romanian-English version):

1-264.

Peters K.E. 1986 - Guidelines for Evaluating Petroleum Source Rock Using Programmed Pyrolysis: 318-329.


63

Petrographic characteristics of the solid bitumen present in the samples

from Cabaços Formation (Lusitanian basin, Portugal)

P.A. Gonçalves1, F.S. da Silva

2, J.G. Mendonça Filho

2, D. Flores

1,3

1Centro de Geologia da Universidade do Porto, Rua Campo Alegre, 687, 4169-007 Porto, Portugal;

[email protected] 2 Laboratório de Palinofácies & Fácies Orgânica (LAFO), Departamento de Geologia, Instituto de Geociências,

Universidade Federal do rio de Janeiro, Av. Athos da Silveira, 274, prédio do CCMN, sala J1020, Campus

Ilha do Fundão, Cidade Universitária, CEP 21.949-900 Rio de Janeiro, RJ, Brasil 3 Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências, Universidade

do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal

Solid bitumens (“migrabitumen”) are secondary organic matter products that filling voids and

fractures in rocks (Jacobs, 1989) and can occur in carbonate and siliciclastic rocks. In the

Lusitanian basin (Portugal), several formations, from the Early Jurassic until the Cretaceous,

revealed the presence of solid bitumen. The study of the Freixial-1 and Benfeito-1 wells

(Arruda sub-basin, Lusitanian basin) revealed large amounts of solid bitumen in the Cabaços

Formation, the lowermost formation of the Upper Jurassic. This formation comprises

limestones and anhydrite-limestone sequence. To study the petrographic characteristics of

solid bitumen present in these samples, microscopy techniques (reflected and transmitted

white light, incident blue light and SEM) were used.

Solid bitumen occurs in all the samples of the Cabaços Formation but it increased in the

anhydrite rich samples in which, when observed in transmitted white light, the solid bitumen

represent over 50% of the organic matter fraction.

In transmitted white light the solid bitumen had amorphous aspect with dark color (Figure

1A) and no fluorescence under incident blue light. SEM observations confirm the amorphous

aspect (Figure 1B). In both methods of observation is possible to notice the cratered aspect of

the solid bitumen resulting from the dissolution of carbonate minerals by the HCl treatment.

In whole rock samples and under reflected white light, these solid bitumens had a grey

color, brittle aspect and appear filling the inter-mineral spaces (Figure 1C). The solid bitumen

shape varies according to the pores shape where it occurs. The bitumen reflectance ranges

from 1.5 to 1.8%Ro. According to the classification proposed by Jacob (1989), and based only

in the %Ro values, the solid bitumen identified in these samples are classified as epi-

impsonites.



64

Fig. 1. Photomicrographs illustrating solid bitumen in Cabaços Formation (Upper Jurassic sediments from the

Lusitanian basin). a) transmitted white light; b) SEM; c) reflected white light.

Geochemical studies will be carried out to provide a better understanding of these solid

bitumens.

Acknowledgments: The first author is grateful to Fundação para a Ciência e Tecnologia (FCT) for the financial

support (scholarship SFRH/BD/60875/2009). This work was sponsored by the Scientific and Technical

Cooperation Agreement FCT (Portugal)/CAPES (Brazil) project titled “Caracterização das variações

organofaciológicas e identificação dos horizontes potencialmente geradores de petróleo no Jurássico da Bacia

Lusitânica”; and partially funded by FEDER funds through the Operational Program Competitiveness Factors -

COMPETE and by national funds through FCT - Fundação para a Ciência e Tecnologia, under the project PEst-

OE/CTE/UI0039/2011.

References

Jacob H. 1989 - Classification, structure, genesis and practical importance of natural solid oil bitumen

(“migrabitumen”). International Journal of Coal Geology 11: 65–79.

b c a Solid Bitumen

20µm 20µm 100µm


65

Changes in optical properties of liptinite macerals from early mature to

post mature stage in Posidonia Shale (Lower Toarcian, NW Germany)

O.O. Gorbanenko1,2

, B. Ligouis1

1Eberhard Karls University Tübingen, Institute for Archaeological Sciences, Work Group of Geoarchaeology,

Laboratory for Organic Petrology, Rümelinstr. 23, 72070 Tübingen, Germany; +49-(0)7071-29-74688,

+49-(0)7071-29-74087; [email protected], [email protected] 2Eberhard Karls University Tübingen, Department of Geosciences, Work Group of Biogeology, Sigwartstr. 10,

72076 Tübingen, Germany

Detailed organo-petrological analysis was carried out on core samples from two wells, which are

located in North-Western Germany. The distance between wells is about 60 km. Organic matter in

one well is early mature, whereas that in the other is post mature. A total of 72 samples of

Posidonia Shale (Lower Toarcian) were analyzed to investigate the optical properties of three

macerals of the liptinite group: telalginite, bituminite and sporinite.

Results of organo-petrological analyses demonstrate that telalginite (Tasmanales alginite)

in early mature oil shales was observed as a disk-shape body with length ranging between 60

and 120 μm. In reflected white light telalginite appears brown to dark brown, whereas in

fluorescence mode it shows yellow color of high intensity. In contrast, in post mature oil

shales, relics of former telalginite occurs in three forms. One consists of a chain of calcareous

crystals or of a completely recrystallized calcareous mass. Both are associated with

homogeneous and heterogeneous reflecting solid bitumen. Second form is composed

completely of epigenetic pyrite. The third form is rare and consists of “telalginite” completely

replaced by reflecting homogeneous bitumen (impsonite; Jacob, 1983, 1989). All forms of

telalginite relics in post mature oil shales show no fluorescence and are non-fluorescing. In

addition, the shape and size of the algae are preserved.

In oil shales of early mature stage, bituminite I (Teichmüller, 1977) is characterized by a

very low reflectance and a brownish fluorescence color. It often includes yellow fluorescent

liptodetrinite. Bituminite I has indinstinct lense shape with length reaching up to 60 μm. On

the contrary, in post mature oil shales on the basis of morphology, it appears as light-grey

lenses, consists of massive micrinite and shows no fluorescence.

Bituminite II (Teichmüller, 1977), in early mature oil shales, occurs as thick elongated

homogeneous lenses associated with carbonate crystals and with yellow-brownish

fluorescence often with greenish fluorescent oil expulsions. In post mature oil shales,

“bituminite II” consists of a network of micrinite and has no fluorescence.


66

Sporinite is very rare in the investigated oil shales. It has very low reflectance and orange-

brown fluorescence of moderate intensity. In post mature oil shales, sporinite is filled with

pyrite crystals which emphasize the sporinite form, is characterized by reddish-orange internal

reflections, and is either non-fluorescent or shows weak fluorescence of mineral origin.

Australian petrologists Cook (1986) and Hutton (1987) has developed the most widely

accepted nomenclature of liptinite macerals in oil shales. Particularly, they proposed the terms

telalginite (Botryococcus, Tasmanites, Leiosphaeridia) and lamalginite (lamellar alginite).

However, their work was focused on the alginite in early mature and mature oil shales.

Teichmüller and Ottenjann in 1977 defined bituminite I, bituminite II and bituminite III in

early mature and mature Toarcian oil shales. They study the modifications in optical

properties of bituminite in several oil shales of increasing maturity, and used the term “meta-

bituminite” to classify the organic substances generated from bituminite (Teichmüller, 1974).

This study demonstrates that the existing terms (micrinite, micritic residues, solid bitumen,

overmature exsudatinite…, Taylor et al, 1998) are not completely suitable to describe the

various organic substances form especially from the telalginite, bituminite and sporinite in the

post mature oil shales.

Acknowledgements: This work was financed by Shell International Exploration and Production B.V.,

Netherlands, which is gratefully acknowledged. We would also like to thank ExxonMobil Production

Deutschland GmbH and Shell Erdgas Beteiligungsgesellschaft mbH for the permission to share the data.

References

Cook A.C., Hutton A.C., Sherwood N.R. 1986 - Classification of oil shales. Bull. Cent. Rech. Explor.- Prod.

Elf.-Aquitaine, 5, 2: 353-382.

Hutton A.C. 1987 - Petrographic classification of oil shales. Int. J. Coal Geol., 8: 203-231.

Jacob H. 1983 - Neuere Untersuchungen zur Genesis natürlicher, fester Erdölbitumina. Geol. Jahrb., D59: 3-61.

Jacob H. 1989 - Classification, structure, genesis and practical importance of natural solid bitumen

(“migrabitumen”). Int. J. Coal Geol., 11, 1: 65-79.

Taylor G.H., Teichmüller M., Davis A., Diessel C.F.K., Littke R., Robert P. 1998 - Organic petrology. Gehrüder

Borntraeger, Berlin, Stuttgart: 1-704.

Teichmüller M. 1974 - Entstehung und Veränderung bituminöser Substanzen in Kohlen in Beziehung zur

Entstehung und Umwandlungdes Erdöls. Fortschr. Geol. Rheinl. u. Westf., 24: 65-112.

Teichmüller M., Ottenjann K. 1977 - Liptinite und lipoid Stoffe in einem Erdölmuttergestein. Erdöl und Kohle,

30, 9: 387-398.


67

Variation of coke optical texture with the addition of artificially prepared

inertinite size fractions

A. Guerrero, M.A. Diez, A.G. Borrego

Instituto Nacional del Carbón (INCAR-CSIC); C/ Francisco Pintado Fe 26, 33011 Oviedo, Spain

The inertinite in coal, and its behavior during the coking process, is a key factor in the

mechanical strength and reactivity of the resultant cokes (Mackowsky 1976). It is generally

considered that the small inertinite particles (<50 m) may be well-integrated in the coke

matrix, having a beneficial effect in the mechanical strength, whereas the large particles

represent surfaces of discontinuity (Brown et al. 1964). This work address the effect of

“inertinite” addition in the optical properties of a good coking coal, having well-controlled

both the particle size and the amount.

For this propose a relatively low fluidity coal (LFC) with Gieseler maximum of 373 ddpm,

1.24% vitrinite reflectance and vitrinite/inertinite content of 77/23 has been selected. The coal

has been blended with charcoal (CH) attempting to represent artificially-prepared inertinite

under controlled conditions. Three fractions have been prepared from the charcoal (Fig.1):

<20m (CH20); 20-80 m (CH80) and 80-212 m (CH212) and have been added to coal in

amounts of 5 and 15 wt%.

Fig.1. SEM images from: a) CH20, b) CH80 c) CH212.

The LFC-CH blends have been carbonized at 500ºC (residue from Gieseler fluidity tests)

and 1000ºC to obtain both semicoke and coke samples. For each sample an optical texture

analysis has been performed recording around 500 counts.

Most inertinite in the coal had low relief, except fusinite and some inertodetrinite. This

give rise to smooth contact edges between the coke matrix and the inertinite in the coke. The

added charcoal particles maintain cell-wall structure, resembling fusinite, but lack any

evidence of deformation/compaction. They typically exhibited high polishing relief and this

feature has been distinguished in the classification scheme, together with their size (Table 1).

The inertinite particles still retain their optical features in the semicoke and therefore they

are more easily distinguished from the charcoal particles than in the coke. In the semicoke the

inertodetrinite can be distinguished from CH20, whereas in the coke most inertodetrinite have

a) b) c)

100μm 200μm 20μm


68

adquired high relief, being virtually indistinguishable from the charcoal. The LFC coke matrix

is mainly formed by domain texture and most of the inertinite have smooth edges. The

addition of charcoal to the coal generally causes a size decrease of the optical texture in the

matrix of both coke and semicoke. A 5% of charcoal addition causes significant decrease in

the size of the optical texture. This decrease is more pronounced adding a higher amount of

charcoal. This effect is more pronounced in the case of the finest charcoal. This can be

explained by both a physical and a chemical effect. On the one hand, close association of

coal-charcoal in the fine sizes impedes the growth of large anisotropic domains. On the other

hand, the small particles provide higher surface area for reaction favoring the nucleation of

larger amount of anisotropic structures.

Table 1. Optical texture (vol %) analyses of cokes and semicokes.

Values in bold refer to the percentage in the sample and the others to the percentage in their respective class.

OG LFC-CH212

15%

LFC -

CH212

5%

LFC -

CH80

15%

LFC -

CH80

5%

LFC -

CH20

15%

LFC -

CH20

5%

SE

MIC

OK

E (

50

0 º

C)

MATRIX 71.6 59.4 71.1 57.0 66.2 54.1 65.2

Isotropic 1.7 3.7 1.9 10.3 5.1 16.7 2.1

Mosaic 3.1 17.5 1.9 42.0 20.2 51.5 16.6

Domain 93.1 74.1 95.3 46.6 74.0 27.7 75.8

Fibers 2.0 4.7 0.9 1.1 0.6 4.2 5.5

INERT INCLUSIONS 26.8 39.4 28.0 41.3 31.6 44.5 32.2

Smooth Edges Inertinite 71.0 40.6 57.6 24.7 36.7 33.2 45.3

Inertodetrinite 18.3 11.2 9.6 8.4 15.2 7.8 13.7

Sharp E. .I. 212-80 µm 6.1 35.5 20.8 7.9 10.8 1.8 5.0

Sharp E. I. 80-20 µm 2.3 7.6 6.4 46.3 25.9 6.0 3.7

Sharp.E. I. <20 µm 2.3 1.5 3.2 10.5 10.8 51.2 31.1

Div. Isotropic Inclusions 0.0 3.6 2.4 2.1 0.6 0.0 1.2

MINERAL MATER 1.6 1.2 0.9 1.7 2.2 1.4 2.6

CO

KE

(100

0 º

C)

MATRIX 70.2 57.2 67.1 62.2 68.2 50.2 63.6

Isotropic 6.4 8.4 6.2 1.9 5.3 23.9 4.4

Mosaic 15.6 39.2 33.5 21.2 26.7 57.0 38.7

Domain 67.6 50.3 56.2 69.1 65.1 17.9 52.8

Fibers 10.4 2.1 4.0 7.7 2.9 1.2 4.1

INERT INCLUSIONS 29.0 41.6 31.0 37.0 31.0 49.0 35.2

Smooth E. Inertinite 65.7 6.7 26.8 24.3 18.7 5.7 18.8

Sharp E. .I. 212-80 µm 13.3 37.5 44.3 8.1 20.0 12.7 22.2

Sharp E. I. 80-20 µm 2.1 33.2 9.4 45.4 30.3 4.9 9.1

Sharp.E. I. <20 µm 14.0 14.9 12.8 20.0 30.3 73.1 50.0

Div. Isotropic Inclusions 4.9 7.7 6.7 2.2 0.6 3.7 0.0

MINERAL MATER 0.8 1.2 1.9 0.8 0.8 0.8 1.2

Acknowledgement: The research leading to these results has received funding from the Research Programme of

the Research Fund for Coal and Steel (Grant Agreement number RFC-PR- 09024). The financial support of

MICINN through a bilateral Spain-Brazil project PIB2010BZ-00418 and PCTI through COF11-39 is also

gratefully acknowledged.

References

Mackowsky,, M-Th. 1976 - Prediction methods in coal and coke microscopy. J. Microscopy 109: 119-137.

Brown H.R., Taylor G.H., Cook A.C., 1964 - Prediction of coke strength from the rank and petrographic

composition of Australian coals. Fuel 43: 43–54.


69

Migration ability of the trace elements from the overburnt mining waste

material depending on the pH of the aqueous environment

B. Hanak, J. Nowak, M. Kokowska-Pawłowska, K. Nowińska Silesian University of Technology

Mining waste materials are the largest group of post-industrial wastes in Poland. From the

petrographic point of view, the mining wastes are mainly sedimentary clastic rocks

(mudstones, sandstones and claystones), which contain a variable amount of organic matter

(carbon). Most of mining wastes produced is currently developed, but in XIX and XX century

this wastes were mainly deposited on the dumping grounds.

Oxidation of organic matter (coal) and ferrous sulfides contained in wastes leads to their

self-heating and consequently to initiating of endogenous fires. During the fires a temperature

on dumping ground increases to hundreds and even up to more than thousand degrees Celsius.

High temperature interaction caused changes of the mineralogical and petrographic

properties of the wastes.

On the basis of the studies conducted on mining wastes dumping ground on the GZW area,

three zones of varying degrees of thermal alteration of wastes were separated. There are:

- Thermally untransformed zone (the wastes with petrographic characteristic

and mineralogical composition close to original, high concentration of organic matter)

- Moderately thermally transformed zone (in the wastes metakaolin is presented, lack

or low concentration of organic matter),

- Intensively thermally transformed zone (in the wastes glaze is presented).

Formations from intensive thermally altered zone, except glaze, are characterized by the

presence of high-temperature minerals, such as cordierite, mullite, sillimanite, magnetite and

other spinels, pyroxene. Pores in different sizes often occur in this formations.

Wastes, depending on presence in one of this zones, exhibit variable properties, which

determine their practical application. One of the most important information, which decide

about the direction of wastes utilization, is determination of their harmful effects on

environment, by the release of trace elements in water presence. It was found that the highest

release of elements take places in the case of waste from intensive thermally altered zone.

Five samples of intensive thermally altered mining wastes of diverse glaze participation

were subjected to leaching tests. Leaching were conducted in water of 5; 6; 7,5 and 8 pH.

Mixture of HCl and H2SO4 1:1 was used for acid reaction, NaOH for alkaline reaction. The

samples were shaken during 24 hours. Concentrations of As, Ba, Cr, Cu, Ni, V were analyzed

in eluates using ICP-AES spectrometer type JY 2000. Concentrations of aforementioned

elements were also analyzed in solutions of dissolved wastes samples.

The highest concentration in wastes of analyzed metals showed barium, whose content in

samples ranged from 313 to 390 ppm (average 357). Average concentration of

vanadium was 78 ppm (min. 30, max. 120 ppm). Relatively high concentration showed also

copper (average 42 ppm, range 30 – 51 ppm) and nickel (average 30 ppm, range 8 – 91 ppm).

Significantly lower concentration of arsenic was found, which averaged 6 ppm (min, 4 max.

9). The lowest concentration showed chromium (1-4 ppm).

On the basis of the studies, high mobility of chromium was found (in spite of the low Cr

concentration); in extreme cases even above 5% chromium contained in the sample have been

leached to solution during 24 hours. This element stronger was eluted in acid environment

(pH 5 or 6) than neutral and alkaline environments.


70

Arsenic was the another element, which easy eluted to solution. During 24 hours of

leaching time, even up to 2,3% of As contained in wastes have been leached to solution.

Clearly marked decline in the ability of arsenic elution with increasing pH.

Although the concentration of barium in analyzed samples was the highest, this

element showed limited ability to leach. During leaching maximally about 0,5% barium

contained in waste eluted to solution. This element concentration clearly decreased with the

increase of pH.

Nickel and vanadium showed much lower capacity to leach. In the cases of nickel only

tenths of percent of this element have been leached to solution, and vanadium only

hundredths of percent. For both of these elements decrease of their concentrations in eluates

with the increase of pH was observed.

The studies showed that least mobile element was copper. In the eluates there was no or

trace concentrations of Cu.

Individual samples also showed differentiation capacity of the elements leaching depend

on glaze content in sample. Unfortunately, dependence between the glaze content and

leaching capacity elements was not confirmed. Probably this capacity depends not only on

glaze content, but also on quantity and type of high-temperature minerals. This problem

requires further, more detailed mineralogical studies.

Studies have been financed in the framework BK-290/RG7/2012.


71

Petrographic and geochemical investigation of coal slurries

and its products as the results of the combustion process

I. Jelonek, Z. Mirkowski

University of Silesia, Faculty of Earth Sciences, 41-200 Sosnowiec, Będzińska 60, Poland;

+48 32 3689498; [email protected]

Coal slurries are a very fine-grained by-products of coal enrichment, which was stored in the

recent past as a waste product in ground ponds. Currently, with the introduction of fluid

boilers into the Polish energy sector, coal slurries are becoming a sought-after fuel. Coal

slurries are a lower quality fuel characterised by a high ash (24-35 %) and moisture (31-38 %)

content, and therefore a low lower heating value (8-11 MJ/kg). Its weak and variable quality

parameters mean that coal slurries are not used in power plants as an independent fuel, but as

an additive to pure coal in quantities from 17 to 40 %.

The maceral content of samples of coal slurries, taken from a single manufacturer but

different times of the year, was tested. One characteristic feature is the high proportion of

macerals from the inertinite group (from 51.7% to 57.6%), with a simultaneous decrease in

the content of macerals from the liptinite group (from 3.0% to 5.5%). There is also a clear

dominance of detrital macerals (up to 71 %), of which the most numerous group is

inertodetrinite (up to 47 %). In the sample of enriched coal from the same producer tested for

comparison, the detrital maceral content reached 20 %.

An analysis was conducted of the forms of unburnt organic materials in samples of ash

obtained from burning a mixture of coal and the coal slurries described above. The results

obtained with regard to mineral content (around 80 %) and carbon content (around 0.6 %)

indicate that even the addition of a significant amount of coal slurries to fuel does not cause it

to burn any less efficiently. Detritus clearly dominates among the unburnt organic material,

alongside smaller amounts of solid forms, networks and cenospheres. In the sample of ash

from coal with added slurries, detritus appears in much smaller quantities alongside every

possible form of unburnt organic material.

Tests of coal slurries samples using a scanning microscope show a similar set of minerals

as in coal samples. There is a clear dominance of iron silicates and sulphates, with a smaller

amount of silty minerals and mica. Analogous tests on ash samples show a dominance of silty

minerals and iron oxides. The varied constitution of volatile and bottom ashes is evident. The

bottom ashes contain larger accumulations of sulphates, silicates and clay silicate enamel. The

mineral phases indicated are confirmed by X-ray analysis which demonstrates a large

proportion of quartz, anhydrite, haematite, illite and feldspar.


72

The relationship between methane contents and variability of coal rank

within the Upper Silesian Coal Basin, Poland

S. Kędzior University of Silesia, Faculty of Earth Sciences; +48 32 36 89 329; [email protected]

The process of coalification results in changes in coal inner structure concerning both

chemical composition and physical properties of coal substance. One of the most important

stages in development of bituminous coal is so called “second coalification jump”

corresponding to medium volatile coals (e.g. Teichmüller 1989), which is distinguished by

decay of aliphatic bonds and expand of aromatic hydrocarbons in vitrinite macerals with

increasing arrangement of them. A distinctive feature of this stage is significant decrease of

volatile matter from 33% to 20% (Kruszewska, Dybova-Jachowicz 1997). Decreasing of

volatiles is accompanied by release of methane, carbon dioxide and water (e.g. Kopp et al.

2000; Moore 2012).

The Upper Silesian Coal Basin (USCB) is characterized by diversity of coalbed methane

occurrence. The outhern, western and central parts of the basin are methane rich while the east

and north parts are poorer in methane. In general, the upper parts of the rock mass in the basin

have a lower methane content, next it increases up with depth and achieves the highest values

within the interval of ca 800-1500 m under the surface of area, whereas deeper it decreases.

The purpose of this study is a comparison between methane spatial distribution (methane

content in coal) and variations of coal rank, represented by vitrinite reflectance (Ro), volatiles

content (Vdaf

) and H/C atomic ratio. The data of methane contents and the parameters given

above, obtained from 21 bore-holes drilled in order to explore the coal deposits within the

USCB Main Syncline, are now archived in Polish Geological Institute.

The comparison results of methane contents and selected parameters of coalification show

that the highest values of methane content (>10 m3/t coal daf) correspond to 35-22% volatiles

range, and to 0.84-1.26 % vitrinite reflectance respectively. The value of 0.70 H/C atomic

ratio matches the highest value of methane content equal 9,1 m3/t coal daf.

The highest values of methane content are more or less in accordance with coalification

parameters corresponding to the second coalification jump (Vdaf

– 29%, Ro – 1.3%), i.e.

cooking coals. Within this stage coal loses about 10% of volatiles, what involves the

producing of significant amount of thermogenic gases (including methane).

In the USCB the configuration of the top of high methane zone (4.5 m3/t coal daf) is quite

similar to the lay of the cooking coals top (Kwarciński, Hadro 2008). That is why increasing

methane contents in the southern and western parts of the basin can be explained by the

increasing percentage of cooking coals towards these directions. The values of volatiles,

vitrinite reflectance and H/C atomic ratio corresponding to the highest methane content (>10

m3/t coal daf) in relation to cooking coals occurrence is shown in Table 1.

Presented data reveal that coalification stage related to the second coalification jump plays

a part in the process of methane generation. Similar results were obtained in Czech part of the

USCB (Hemza et al. 2009). However, quite weak correlation between present methane

content and individual parameters of coal rank (correlation coefficient about 0.3) results in

subsequent processes including gas migration and accumulation caused by such geological

conditions like lithology, tectonics, maceral composition of coal, hydrodynamics etc. (eg

Kędzior 2009; Moore 2012).



73

Table 1. The intervals of volatiles (V

daf) and vitrinite reflectance (Ro) correspond to the highest values of

methane content (>10 m3/t coal daf) in relation to presence of cooking coals

Areas

Without cooking coal With cooking coal below

top surface of the

Carboniferous strata

With cooking coal

reaching the top surface

of Carboniferous strata

Vdaf

[%] - 35-23 28-23

Ro [%] - 0.82-1.25 1.05-1.25

“-“ no value of methane content > 10 m3/t coal daf

References

Hemza P., Sivek M., Jirásek P. 2009 - Factors influencing the methane content of coal beds of the Czech part of

the Upper Silesian Coal Basin, Czech Republic. International Journal of Coal Geology, 79: 29 – 39.

Kędzior S. 2009 - Accumulation of coal-bed methane in the south-west part of the Upper Silesian Coal Basin

(southern Poland). International Journal of Coal Geology, 80: 20 – 34.

Kopp O.C., Bennett III M.E., Clark C.E. 2000 - Volatiles lost during coalification. International Journal of Coal

Geology, 44, 69 – 84.

Kruszewska K., Dybova-Jachowicz S. 1997 - The outline of coal petrology. Wyd. Uniw. Śląskiego, Katowice

[in Polish].

Kwarciński J., Hadro J. 2008 - Coalbed methane in the Upper Silesian Coal Basin. Przegląd Geologiczny, 56:

485 – 490 [in Polish with English abstract].

Moore T. A. 2012 - Coalbed Methane: A review. International Journal of Coal Geology, 101: 36-81.

Teichmüller M., 1989 - The genesis of coal from the viewpoint of coal petrology. International Journal of Coal

Geology, 12: 1 – 87.


74

Relationship between the content of trace elements in coal lithotypes

and their ashes (405 coal seam, USCB)

M. Kokowska-Pawłowska

Institute of Applied Geology, Faculty of Mining and Geology, Silesian University of Technology, Akademicka 2,

44-100 Gliwice, Poland

Variable concentrations of trace elements in coal seams depend mainly on their genesis and

differentiated geochemical affinity with the organic and mineral matters of coal (Winnicki

1973; Widawska-Kuśmierska 1981; Różkowska, Ptak 1995; Lewińska-Preis et al., 2001;

Hanak, Kokowska-Pawłowska, 2006).It has been found that a variable level of mineralization

and composition of mineral matter in coal influences the differentiation of trace elements

contents in the lithotypes. Most frequently, the highest concentrations of trace elements have

been observed in dull coal, a lower one in semi-vitrous and vitrous coals (Hanak, Kokowska-

Pawłowska, 2007).

Because of differentiated character of mineralization in individual lithotypes, a decision

has been taken to investigate dependence between variability of trace elements concentrations

in lithotypes and in the ashes on the basis of coal samples from the 405 coal seam (Załęże

beds). 61 piece-form samples of petrographic types of coal from 6 profiles from 405 coal

seam have been investigated. Geochemical measurements of samples representing

distinguished lithotypes have been conducted by the Geoanaliza company with use of

Instrumental Neutron Activation Analysis (INAA). In lithotypes and ashes the following trace

elements concentrations have been measured: Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn, Mn, Be, Li, V,

As, and Ga.

To demonstrate a relationship between contents of elements in the lithotypes with organic

or mineral matter in coal, enrichment coefficient (W) values have been calculated for the

ashes of lithotypes as a ratio of an element contents in the ash to its contents in the lithotype.

The assumption was that coefficient W values increase with increasing contents of an element

related to the organic matter of coal.

In samples of lithotypes from 405 coal seam and their ashes, analyzed trace elements

exhibited variable concentration in a differentiated range.

Within all distinguished lithotypes the highest contents was shown by elements Ba and

Mn. The other evaluated elements could be categorized due to average contents in the

lithotypes in following order: Zn<Pb<V<Cu<Ni<Cr<Ga<Co<Be<Li<As<Cd. The similar

trend of elements contents has been observed also by the ashes from the lithotypes.

Variability of the enrichment coefficient values is also quite evident. The highest values of

these coefficients (from 5 to 7) were shown by Cr, Be, Cd, and Cu. The other elements exhibit

lower values (from about 2 to about 3) and the lowest values of the enrichment coefficient

most frequently were observed in case of Co, Li, and Mn.

On the basis of calculated enrichment coefficient values in the ashes it has been found out

that such elements as Ba, Mn, Li, As, Co, Ga, Ni, Pb, and Zn demonstrated high affinity to the


75

mineral substance (low enrichment coefficient in the ash). Their maximal concentrations

decreased for the strongly mineralised lithotypes – dull coal or semi-vitrous coal.

However, a small number of elements as Cr, Be, Cd, and Cu demonstrated high affinity to

organic matter of coal (high enrichment coefficient in the ash) and a trend to maximal

concentration in vitrous lithotype.

References

Hanak B., Kokowska -Pawłowska M. 2006 - Variability of the trace element contents in the coal lithotypes and

their ashes presented on the background of the 630 coal seam (U.S.C.B.). Gospodarka Surowcami

Mineralnymi, 22, 3, Kraków: 68-77.

Hanak B., Kokowska-Pawłowska M. 2007 - The influence of the mineral substance on the content of the

selected trace elements of the lithotypes from the coal seam 308 (Ziemowit Coal Mine). Kwartalnik, seria

Górnictwo i Geologia, 3, 2, Gliwice: 31-41.

Lewińska-Preis L., Biedroń J., Fabiańska M. 2001- Geochemical assessment of the trace elements concentrations

distribution in fractions of coal after bio-desulfurization process. Zeszyty Naukowe Politechniki Śląskiej.

Seria: Górnictwo, 249.

Różkowska A., Ptak B.1995 - Minor and trace elements in the Upper Silesian coal. Przegląd Geologiczny, 43, 6:

478-481.

Widawska – Kuśmierska J. 1981 - The occurrence of trace elements in Polish coal. Przegląd Górniczy, 7-8:

455-459.

Winnicki J. 1973 - Presence and the way of occurrence of the rare elements in the national coals. Scientific

Papers of the Institute of Inorganic Chemistry and Metallurgy of Rare Elements. Conferences no. 8: 3-71.


76

Changes of the vitrinite and liptinite structures during heating

under inert conditions according to the results of Micro-FTIR spectroscopy

J. Komorek

Silesian University of Technology, Faculty of Mining and Geology, Institute of Applied Geology, Akademicka 2,

44-100 Gliwice, Poland; [email protected]

The examination was performed on vitrinite and liptinite concentrates. They were prepared

from three channel steam coal samples from Upper Silesian Coal Basin. The samples were

collected from the coal seam 405. The concentrates were obtained by gravity separation in the

mixture of toluene and tetrachloroethylene. About 500mg of each concentrate was heated in a

Carbolite pipe oven at temperatures 400, 500, 600, 800, 1000 and 1200oC for 1h in an argon

atmosphere. The concentrates were inserted in the oven at room temperature. The rate of

temperature increase was 60oC/min.

Micro-FTIR analysis was performed on individual raw and carbonized vitrinite and

liptinite (sporinite) grains. Micro-FTIR measurements were performed in reflectance mode

with use of Bio-Rad FTS-6000 spectrometer equipped in the Bio-Rad UMA-500 microscope.

Spectra were obtained within range 4500-700cm-1

, with resolution 4cm-1

. Interferograms were

collected by cumulating of 512 scans. The spectra were converted using a Fourier and Kramer

Kronig transformation.

To analyze the micro - FTIR spectra it was necessary to take into account absorption bands

present in the the following ranges:

- 3030-2800 cm-1

– band associated with the stretching of aliphatic groups

(CH2+CH3),

- 1650-1500 cm-1

– band associated with the aromatic rings C=C stretching,

- 900-750 cm-1

– band associated with the aromatic groups CHar out of plane

deformations.

Changes in the vitrinite and sporinite structure after heating were described by the

following ratios of spectral bands integrations areas:

i . These ratios were used to

demonstrate relative content of aliphatic and aromatic components.

Changes of the condensation structure aromatic rings were described by the ratio

(Guo & Bustin, 1998).

It was found that raw vitrinite is characterized by higher relative content of aromatic than

aliphatic components. Whereas the structure of raw sporinite is characterized by higher

content of aliphatic than aromatic bonds. The results show that when the temperature rises the

relative content of aromatic hydrogen functional group CHar and condensation of the structure

of carbonized vitrinite and liptinite increase.


77

The significant negative correlation between I3 and I2 ratios calculated for all examined raw

and heated vitrinites was observed. With increase of the aromatic hydrogen group CHar

content aromatic ring C=C stretching decreases. This phenomenon has been observed by

Amijaya et.al. (2006) and Vassallo et.al.(1991). The decrease of absorbance in the 1600 cm-1

band is probably a consequence of the loss of phenolic OH bond than/or the change of

aromatic ring content.

Studies have shown that in the structure of carbonized liptinite, with the increase of CHar

aromatic hydrogen group relative content, aliphatic components (CH2+CH3) relative content

decrease. It can be concluded that the increase in aromaticity of carbonized liptinite with the

rises of temperature causes the loss of aliphatic components.

It was found that although apparent differences in the structure of vitrinite and liptinite

before heating was observed, the final products of thermal treatment of analyzed samples

(concentrates after heating at 1000 and 1200°C) are characterized by similar participation of

particular functional groups (CH2+CH3), C=C, CHar. Likewise, the degree of condensation of

aromatic rings expressed by a ratio I4, for the products carbonization vitrinite and liptinite

after heating of samples at 1200oC present similar values, take into account the standard

deviation.

References

Amijaya H., Littke R. 2006 - Properties of thermally metamorphosed coal from Tajung Enim area South Sumatr

Basin, Indonesja with special reference to the coalificaton path of macerals. Int. Journal of Coal Geology, 66:

271-295.

Guo Y., Bustin R.M. 1998 - FTIR spectroscopy and reflectance of modern charcoals and fungal decayed woods:

implication for studies of inertinite coals. Int. Journal of Coal Geology, 37: 29-53.

Vassallo A. M., Liu Y. L., Pang L. S. K., Wilson M 1991 - A infrared spectroscopy of coal macerals

concentrates at elevated temperatures. Fuel, 70: 635-639.


78

Application of confocal laser-scanning microscopy (CLSM) to qualitative

and quantitative examination of bituminite in Jurassic oil shales

J. Kus, Ch. Ostertag-Henning Federal Institute of Geosciences and Natural Resources, Stilleweg 2, D-30655 Hannover; 0049 (0) 511

6432629; [email protected]

Oil shales represent conventional and unconventional source rocks and are expected to

become far more relevant resources in the global and national economies, especially in the

Austral-Asian region as strong demand from the emerging economies of China and India

impacts on the upwards trend of the “Brent” crude oil and the OPEC basket price, (BGR

2012).

Within the currently undertaken study by the Federal Institute for Geosciences and Natural

Resources on the Gas and Oil Potential from Shales (NIKO), assessment of untapped

potential in unconventional oil shale resources of Germany is conducted (BGR 2011). The

multidisciplinary survey explores also novel techniques in characterisation of intra- and

intergranular pore space in siliciclastic and carbonate sedimentary source rocks as well as

cementation processes and adsorption characteristics.

The aim of this study is the in-depth investigation of bituminite enclosed in organic-rich,

marine, Mesozoic oil shales with the aid of the CLSM method. The studied samples

correspond to immature and mature source rocks of Posidonia Shale (Lower Jurassic,

Toarcian, Lower Saxony, Germany), Kimmeridge Clay (Upper Jurassic, Kimmeridge, Dorset,

UK) and black shales of the Agua de Madeiros Formation (Lower Jurassic, Sinemurian,

Lisbon District, Portugal).

The current study examines appearance, ultrastructure and spectral fluorescence of

autofluorescent bituminite present in the investigated oil shale samples. The qualitative

CLSM analysis reveals distinct appearance of bituminite at micron scale as observed in

polished particulate pellets. The overall appearance of detected bituminite excited at various

visible laser wavelengths varies markedly displaying the highest contrast at excitation laser

lines of 496 and 633 nm. The most dominant appearance of bituminite exhibits streaks

(“Schlieren”), stringers and lenses and that are tightly packed among the surrounding

inorganic mineral grains. As opposed to its amorphous appearance observed under

conventional incident light microscopes, bituminite can exhibit well defined and differentiated

margins under CLSM. At the ultrastructural level, bituminite stringers or lenses are generally

composed of fine lensoidal to laminae-like constituents of various sizes and fluorescence

spectras being embedded in a fluorescent organic matrix. This network-like character of

bituminite ultrastructure resembles to a certain degree larger bundles of ultralaminae detected

in TEM studies by Largeau et al. (1989). The quantitative CLSM analysis involved

application of spectral fluorescence laser scanning microscopy method enabling

measurements of fluorescence intensity and fluorescence intensity alteration at various laser

wavelengths and time.

The in depth qualitative characterisation of the in general second most abundant maceral

type in oil shales with aid of CLSM method complements multidisciplinary approach of

ultrastructural analysis of mineral and kerogen framework as well as pore systems. Further, it

can support detection of micropores as intraparticle organic porosity in autofluorescent

bituminite.



79

References

BGR 2012 - DERA Rohstoffinformationen 15 (2012). Energy Study. Reserves, Resources and Availability of

Energy Resources 2012.

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/DERA_Rohstoffinformationen/rohstoffinformat

ionen-15e.pdf?__blob=publicationFile&v=3

BGR 2011 - Aktuelle Projekte der Bundesanstalt für Geowissenschaften und Rohstoffe 2012-2016.

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/Resource/resource-2012-

2016.pdf?__blob=publicationFile&v=4

Largeau C., Derenne S., Casadevall E., Berkaloff C., Corolleur M., Lugardon B., Raynaud J.F., Connan J. 1989 -

Occurrence and origin of ‘ultralaminar’ structures in ‘amorphous’ kerogens of various source rocks and oil

shales. Organic Geochemistry, 16: 889–895.

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/DERA_Rohstoffinformationen/rohstoffinformationen-15e.pdf?__blob=publicationFile&v=3

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/DERA_Rohstoffinformationen/rohstoffinformationen-15e.pdf?__blob=publicationFile&v=3

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/Resource/resource-2012-2016.pdf?__blob=publicationFile&v=4

http://www.bgr.bund.de/DE/Gemeinsames/Produkte/Downloads/Resource/resource-2012-2016.pdf?__blob=publicationFile&v=4


80

Highly metamorphosed organic matter – origin and some properties

B. Kwiecińska1, S. Pusz

2

1AGH-Technical University, Al. Mickiewicza 30, PL-30059 Krakow, Poland, [email protected]

2Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Skłodowskiej 34,

41-819 Zabrze, Poland

The group of highly metamorphosed organic matter comprises: graphites, semi-graphites,

anthracites, natural cokes and chars, pyrocarbons and shungites. Investigations made with

OM, SEM and TEM revealed transitional forms: anthracite, meta-anthracite semi-graphite

and graphite (A-MA-SG-G) according to intensification of metamorphism. The stage A has

the greatest interlayer spacing (d002 > 3.40 Ǻ), the lowest degree of graphitization (u < 0.3)

and the smallest crystallite size (Lc and La < 50 Ǻ).

The most metamorphosed form of organic matter is graphite that can have biogenic or

inorganic origin. Biogenic graphite is formed through transformation of carbonaceous

sediments that are usually rich in organic remnants. Inorganic way of formation of graphite is

more difficult to prove, thus several hypotheses concerning the mechanism of deposition of

graphite from gaseous emanations exist. Pure graphite is composed solely of carbon atoms

bonded in a honeycomb network within each graphene sheet. The model of graphitic structure

assumes the existence of the basal hexagonal crystalline lattice of the A9 type.

Graphite shows an amazing versatility to form a wide variety of unusual morphologies,

textures and structures from the macroscopic to the nanoscale. In nature one can find e.g.

tabular hexagonal flakes, plates, irregular impregnations, barrel-shaped crystals, fibrous

crystals, rosette structure or spherical aggregates, ranging from sub-micrometers to 2 cm

across. The variety of morphologies and microstructures results from distortions of the

graphene sheets during growth and by the incorporation of dislocations, disclinations, twin

planes, pentagonal and heptagonal rings.

Specific structure of graphite causes its peculiar properties. Graphite is opaque to the light

- reflectance measurements made on natural cleavage surfaces reveal the value Rmax 17.5%. It

is a good conductor of heat and electricity, resistant to chemicals, with ability to absorb fast-

moving neutrons. Hence, natural graphite is used in variety of application, e.g. as lubricants,

insulation, fillers, refractories, electrodes, moderators in nuclear reactors and others.

Anthracites, from one side, are the final stage of metamorphism of bituminous coals and

from the other side the precursor of the series A-MA-SG-G. They contain more than 91% by

weight of element C and their basic structure consists of stacks of parallel graphene layers,

with the size of about several nanometers. Spatial organization of graphene stacks in

anthracites depends on the degree of their metamorphism and transform gradually from

poorly ordered turbostratic structure up to better-ordered graphite-like structure. In sufficient

thermal-pressure conditions certain anthracites pass to semi-graphite or graphite. Some others

not, dependently on the character of initial organic materials and metamorphic process.

Together with structural alteration of anthracites, the changes in their physical and

chemical properties are observed.



81

Shungite represents strongly metamorphosed, highly condensed carbonaceous matter

occurring in Precambrian sediments in Karelia, Russia. Shungite-bearing rocks have been

classified on their carbon content that can change from above 90 to 10 wt. %. In a further

classification, shungite is subdivided into bright, semi-bright, semi-dull and dull on the basis

of their luster. There are a lot of hypothesis of shungite origin, from being a noncrystalline

carbon form, through some type of bituminous coal, kerogen, bitumen or carbonized

hydrocarbon. Shungites are characterized by curved carbon layers similar to that in natural or

synthetic cokes, organized in turbostratic structure. In individual cases one can see the

relationships between morphology, structure and physical properties of shungites. According

to the Franklin classification, shungites seem to be non-graphitizable variety of carbon. In

shungites, there were found carbon forms very similar to fullerenes.

Because of their specific properties shungites are widely applied as water purifier, paint

pigment, fillers, insulating material and many others.

The term natural coke has been used to describe coal thermally affected by an igneous

intrusive body. The kind of coal alteration depends on the temperature of the intrusion, the

duration of magmatic heating and the distance from direct contact with the igneous rock.

Natural coke is usually dull, compact and hard. It has vacuoles (pores) which are empty or

filled with mineral matter. Close to intrusions there were found small amounts of

carbonaceous materials deposited from a gas phase – natural pyrocarbon.

Natural chars are organic particles with pyrolysis chars morphology occurring in coal

seams and carbonaceous mudstones independently on geological age of the deposits. The rank

of the deposits ranges from lignite to medium volatile bituminous coals. They are formed in

relatively low temperatures while fire on coals or peats.

Natural carbon materials are very important from practical point of view because they are

used as precursors or substitutes of energy- and time-consuming man-made carbon materials.

Natural cokes and chars occurring in nature in rather small amounts are indicators of

paleoenvironments.

References

Jaszczak J.A., Robinson G.W., Dimovski S., Gogotsi Y. 2003 - Naturally occurring graphite cones. Carbon, 41:

2085-92.

Kwiecinska B.K., Murchison D.G., Scott E. 1977 - Optical properties of graphite. Journ.Microscopy, 109.

Kwiecińska B.K., Petersen H.I. 2004 - Graphite, semi-graphite, natural cokes, and natural chars classification –

ICCP system. Int. J. Coal Geol., 57: 99-116.

Duber S., Pusz S., Kwiecińska B.K., Rouzaud J.N. 2000 – On the optically biaxial character and heterogeneity of

anthracites. Int J. Coal Geol., 44: 227-250.

Kwiecińska B.K., Pusz S., Krzesińska M., Pilawa B. 2007 - Physical properties of shungite. IJCG, 77: 455-461.

Melezhik V.A., Fallick A.E., Fillipov M.M., Larsen O. 1999 – Karelian shungite – an indication of 2.0-Ga-old

metamorphosed oil-shale and generation of petroleum: geology, lithology and geochemistry. Earth-Science

Reviews, 47: 1-40.

Kovalevski V.V., Buseck P.R., Cowley J.M. 2001 - Comparison of carbon in shungite rocks to other natural

carbons: An X-ray and TEM study. Carbon, 39: 243-256.


82

Changes in concentrations of selected heavy metals and trace elements

in microbial desulphurization of bituminous coals

(the Lublin Coal Basin, Poland)

L. Lewińska-Preis1, M.J. Fabiańska

1, R. Galimska-Stypa

2, A. Kita

3

1Faculty of Earth Sciences, University of Silesia, 41-200 Sosnowiec, 60 Będzińska Street, Poland

2University of Silesia,

2) Faculty of Biology and Environmental Protection, 4 Jagiellońska Street,

42-700 Katowice, Poland 3 Faculty of Mathematics, Physics and Chemistry, University of Silesia, 40-006 Katowice, 9 Szkolna Street,

Poland

The improvement of environmental and economic coal combustion efficiency is related to a

number of factors from improving the quality of coal, combustion technologies, controlling

devices to emission reducing. So called Clean Coal Technologies (CCT) are defined as

processes and technologies that reduce the negative impact of burning coal in three stages:

pre-combustion, the combustion and post-combustion (Lorenz 2005). One of these methods

improving the quality of the coal (i.e. removing harmful components emitted to the

atmosphere) before its combustion is a method of microbial desulfurization of coal. This

method relies primarily on the removal of pyritic sulfur from coal by oxidation of sulfides to

sulfates, with the participation of microorganisms. Bioleaching process efficiency is very

high. The reduction of pyritic sulfur by leaching with bacteria of the genus Thiobacillus

ferrooxidans and Thiobacillus thiooxidans, can reach up to 97% (Acharya et al. 2001). An

additional effect of this process is the reduction of heavy metals and trace elements

concentrations (Bos et al. 1992; Naganoka et al. 1999; Lewińska-Preis et al. 2008). Trace

elements and metals released by coal combustion are a potential source of pollution. These

elements are mainly concentrated in fly ash. For coals of the Upper Silesian Coal Basin the

estimated emissions of trace elements in fly ash are 32.6-121.5 Mg/y for Cr, 46.5-1287.7

Mg/y for Zn, 3.6 Mg/y for Cd, 17.5-68.7 Mg/y for Co, 38.9-185.1 Mg/y for Cu, 1.6-6.4 Mg/y

for Mo, 19.9-79.4 Mg/y for Pb, and 72.3-237.1 Mg/y for V (Staisz et al. 2000). The use of

biodesulphurized coal can significantly decrease these elements emissions to the atmosphere.

In the projects bituminous coals from the Lublin Coal Basin (LCB) were studied, which

were subjected to microbiological leaching. The process was carried out using a suspension

bioreactor. The ratio of powdered coal to the number of bacteria was 1:2. The suspension was

prepared from the strains of bacteria Thiobacillus ferrooxidans, and Thiobacillus thiooxidans

HR27 KH45 (1:1), a density of 108 cells in 1 cm

3. Samples were introduced into the

Silverman and Waksman modified medium containing the suspension of bacteria in a ratio of

1: 1. The samples of raw (not desulphurized) coal and desulphuriozed coals were combusted

at 525oC. In coal ash, the selected elements (Be, Cd, Co, Cr, Cu, Mo, Pb, V, and Zn) were

investigated by Inductively Coupled Plasma - Atomic Emmision Spectrometry (ICP) whereas

C and S contents were found using the Eltra CS 530 analyser.

The concentrations of the selected elements in raw coals and their ashes are at the level of

the average concentration of these elements in coals and ash coals in the world. In the

biodesulphurization ash content and the concentration of Be, Cd, Co, Cr, Cu, Mo, Pb, V, Zn

were reduced. The highest degree of reduction is shown by Co (90%), Mo (85%), and Be

(84%) and the lowest Cr (36%) and V (46%). For Cd concentration reduction degree is 74%,

for Cu - 67%, for Zn - 66% Pb - 60%, and for total ash content - 16%.

As a result of microbial desulfurization of LCB bituminous coals there were also changes

in the occurrence variability of elements and the degree of their affinity for organic matter and


83

mineral matter of coal. In general, the elements variability of after the biodesulphurization

decreases; only Zn and Cd show an increase of over 100%. Changes in the elements affinity

to organic and mineral matter of desulphurized coals indicate that these elements are leached

mainly from coal inorganic substances, and only to a lesser extent from organic matter.

Coals with high ash contents have the highest degree of reduction in the concentrations of

elements, apart from Zn, Cd and Be. For Zn and Cd the highest concentration decrease was

observed for low-ash coals (ash content less than 10%). For Be concentrations decrease was

the same in low-and high ash coals (> 20%).

References

Acharya C., Kar R.N., Sukla L.B. 2001 - Bacterial removal of sulphur from three different coals. Fuel, 80: 2207-

2216.

Bos P., Boogerd F., Kunen J.G. 1992 - Microbiol desulfurization of coal. In: Environmetal Microbiolagy, Ed: R.

Mitchell, Wiley-Lisse, Jnc., New York: 375 – 403.

Lewińska-Preis L., Fabiańska M.J., Parzentny H., Kita A. 2008 - Geochemical characteristics of the

macromolecular part of crude and biodesulphurised flame coal density fractions. Chemie der Erde, 68:

279-293.

Lorenz U., 2005 - Skutki spalania węgla kamiennego dla środowiska przyrodniczego i możliwości ich

ograniczania. Materiały Szkoły Eksploatacji Podziemnej. Sympozja i Konferencje, 64, Wyd. Instytut

GSMiE PAN, Kraków: 97-112.

Nagaoka T., Ohmura N., Saiki H. 1999 - A Novel Mineral Flotation Process Using Thiobacillus ferrrooxidans.

Applied and Environmental Microbiology, 65: 3588-3593.

Staisz J., Pasoń-Konieczyńska A., Konieczyński J. 2000 - Wstępna ocena emisji pierwiastków śladowych

w wyniku spalania węgla kamiennego. Archiwum Ochrony Środowiska, 26, 1: 7-20.


84

Organic petrology of two condensed Middle Holocene peat deposits

in N Spain in relation to their origin

V. López-Dias, J. Urbanczyk, C.G. Blanco, A.G. Borrego

Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain; [email protected]

Peatlands have been successfully used to study the evolution of climate during the Holocene

(Barber et al. 2003). Peatlands formation require a positive balance of organic matter

accumulation and are particularly abundant in cold to temperate humid regions in which the

rate of organic matter destruction is relatively low or in tropical regions where the rate of

organic matter accumulation is particularly high. The north of Spain is the southernmost limit

for ombrothrophic blanket bogs in the Atlantic region and provides the opportunity to study

their palaeoenvironmental evolution in an area in contact with the more arid Mediterranean

region. A number of peats have been developed in the plane reliefs of Asturias ranging in age

from around 10000 cal. yr BP to present day. They are either raised bogs or blanket bogs and

show growth rates ranging from 0.7 and 0.05 mm/yr (López-Días et al. 2013a).

This study focuses on the Buelna and La Borbolla peat profiles, both exhibiting a very low

growth rate (0.05-0.07 mm/yr) and having profiles whose record extends from around 9000 to

2500 cal. yr BP. La Borbolla bog (UTM 30 T 365813 4804949) has an extension of 6 ha, is

situated 227 m above sea level (masl) and the profile reaches a depth of 56 cm, consisting of

around 8 cm of living vegetation dominated by Sphagnum, followed by a 20 cm interval of

bryophytic reddish peat with abundant roots and by 14 cm of darker and clayish peat, which

becomes lighter towards the end. The Buelna bog (UTM 30T 369898 4805333) has a surface

of around 9 ha and is located at a height of 133 masl. The sampled core reaches a depth of 87

cm, The first 15 cm consisting of unconsolidated living vegetation with many roots, followed

by 9 cm of more bryophytic peat with common roots. The next 36 cm consist of compact dark

reddish peat. This interval is followed by 8 cm of dark clayish material and the last 20 cm are

a light grey siltstone with low organic content. The two profiles differ in the type of organic

matter which is more bryophytic in La Borbolla and more herbaceous in Buelna (López-Dias

et al., 2013b).

Alternating humid/dry periods have been established in the two profiles based on lipid

concentrations. The main humid intervals detected are dated as 5000-7500 cal. yr BP in

Buelna and as 6000-3500 cal. yr BP and 2500 cal. yr BP in La Borbolla and correlate with the

humid periods detected in other peat locations in the region (López-Dias et al., 2013a). The

study of linear lipids indicates that the Sphagnum-rich intervals are more sensitive than

herbaceous peat to humid/dry variations. The transition Middle-to-Late Holocene is

characterized by humid conditions in the region which favoured the Sphagnum growth in the

peats.

The petrographic analyses were used to determine the degree of humification in the peat

profiles through the measurement of huminite reflectance and the degree of preservation of

the different components. Both telohuminite, detrohuminite and corpohuminite components


85

were identified in the profiles in addition to their translucent ungelified precursors. The

reflectance of huminite was very low (0.25-0.12%) and without significant differences

between telohuminite and detrohuminite. Corpo-huminite reflectances were systematically

higher. The reflectances tended to be higher towards the top, where humification processes

could have been intensified as consequence of the stopping of peat growth. The level of tissue

preservation was observed to be lower in La Borbolla, in which extensive tissue destruction

resulted in comminute organic debris. This was accompanied in this profile by abundant

inertodetrinite, particularly concentrated at around 5000 cal. yr BP, a period character-rized

by a marked change from higher-plants derived n-alkane to Sphagnum-derived n-alkane

(López-Dias et al., 2013b). The Buelna profile, with a more herbaceous vegetation, and higher

mineral matter content throughout the profile, shows a higher level of tissue preservation

(dominance of telohuminite) and lower inertinite content.

Acknowledgement: Financial support from MICINN (CGL2009-13990-C02-01/02) is gratefully acknowledged.

J. Urbanczyk thanks MEC for a FPU fellowship.

REFERENCES

Barber K.E., Chambers F.M., Maddy D. 2003 - Holocene palaeoclimates from peat stratigraphy: macrofossil

proxy climate records from three oceanic raised bogs in England and Ireland. Quaternary Science Reviews

22: 521–539.

Lopez-Dias V., Urbanczyk J., Blanco C.G., Borrego A.G. 2013a - Biomarkers as palaeoclimate proxies in

peatlands from coastal high plains in Asturias, N Spain. Int J. Coal Geol.

dx.doi.org/10.1016/j.coal.2013.04.006.

Lopez-Dias V., Urbanczyk J., Blanco C.G., Borrego A.G. 2013b - Palaeohydrological evolution of the Middle-

to-Late Holocene transition in North Spain as recorded by biomarkers in peat bogs. Palaeogeography

Palaeoclimatology Palaeoecology (submitted).

Fig.1. Images showing inertinite-rich levels in La Borbolla at ~5000 cal. yr BP.

Arrows mark inertinite, Ul=Ulminite. Incident white light


86

Transmittance Color Index of Amorphous Organic Matter (TCIAOM)

as thermal maturity parameter: a new approach

J.G. Mendonça Filho1, J.O. Mendonça

1, T.R. Menezes

2, F.S. Silva

1

1Palynofacies & Organic Facies Laboratory (LAFO), Federal University of Rio de Janeiro (UFRJ), Brazil;,

[email protected] 2Research and Development Center, PETROBRAS, Brazil

The Transmittance Color Index (TCI) of Amorphous Organic Matter (AOM) was proposed firstly

by Van Gijzel (1989) as a new thermal maturity indicator for hydrocarbon source rocks, due to the

need for an improvement to assess the thermal history in petroleum basins and the lack of

accuracy in the current techniques for determining thermal maturity on severe limitations, i.e. lack

of vitrinite particles or sporomorphs, presence of supressed vitrinite in Type I/II kerogen, etc.

TCI eliminates most limitations of these techniques and it is measured on amorphous material,

the most abundant type of organic matter in hydrocarbon source rocks of all geologic ages and for

instance where vitrinite is scarce. According to Van Gijzel et al. (1992), TCI is measured by

quantitative microscope spectrophotometry (the quantitative measurement of the reflection or

transmission properties of a material as a function of wavelength), making it easy to develop

standards among different laboratories.

Based on Robison et al. (2000), the range of TCI values covers all zones of petroleum

generation and preservation. However, it can be more useful in those situations where the rocks

have not yet reached the semi-anthracite coalification stage (about 2.0% vitrinite reflectance). TCI

can provide an accurate basis for maturation interpretations equivalent in quality to those obtained

from vitrinite reflectance, zooclast reflectance (graptolites, chitinozoans), Spore Color Index

(SCI), Thermal Alteration Index (TAI) or Conodont Color Index (CAI). In addition, TCI

correlates with conventional organic petrologic maturity parameters such as TAI/SCI and vitrinite

reflectance. Thus, TCI is a quantitative method to determine the thermal stress and it can be used

as an indicator of thermal maturity in sapropelic organic facies, where other elements such as

vitrinites and sporomorphs are scarce or even absent.

According to Suárez-Ruiz et al. (2012), this method is applied to oil-prone amorphous kerogen

in transmitted light. The assignment of particular TCI values is based on the increasing curvature

of spectra with increasing maturity. TCI curves shift from a peak wavelength at around 580 nm

for samples of immature, amorphous kerogen (mean random vitrinite reflectance equivalent of

about 0.20%) to about 660 nm for samples containing very dark brown to some black particulate

material (mean random vitrinite reflectance equivalent of about 2.15%).

This work is part of the activities of a research project financially supported by PETROBRAS-

Brazil´s Research and Development Center and, for this new approach, more than 150 samples

from different ages (Carboniferous, Permian, Jurassic, Cretaceous, Oligocene and Eocene) with

vitrinite reflectance measured were tested for use in the development of the Linear Equation in

two variables for correlation between TCI and Equivalent Vitrinite Reflectance (Req), i.e. these

samples were used to build the Straight-Line Equation ("slope-intercept" form), represented by y

= m.x+b, where m and b assign constants (parameters). In this particular equation, the constant m

determines the slope or gradient of that line, and the constant term b determines the point at which



87

the line crosses the y-axis, also known as the y-intercept. Thus, the equation for correlation can be

written as %Req = slope x TCIAOM - (Y intercept).

Out of the total samples, only 80, appointed the following equation: %Req = 0.0217 x TCIAOM –

11.327 (against that obtained by Robson et al., 2000; %Req = 0.0253 x TCI – 14.35), where the

linear correlation coefficient obtained, r, which measures the strength and direction of a linear

relationship between two variables) was 0.978. This was obtained by comprising both vitrinite

measurable particles and AOM, covering different values of thermal maturity. The value of r is

such that -1 < r < +1. The + and – signs are used for positive linear correlations and negative

linear correlations, respectively. For our equation the value of r = 0.978 indicates a strong positive

linear correlation between x and y variables such that as values for TCIAOM increase, as well

as Req. Now, the coefficient of determination, r2, which is useful because gives the proportion

of the variance (fluctuation) of one variable that is predictable from another, is 0.959. It is a

measure that allows us to determine how certain one can be in making predictions from a certain

model/graph. The coefficient of determination (r2) is the ratio of the explained variation to the

total variation. The coefficient of determination is such that 0 < r2 < 1, and denotes the strength of

the linear association between x and y. The coefficient of determination represents the percent of

the data that is the closest to the line of best fit. In this case, if r = 0.978, then r2 = 0.959, which

means that approximately 96% of the total variation in Req can be explained by the linear

relationship between Req and TCIAOM (as described by the regression equation). The other 4% of

the total variation in Req remains unknown.

TCI values are obtained by the analysis of white light originating from a 100-W 6-V tungsten

lamp attached to a microscope (Axioskop 2 plus Zeiss) and photometric (J&M – MSP 200 –

TidasDAQ). Measurements for 30 to 40 particles are sufficient to produce good data and TCIAOM

measurements were made on AOM in those samples in which vitrinite reflectance measurements

were reliable. Based on the Linear Equation, values obtained for TCIAOM between 532 and 544

can be correlated to Req varying between 0.16 and 0.45% Req, TCIAOM from 550 to 576 can be

correlated to 0.7-1.1 %Req and TCIAOM values from 583 to 593 correlates 1.4-1.6%Req.

Acknowledgments: The authors are grateful to PETROBRAS-Brazil for the financial support through the

project entitled “Faciologia Orgânica, Maturação Térmica e Modelagem Geológico-Geoquímica de Seqüências

Sedimentares Paleozóicas, Mesozóicas e Cenozóicas".

References

Robison C.R., Van Gizel P., Darnell L.M. 2000 - The Transmittance Color Index of amorphous organic matter:

a thermal maturity indicator for petroleum source rocks. International Journal of Coal Geology, 43: 83-103.

Súarez-Ruiz I., Flores D., Mendonça Filho J.G., Hackley P.C. 2012 - Review and update of the applications of

organic petrology: Part 1, Geological Applications. International Journal of Coal Geology 99: 54-112.

Van Gijzel P. 1989 - Transmittance Color Index _TCI. of amorphous organic matter: new thermal maturity

indicator for hydrocarbon source rocks-correlation with mean vitrinite reflectance and thermal alteration

index _TAI. AAPG Bull. 73: 1177.

Van Gijzel P., Robison C.R., Smith M.A., Bissada K.K., Lerche I., Liu J.-C. 1992 - Thermal history modeling of

the Georges Bank, U.S.A.: thermal inversion of transmittance color index _TCI. Vitrinita reflectance _VR.

data. Appl. Geochem. 7: 135–143.


88

Offshore from the Lusitanian Basin, Portugal:

new insights into depositional settings and hydrocarbon source potential

based on palynofacies and organic geochemistry

T.R. Menezes1, J.G. Mendonça Filho

2, D. Flores

3, L.A.F. Trindade

4

1Research and Development Center, PETROBRAS,[email protected]

2Palynofacies & Organic Facies Laboratory, Federal University of Rio de Janeiro (UFRJ), Brazil

3Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências, Universidade

do Porto, Portugal 4PESA, Petrobras Argentina

This study provides an organic facies characterization using palynofacies and organic

geochemical parameters of the Mesozoic sedimentary sections offshore part of the Lusitanian

Basin (Portugal) in order to obtain new insights into depositional paleoenvironments and

hydrocarbon source potential. The studied samples were collected from two exploratory wells

(MO-1 and 14A-1) at shallow water depth. This basin is one of a family of Atlantic margin

rift-basins and it is located along the western Iberian margin which has formed as a response

to Mesozoic extension and subsequent opening of the North Atlantic Ocean, covering some

20.000 km2 in the west-central part of the Portuguese mainland and the adjacent continental

shelf (e.g. Wilson et al., 1989, Rasmussen et al., 2008). The geological database was based on

Well Geological Report from company completion logs available on request at GPEP

(Gabinete para a Pesquisa e Exploração de Petróleo).The discussion below will focus on the

characterization of sedimentary organic matter based on Total Organic Carbon (TOC%),

Rock-Eval Pyrolysis, kerogen assemblages characterized by palynofacies analyses, thermal

maturity (Vitrinite Reflectance –%Ro, Spore Coloration Index – SCI) and biomarker

parameters. The studied samples in both sections shown TOC values less than 1.00wt % and

insoluble residue values (IR) indicated mainly carbonate/marls deposits. Indeed, the bulk

TOC values reflected strong dilution effects ordinarily in carbonate facies. In general, the

main palynofacies assemblage has a predominance of macrophytes tissues remains

(Phytoclast Group). The differences detected in microscopic examination along the two

analyzed sedimentary sections point out variations in depositional settings: The palynofacies

from the Dagorda Formation (Upper Triassic-Lower Jurassic deposits) consists predominantly

of coarse to medium sized woody organic matter (non-opaque non-biostructured phytoclats)

and has a high relative abundance of tetrads of Classopollis and Amorphours Organic Matter

(AOM) with inclusions of palynomorphs debris. Marine palynomorphs are rare (acritarchs,

foraminiferal test linings and dynocist). Under reflected white light a significant proportion of

inertinite maceral was identified. The kerogen assemblage suggests a depositional set

associated with an aridity trend and nearest to the source area from the studied intervals. By

contrast, some samples from the MO-1 well are represented by carbonaceous marls, presented

TOC values from 6.4 to 30 wt%, which could be related to a more humid episode. The

Sinemurian age (Coimbra Formation) is characterized by a major percentage of AOM and a

predominance of biostructured phytoclasts. It was observed a decrease of relative abundance


89

of terrestrial palynomorphs. The palynofacies signature indicates moderately deeper water

than that of the Dagorda Formation. In the Brenha Formation, from Lower Jurassic-Middle

Jurassic, the MO-1 well kerogen assemblage has shown a balanced content of orange

fluorescing AOM and phytoclasts. It was identified the presence of continental palynomorphs

(e.g. Botryococcus, spores from Zygnemataceae Family, Azolla sp.) and rare marine

palynomorphs. Moreover, the palynofacies from 14A-1 is overwhelmingly dominated by

biostructured phytoclast. Thus, the organic facies of this unit suggested a variation in the

hydrodynamic regime between two depositional settings. The Oxfordian section was

described in the 14A-1 well. In this interval, the palynofacies reveals, from the base to the top,

the increase of poorly preserved sporomorphs and a high relative abundance of dynocists due

to probably a fluvial-deltaic progradation. The Kimmeridgian and Upper Cretaceous

sediments were found only in the MO-1 well, where sedimentation is more influenced by

terrigeneous contribution and reflected a poorly preserved organic matter with very low TOC

values and IR > 70, indicating a siliciclastic sedimentation and high energy environment in

oxic conditions. Concerning biomarkers characterization, though based on a restricted number

of samples, the study showed a good correlation with palynofacies data. The main biomarkers

parameters e.g., Hopane/Sterane ratio < 0.5, C21Tricyclic/C23Tricyclic and

C26Tricyclic/C25Tricyclic ratios< 1, TPP/TPP+DIA < 0.4, low occurrence of methylsteranes,

C29 sterane > C27 and C28, C24 Tetracyclic Terpane/C26 Tricyclic Terpane ratio > 0.5, C35

homohopane/C34 homohopane ratio varies from 0.52 to 1.09, pointing to a carbonate marine

deposition with strong contribution of continental organic matter. The source rock potential

represented by S2 peak from pyrolysis are very poor (< 5 mg HC/g rock) and Hydrogen Index

(HI) are typical from type III-IV kerogen. In contrast, the carbonaceous marls from the MO-1

well presenting a S2 values reaching up 40 mg HC/g rock showed an excellent potential for

hydrocarbon generation. Now, the correlation of optical thermal maturity parameters (%Ro

and SCI) to 20S/(20S+20R) sterane, C29βββ/(αα+ββ) steranes, and Ts/Ts+Tm ratios indicated

that the studied sedimentary sections are in the oil window.

Acknowledgments: This work has been sponsored by the Scientific and Technical Cooperation Agreement

CAPES (Brazil)/FCT (Portugal), through the project entitled “Caracterização das variações organofaciológicas e

identificação dos horizontes potencialmente geradores de petróleo no Jurássico da Bacia Lusitânica”.

References

GPEP (Gabinete para a Pesquisa e Exploração de Petróleo) 1986 - Petroleum potential of Portugal: 1-62.

Rasmussen E.S., Lomholt S., Andersen C., Vejbæk O.L. 1998 - Aspects of the structural evolution of the

Lusitanian Basin in Portugal and the shelf and slope area offshore Portugal. Tectonophysics, 300: 199 – 225.

Wilson R.C.L., Hiscott R.N., Willis M.G., Gradstein F.M. 1989 - The LusitanianBasin of west-Central Portugal:

Mesozoic and Tertiary tectonic, stratigraphic and subsidence history. AAPG Bulletin 46: 341–362.


90

Preliminary organic geochemical study of lignites

from Smederevsko Pomoravlje field, Kostolac Basin, Serbia

D. Mitrović1, N. Đoković

1, K. Stojanović

2, S.K. Das

3, A. Ekblad

4, A. Mikusinska

4,

D. Životić5

1University of Belgrade, Innovation Center of the Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade,

Serbia 2University of Belgrade, Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia;

[email protected] 3Presidency University, Department of Geology, College Street 86/1, 700073 Kolkata, India

4School of Science & Technology, Örebro University, S-701 82 Örebro, Sweden

5University of Belgrade, Faculty of Mining and Geology, Djušina 7, 11000 Belgrade, Serbia;

[email protected]

The Kostolac Coal Basin, covering an area of 145 km2, is located about 90 km east of

Belgrade. The coal basin is divided into Drmno, Ćirikovac and Smederevsko Podunavlje

fields situated in eastern, central and western part of the basin, respectively. Drmno and

Ćirikovac fields were exploited, while Smederevsko Podunavlje field is still under

preliminary exploration.

Lignite samples of Pontian age (Upper Miocene) from 27.40 to 85.20 m depth in two

boreholes (A1J-369 and A2I-414) at Smederevsko Pomoravlje field were investigated.

Organic geochemical (organic carbon content, ash yield, moisture, sulfur and nitrogen

contents, extract yield and content of hydrocarbons) and bulk stable carbon and nitrogen

isotopes (δ13

C and δ15

N, respectively) in the samples were analyzed. Objectives of the study

were to understand depositional conditions of the peat in the study area, and compare the

results with similar studies in other coal basins in Serbia and worldwide. Moreover, based on

bulk and specific organic geochemical data, the possibility of exploitation of lignite from

Smederevsko Pomoravlje field in future was considered.

Organic carbon content, ash yield, moisture, sulfur and nitrogen contents, extract yield and

content of hydrocarbons in lignites of Smederevsko Pomoravlje field fall within the range of

corresponding parameters for lignites from other deposits in Serbia (Stojanović, Životić,

2013). High yield of soluble organic matter (bitumen), represented by asphaltenes and polar,

NSO compounds, is attributed to high proportion of biogenic and diagenetic compounds.

16(H)-Phyllocladane and pimarane are dominant in saturated hydrocarbon fractions. A high

amount of 16α(H)-phyllocladane and pimarane, as well as presence of ferruginol, totarane and

hibaene indicate conifers (Taxodiaceae, Podocarpaceae, Cupressaceae, Phyllocladaceae and

Pinaceae) as primary constituent of the peat forming plants. Presence of diterpenoids as the

main constituents of both saturated and aromatic fractions supports our finding. Aromatic

diterpenoids consist predominantly of aromatized abietane derivatives. Long-chain

homologues (C27-C31, maximum at n-C29) n-alkanes with marked odd over even

predominance indicate significant contribution of epicuticular waxes to the organic matter

(OM) pool. Pristane to phytane, Pr/Ph ratio (0.72−1.65) most likely indicates changing redox

(Eh) setting from anoxic to slightly oxic conditions during peat deposition.



91

Samples contain very low amount of non-hopanoid triterpenoids and des-A-ring degraded

triterpenoids. Hopanoid patterns are characterized by occurrence of C2717(21)-hop-ene,

17α,21β(H)- and 17β,21β(H)- hopanes from C27 to C32 (C28 was absent). Steroid biomarkers

consist of C27-C29 Δ2-, Δ

4- and Δ

5-sterenes with sharp domination of C29 homologues.

Bulk δ13

C values vary from −26.66 to −25.25‰. Average carbon isotopic composition of

all samples (δ13

C=−26.01‰) falls within the range of δ13

C values reported for the upper

Oligocene Trbovlje coal seam in Slovenia (Bechtel et al., 2004), early Miocene Oberdorf

lignite in Austria (Bechtel et al., 2002) and Oligocene-Miocene lignites from New Zealand

(Vu et al., 2009). The δ13

C isotope values of Smederevsko Pomoravlje lignites do not vary

much with age and borehole location, and lie within the range of typical terrestrial OM in

Cenozoic sediments (Hoefs, 1997). δ15

N values range from 2.81 to 5.54 ‰. A lack of

systematic trend in δ13

C and δ15

N values with depth suggests that climate and/or

environmental conditions did not vary drastically during the deposition of peat although the

variations in δ13

C and δ15

N may reflect seasonal changes in climate condition (cycling change

of humid/dryer and warmer/cooler conditions; Ivanov et al., 2011). Pronounced seasonal

changes in local climate can affect ground water table resulting in changes in the Eh

conditions and microbial activity during peatification. Positive correlation between δ13

C and

δ15

N and Pr/Ph ratio, and negative correlation between δ13

C and δ15

N and C30ββ/(αβ+ββ)

hopane ratio support our assumption. Nonetheless, significant positive correlation between

C/N and δ13

C, and abundance of hopanes in the lignite extracts indicate influence of microbial

degradation on the stable isotope records.

Bulk organic geochemical data and distribution of biomarkers in lignite extracts from

Smederevsko Pomoravlje field are very similar to those, observed in other Pontian lignite

fields in Serbia (e.g. Drmno field, Kostolac Basin and A field, Kovin deposit; Stojanović,

Životić, 2013) indicating a similar genesis and geological evolution. Obtained results could

imply that lignite from Smederevsko Pomoravlje field can also be used in the large scale,

particularly for electricity generation in thermal power plants.

References

Bechtel A., Sachsenhofer R.F., Gratzer R., Lücke A., Püttmann W. 2002 - Parameters determining the carbon isotopic

composition of coal and fossil wood in the Early Miocene Oberdorf lignite seam (Styrian Basin, Austria). Org.

Geochem., 33: 1001–1024.

Bechtel A., Markic M., Sachsenhofer R.F., Jelen B., Gratzer R., Lücke A., Püttmann W. 2004 - Paleoenvironment of the

upper Oligocene Trbovlje coal seam (Slovenia). Int. J. Coal Geol., 57: 23– 48.

Hoefs J., 1997 - Stable Isotope Geochemistry. Springer-Verlag, Berlin: 1-201.

Ivanov D., Utescher T., Mosbrugger V., Djordjević-Milutinović D., Molchanoff S. 2011 - Miocene vegetation and climate

dynamics in Eastern and Central Paratethys (Southeastern Europe). Palaeogeogr. Palaeoclimatol. Palaeoecol., 304: 262–275.

Stojanović, K., Životić, D., 2013. Comparative study of Serbian Miocene coals – insights from biomarker composition. Int. J.

Coal Geol.107, 3–23.

Vu T.T.A., Zink K.-G., Mangelsdorf K., Sykes R., Wilkes H., Horsfield B. 2009 - Changes in bulk properties and molecular

compositions within New Zealand Coal Band solvent extracts from early diagenetic to catagenetic maturity levels. Org.

Geochem., 40: 963–977.


92

Raman microspectroscopy of funginite from the Upper Silesian Coal Basin

(Poland) - preliminary results

R. Morga

Silesian University of Technology, Gliwice, Poland; [email protected]

Introduction

Funginite is a relatively rare but also weakly recognized coal maceral from the inertinite

group. The purpose of this study was to obtain, for the first time worldwide, structural

characteristics of funginite with the use of the micro-Raman spectroscopy.

Method

Examination was performed on inertinite concentrates (I content: 80 – 84%) prepared from

four samples of the coking coal from the Upper Silesian Coal Basin of Poland. Selected

properties of the parent coals are summarized in Table 1. Micro-Raman measurements were

carried out with the use of a Renishaw inVia spectrometer (excitation line λ0=514 nm) on

6-10 funginite grains in each mount. Spectral range was 1000-1800cm-1

, and resolution 2cm-1

.

During each measurement four acquisitions of 10s were co-added. Measurement area was

2x2μm. The spectra were deconvoluted with the use of GRAMS 32 software, following the

Sadezky's et al. (2005) method. Four Lorentzian (G, D1, D2 and D4 band) and one Gaussian

(D3 band) lines were used. Goodness of fit was checked by χ2 test. Based on that, position of

the Raman bands and their width (FWHM) were found. Following spectral parameters were

determined: AG/AALL, AD1/AALL, AD2/AALL, AD3/AALL and AD4/AALL (all calculated as the area

ratios) as well as ID1/IG and ID2/IG (both calculated as the band height ratios). The results were

compared with those, obtained during previous examination of semifusinite and fusinite

(Morga, 2011). For this purpose, the t-Student test was performed, preceded by the Shapiro-

Wilk normality test and the Fisher-Snedecor test to assess the equality of variance.

Table 1. Selected properties of the parent coals used in the study

Sample

Seam

Age

Rr

%

sr

%

Vdaf

%

RI

Vitrinite

%

Liptinite

%

Inertinite

%

MM

%

1 358/1 Westphalian A 0,92 0.05 33.81 71 73 6 19 2

2 703 Namurian A 0,94 0.06 33.70 75 70 8 20 2

3 358/1 Westphalian A 0,97 0.05 30.83 80 65 9 24 2

4 403/1 Westphalian A 1,11 0.06 26.25 64 66 3 29 2

Results

The D2 band position in the Raman spectra of funginite is situated between 1612cm-1

and

1613cm-1

. The G band falls between 1587cm-1

and 1591cm-1

. The other bands occur within

the following spectral ranges: D3 – 1441-1489cm-1

, D1 – 1343-1348cm-1

and D4 – 1238-

1254cm-1

. The G band FWHM varies between 55cm-1

and 61cm-1

and that of the D1 band

between 119cm-1

and 147cm-1

. The other bandwiths are presented in Table 2. The AD2/AALL


93

ratio ranges from 0.12 to 0.15. The values of the other structural ratios are: AG/AALL – 0.15-

0.18, AD3/AALL – 0.13-0.17, AD1/AALL – 0.29-0.44, AD4/AALL – 0.13-0.22, ID1/IG – 0.83-1.18

and ID2/IG – 0.97-1.34 (Table 3).

When samples 1 and 3 are considered, results obtained for funginite do not vary

significantly from those recorded for fusinite (Morga, 2011). In the case of sample 2 there are

only minor differences in the spectral parameters between these two macerals, but much more

important betwee funginite and semifusinite (Morga, 2011). Spectral parameters of funginite

obtained from sample 4 show very close similarity to those of semifusinite.

Conclusion

Funginite microstructure may have many common features with that of fusinite or

semifusinite. Broader demonstration of these similarities requires further investigation.

Table 2. Position and the FWHM of the Raman bands for funginite

Sample

D2 band

position

[cm-1

]

D2 band

FWHM

[cm-1

]

G

band

position

[cm-1

]

G

band

FWHM

[cm-1

]

D3 band

position

[cm-1

]

D3 band

FWHM

[cm-1

]

D1 band

position

[cm-1

]

D1 band

FWHM

[cm-1

]

D4 band

position

[cm-1

]

D4 band

FWHM

[cm-1

]

1 1613.3 40.0 1590.5 59.2 1485.2 184.6 1343.7 132.4 1238.0 181.1

1.04 5.07 2.78 3.96 34.76 18.68 1.99 13.38 9.90 16.08

2 1611.7 41.6 1587.3 61.4 1489.2 180.6 1343.3 147.3 1237.7 177.3

0.97 3.76 2.39 3.07 23.22 19.41 2.26 15.16 9.25 12.51

3 1611.6 40 1588.9 55.2 1472.1 187.4 1345.0 125.6 1248.6 171.7

0.65 1.44 1.28 1.11 21.04 17.50 2.60 12.04 5.00 13.44

4 1612.0 42.0 1588.4 58.3 1440.8 188.5 1347.5 119.1 1253.6 179.4

0.48 3.69 1.88 3.02 9.45 15.66 1.78 9.31 3.37 7.91

Table 3. Values of the Raman spectral ratios for funginite

Sample AD2/AALL AG/AALL AD3/AALL AD1/AALL AD4/AALL ID1/IG ID2/IG

1 0.12 0.18 0.16 0.39 0.16 1.07 0.97

0.02 0.02 0.06 0.15 0.07 0.28 0.16

2 0.12 0.18 0.13 0.44 0.13 1.12 1.00

0.02 0.02 0.03 0.12 0.06 0.32 0.12

3 0.15 0.15 0.14 0.39 0.17 1.18 1.34

0.01 0.01 0.03 0.09 0.05 0.25 0.16

4 0.14 0.18 0.17 0.29 0.22 0.83 1.12

0.01 0.01 0.03 0.04 0.04 0.11 0.09

References

Morga R. 2011 - Reactivity of semifusinite and fusinite in the view of micro-Raman spectroscopy examination.

Int. Journal of Coal Geol., 88: 194-203.


94

Influence of temperature on mineral composition changes of coal mine

waste; an example of waste dump sites in Upper Silesia Coal Basin (Poland)

J. Nowak

Silesian University of Technology; [email protected]

Extraction of hard coal is being inseparably bound with generation of large amounts of mineral

waste. These are mainly waste rock mined out directly during driving development headings,

preparation workings and coal faces or being removed from the output during its processing.

Coal mine waste in the Upper Silesia Coal Basin (USCB) area consists mainly of claystones,

mudstones, and sandstones. In these rocks there is also different, frequently high, amount of

organic matter – coal. In the mineral composition of these waste quartz and clayey minerals

dominate, mainly kaolinite, illite and other. Among the carbonates most frequently siderite occurs,

but also calcite and dolomite are present. Among the other minerals pyrite, feldspars, and

muscovite should be mentioned.

Due to the influence of hypergenic factors, especially precipitation waters and atmospheric

oxygen, weathering processes take place. At this stage, in the waste dumps grain-size

decomposition is dominating and the mineral composition undergoes only small transformations.

The most vulnerable for weathering processes are sulphides, which undergo transformation into

sulphates, gypsum, jarosite, and others. Also organic matter undergoes weathering. Oxidation of

coal and pyrite being contained in the coal mine waste is an exothermal reaction. As a result of

this process, self-heating of the waste takes place. In advantageous conditions, the temperature is

able to exceed temperature of ignition of the waste, which equals of about 250-350oC, what in a

consequence leads to generation of endogenic fires at the coal waste dumps. Combustion of coal

contained in the waste generates large amounts of heat, what contributes further increase of

temperature in the dump, even over one thousand degree Celsius.

The first mineral metamorphoses, which occur as the result of organic matter combustion are

decomposition of carbonates and dehydroxylation of clayey minerals.

Siderite, commonly present in the rocks accompanying coal seams, decays into FeO and CO2.

The process begins in the temperature of 380oC and ends in about 550oC. Simultaneously occurs

oxidation of FeO into Fe2O3. As a result of FeO oxidation, hematite, maghemite, or their mixture

may be created.

Hematite may be also a product of thermal transformations of pyrite. If pyrite is located in a

fire zone, then in the range of temperatures from 400 to 650oC, its decomposition into iron and

sulphur occurs. Sulphur oxidases into SO2, while iron into Fe2O3.

Presence of hematite and maghemitetaints overburnt coal mine waste are reflected by its

colours from pale pink, through orange, up to cherry red.

Kaolinite, the most frequent clayey mineral present in coal mine waste, in the result of high

temperature undergoes a range of transitions. The first of these reactions, which occurs in

temperature of round 800oC relates to its dehydroxylation. Amorphic metakaolinite is being

created as its result.

Quartz, which belongs to the main mineral components of coal mine waste, exhibits high

tolerance to high temperatures. Changes that take place in this mineral are of polymorphic


95

transitions character. Their effect is the volume change of quartz grains, which may lead to

generation of tensions and fractures.

When the temperature of the dump does not reach one thousand degree Celsius, coal mine

waste does keep its original structure and texture, which it possessed at the moment of its

dumping on the site. Only the colour and mineral composition undergoes changes. Properties of

the overburnt coal mine wastes make them similar to the clinker.

Further increase of temperature leads to another transitions of mineral composition of the

waste. In temperature of about 980oC metakaolinite melts into spinel Si-Al and mullite. Around

1100oC sillimanite phase appears, from which, in case of increasing of temperature by next

100oC, another generation of mullite occurs. The last exogenous reaction, which occurs in

temperature of about 1250 – 1350oC is being interpreted by researchers as crystallization of

cristobalite.

When the temperature increased to more than 1050oC destruction of internal structure of illite

takes place and its melting. Melting of illite, feldspars, muscovite, and other minerals followed by

fast cooling of the alloy, leads to creation of glass. From the alloy minerals from the spinel group

may crystalize: magnetite, hercynite, magnesioferrite and also from the pyroxene group:

clinoferrosilite, hedenbergite, and other. Favourable for the creation of spinels and pyroxenes in

coal mine waste are the reduction conditions resulted from the presence of fire gases, which are

reach in CH4, H2, and CO2. High temperature and reduction conditions lead to generation of small

aggregations of metallic iron.

Coal mine waste, which underwent described above transformations, lost their original

structures and textures. Most frequently they resemble metallurgical slags, sometimes they are

also being referred as paralava.

On the basis of the colour, structural properties, and especially mineral composition, three

zones of different thermal transformation levels may be distinguishedon a coal mine waste dumps,

namely:

Thermally untransformed zone (characterised by grey-black colour and preservation of the

original mineral composition and structures of the waste),

Moderately thermally transformed zone (characterised by orange-brick red colour, burnout of

coal, presence of metakaolinite and hematite/ maghemite),

Intensively thermally transformed zone (characterised by disappearance of original textures

of rocks, presence of glass, and high temperature minerals).

Precipitation waters, which infiltrate the coal mine waste dumps, are warmed up by the rocks

heated due to fires and create pseudo-hydrothermal conditions in the dump. These waters are able

to leach substances from the waste and transport them into the body of a dump. When the

conditions change, minerals may precipitate from these solutions, especially carbonates and

sulphates. In thermally transformed coal mine waste, between other, calcite, aragonite,

hydromagnesite, gypsum, and anhydrite have been identified.

On the coal mine waste dumps, nearly active fire areas, minerals generated by the

resublimation of fire gases may to be found also. Between them, native sulphur and sal ammoniac

have been identified.


96

Rare Earth Elements (REE) in the overburnt mining waste material

J. Nowak

Silesian University of Technology; [email protected]

Rare Earth Elements (REE) represent nowadays an important raw material being used in

many areas of life related to modern technologies. Although they are rather widely spread in

the Earth’s crust, due to their dispersion, it is highly difficult to extract them. All over the

world there are sparsely occurred natural beds of concentration being high enough to make

their mining justified. Increasing demand for REE together with their reduced supply from

China – the main producer of REE, results in the necessity of searching for new sources of

REE as well as tracking of their concentration changes in various processes both natural and

technological.

The paper presents variability of selected REE contents in coal mining waste thermally

transformed in the results of endogenous fires, which occur in the waste dump sites. The

research has been granted by the Ministry of Science and Higher Education of Poland within

the research project N 525 035 32/3750.

For the investigation 33 mining waste samples have been collected from the dump site No.

IV of the Nowy Wirek coal mine. The site contains rocks coexisting with coal seams of the

Ruda and Saddle beds of the Upper Silesia Coal Basin; mainly there were claystones, but also

mudstones and sandstones. The waste on the dump underwent self-heating resulted in

endogenous fires. Influence of high temperature led to transformation of the wastes, changing

their mineral composition and petrographic properties. Samples have been taken from the

zones of different thermal transformation level: macroscopically thermally untransformed

zone (unburnt), moderately thermally transformed zone (overburnt), and intensively thermally

transformed zone (sintered).

Contents of selected REE have been determined with use of the Instrumental Neutron

Activation Analysis (INAA). Due to limitations of this method following elements have been

measured: scandium (Sc), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm),

europium (Eu), terbium (Tb), ytterbium (Yb), and lutetium (Lu). Presence of yttrium (Y) has

been determined with use of the Fusion-Inductively-Coupled Plasms method (FUS-ICP).

With the use of the latter method main chemical components have been also assessed: SiO2,

Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, TiO2, P2O5, and the loss of ignition (LOI).

In the Table 1 arithmetic means of contents of each REE and their standard deviations have

been presented. Additionally, waste from the moderately thermally transformed zone has been

divided accordingly to their petrographic character, showing average values for sandstones,

mudstones, and claystones.

Average REE contents in the investigated waste (Table 1) amount: cerium Ce (58 –

70 ppm), lanthanum La (30 – 40 ppm), yttrium Y (35 – 56 ppm), neodymium Nd (24 – 33

ppm), and scandium Sc (13 – 17 ppm). In case of samarium Sm it was 5 ppm, ytterbium Yb

round 3 ppm, and amounts of terbium Tb and lutetium Lu did not exceed 1 ppm. REE


97

concentrations exhibited high differentiation indicated by high standard deviations. This is

reasoned by high heterogeneity of the waste, which originated from different seams, mining

levels, mine parts, as well as different mining and processing procedures.

The sum of contents of investigated REE in the thermally untransformed waste (193 ppm)

is slightly higher than in average REE sum in the moderately thermally transformed waste

(181 ppm). Burning of organic matter together with dehydroxylation of clay minerals and

thermal decomposition of minerals (i.e. from carbonates group) implicate loss of mass of the

waste, what is supposed to influence relative increase of concentration of the components.

Such a relation takes place in the case of the main chemical components – decreasing LOI

contents is accompanying by a significant increase of the contents of other components.

However, such relation does not occur in case of REE. Lower REE contents in the moderately

thermally transformed waste, could indicate smaller sorption properties of clayey minerals,

resulted from high temperature influence, what implicates the increased mobility of REE, and

partial removal of the REE out of the dump site area could happened. Within the thermally

untransformed waste all investigated REE, except yttrium (Y), exhibited highly positive

correlation with Al2O3, K2O, and TiO2, while in the thermally transformed waste this

correlation was significantly weaker or even vanished. This observation confirms the

connection between REE (except Y) with clayey minerals.

Tab. 1 Contents of investigated REE in the waste of various thermal transformation level

Ele

men

t

Waste from the

thermally

untransformed

zone

(9 samples)

Waste from the

moderately

thermally

transformed

zone

(17 samples)

Sandstones from

the moderately

thermally

transformed zone

(7 samples)

Mudstones from

the moderately

thermally

transformed zone

(5 samples)

Claystones from

the moderately

thermally

transformed zone

(5 samples)

Waste from the

intensively

thermally

transformed zone

(7 samples)

Mean

[ppm]

Std.

dev.

Mean

[ppm]

Std.

dev.

Mean

[ppm]

Std.

dev.

Mean

[ppm]

Std.

dev.

Mean

[ppm]

Std.

dev.

Mean

[ppm]

Std.

dev.

Sc 14.7 6.0 15.5 5.2 14.6 6.6 13.2 4.1 19.2 1.2 17.4 5.1

Y 35.0 6.4 36.2 9.8 36.3 9.2 38.0 15.4 34.2 3.3 55.6 11.4

La 35.8 13.1 32.9 9.3 30.4 10.2 32.3 12.2 36.8 3.1 40.1 7.1

Ce 70.1 25.7 61.5 17.3 57.7 18.6 61.4 24.1 66.8 6.6 67.7 14.0

Nd 27.3 11.0 25.6 6.6 23.7 7.8 26.0 8.1 28.0 1.9 32.9 6.6

Sm 5.0 2.0 4.6 1.3 4.2 1.4 4.8 1.6 4.8 0.5 5.8 1.0

Eu 1.3 0.5 1.1 0.3 1.1 0.3 1.1 0.3 1.2 0.2 1.3 0.3

Tb 0.3 0.5 0.6 0.3 0.6 0.4 0.6 0.3 0.7 0.1 0.6 0.5

Yb 3.2 0.9 2.8 0.7 2.6 0.6 2.9 1.1 3.0 0.2 3.7 0.6

Lu 0.4 0.1 0.4 0.1 0.4 0.1 0.4 0.2 0.5 0.0 0.5 0.1

∑* 193.0 181.2 171.6 180.7 195.2 254.4

*The sum relates to 10 investigated elements instead of all REE

In the waste from moderately thermally transformed zone, three main lithological types of

rocks may be distinguished: sandstones, mudstones, and claystones. All the types are

characterized by insignificant differentiation of the REE contents, although claystones exhibit

the highest one. This is probably related to the sorption properties of clay minerals.


98

In the waste form the intensively thermally transformed zone, where high amount of glass

is present, largely higher amount of REE has bee noticed. Average sum of investigated range

of REE from this zone amounted 254 ppm. Increased contents of REE in the waste from the

intensively thermally transformed zone probably results from the loss of mass, which occurs

during the fires, with simultaneously occurring binding of REE in high temperature minerals

or the glass, what prevented their migration out of the dump site.


99

Rare Earth Elements (REE) in the rocks accompanying selected coal seams

of the Mudstone and Sandstone Series of the Upper Silesian Coal Basin

J. Nowak, M. Kokowska-Pawłowska, B. Hanak

Silesian University of Technology

Rare Earth Elements (REE) form a group of 17 elements, to which belong lanthanides

together with scandium and yttrium – elements, which coexist in minerals with lanthanides

and possess similar chemical properties. These metals are not present on the Earth so rarely as

it suggested by their name, however they are strongly dispersed and they should occur at

significant concentration to make their mining production feasible. Due to their properties,

REE are of great importance by the use of advanced technologies, so they became considered

as strategic raw materials. Increased demand for REE together with reduced supply of them

from China – their major producer, result in prioritizing of the searching for new sources of

these raw materials.

In this paper results of investigation on the variability of REE contents in the rocks

accompanying selected coal seams from Zaleskie and Ruda beds of western part of Upper

Silesia Coal Basin (USCB) have been presented. 116 samples have been analysed from the

rocks coexisting with coal seams 405 and 408 collected from the USCB area.

Contents of selected REE have been assessed with a use of the Instrumental Neutron

Activation Analysis (INAA). In regard to the constraints of this method following elements

underwent evaluation: scandium (Sc), lanthanum (La), cerium (Ce), neodymium (Nd),

samarium (Sm), Europium (Eu), terbium (Tb), ytterbium (Yb), and lutetium (Lu). Contents of

yttrium (Y) was determined with a use of the Fusion-Inductively-Coupled Plasma (FUS-ICP)

method.

As it can be seen from the data listed in Table 1, the highest mean contents of the 10

considered REE has been observed by claystones (222 ppm). Slightly lower was the sum of

mean contents of analysed REE in sandy claystones (216 ppm), mudstoned (213 ppm) and

sideritic claystones (207 ppm). Probably it results from high amount of clayey minerals in

these rocks, which express high sorption properties. Significantly lower REE contents have

been observed by sandstones (183 ppm) and coal shales 9179 ppm). The lowest contents

have been noticed for clayey siderites, where mean sum of analysed REE amounted only

105 ppm.

Considering amounts of each particular element, the conclusion is that independently to the

petrographic character of a rock, the highest contents exhibited Ce, La, Y, Nd, and Sc.

Contents of the other REE are definitely smaller (by one or two orders of magnitude). Also,

high differentiation of REE contents have been observed between individual samples, what is

reflected by large values of standard deviations. This differentiation results probably from the

large area of research.


100

Table 1. REE contents[ppm] in analysed samples of rocks coexisted with coal seams

Ele

men

t

Claystones

46 samples

Sandy

claystones

17 samples

Sideritic

claystones

12 samples

Coal shales

10 samples

Mudstones

14 samples

Sandstones

9 samples

Siderites

8 samples

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Mea

n v

alu

e

Std

. d

ev.

Sc 20.7 2.2 19.2 2.0 19.8 2.3 14.5 4.6 20.2 2.0 14.3 3.0 11.5 5.2

Y 28.9 6.5 28.7 3.7 28.5 5.1 22.2 10.6 30.9 4.8 32.1 7.4 19.0 11.3

La 47.5 7.1 45.4 4.1 42.7 4.5 36.4 9.0 46.5 3.6 39.9 11.6 19.8 11.6

Ce 82.4 14.4 80.1 8.6 77.6 14.4 68.3 19.0 77.2 6.3 68.6 20.0 36.6 19.2

Nd 30.8 9.3 31.6 6.8 27.5 8.6 27.6 10.3 27.4 5.8 18.7 14.7 12.0 9.8

Sm 5.9 1.5 5.9 1.4 5.4 1.4 5.1 2.2 5.4 1.1 5.0 1.6 2.9 2.0

Eu 1.6 0.4 1.6 0.3 1.7 0.4 1.6 0.7 1.6 0.2 1.2 0.6 0.9 0.5

Tb 0.3 0.4 0.3 0.5 0.3 0.5 0.4 0.6 0.4 0.5 0.1 0.3 0.2 0.4

Yb 3.0 0.6 3.0 0.5 3.0 0.7 2.4 1.1 2.9 0.6 2.7 0.7 1.8 1.1

Lu 0.5 0.1 0.5 0.0 0.5 0.1 0.4 0.2 0.5 0.0 0.4 0.1 0.3 0.1

Suma* 221.6

216.2

206.8

178.9

212.8

183.0

105.0

*listed sum covers only 10 investigated REE

As concluded, most of the analysed REE exhibit increased concentrations in roof strata in

relation to their presence in floors and interburden. Higher mean contents in claystones from

roof strata demonstrated La and Y, in sideritic claystones La, Nd, and Ce. Higher amounts of

Sc, Y, La, Nd and Ce have been noticed for clayey siderites from roof strata In mudstones

from roof strata Nd were dominating. In roof sandstones mean contents of Sc, Y and La were

the highest.

Increased concentration of such numerous elements in the roof strata suggests their

infiltration origin.

The research has been granted by the Polish Ministry of Science and Higher Education in the frame of the

research project No. N524 463236.


101

Nano-compounds from Brazilian Coal Fires

M.L.S. Oliveira1, S.R. Taffarel

2, C.M.N.L. Cutruneo

2, L.F.O. Silva

1,2

1Institute of Environmental Research and Human Development – IPADH, Capivari de Baixo, Santa Catarina,

Brazil 2Laboratory of Environmental Researches and Nanotechnology Development, Centro Universitário La Salle.

Victor Barreto, 2288 Centro 92010-000 - Canoas, RS – Brasil

Burning coal-waste (spoil) heaps produce atmospheric pollution, environmental degradation,

and may seriously threaten the health and life of residents living nearby.

Coal fires can occur within in-situ coal deposits, active or abandoned coal mines, and in

waste piles produced from coal mining. Ignition sources may include forest fires, lightning

strikes, spontaneous combustion due to exothermic oxidation in the coal, and human activity.

Some coal fires are difficult to extinguish and individual fires can burn for decades or even

centuries. However, can be the consequence of spontaneous combustion; incidental natural

sparks (lightening strikes, forest fires); or malicious, negligent, or accidental human

intervention. A number of coal properties, often interrelated, affect the potential for

spontaneous combustion, including:

(1) Moisture content and volatile matter,

(2) Particle size and available surface area,

(3) Mineral matter type and pyrite content in particular,

(4) Coal rank,

(5) Petrographic composition (coal type).

This study describes nanominerals and associated trace elements in minerals nucleated in

conjunction with Brazilian coal fires. Petrological and geochemical analysis of the organic

and mineral matter from burning and unburnt zones in coal-waste piles have allowed

preliminary identification of the mineral and gas products that resulted from the combustion

process. The present work complements previous studies by identifying and providing

detailed characterization of carbon nanoparticles, agglomerates and mineral phases formed in

the burning waste piles. Any health and environmental consequences associated with these

particles would be expected to have a close relationship to their physical and chemical

characteristics, such as their size, morphology, composition, solubility, and oxidation state.

The study provides data not previously available from bulk characterization, and thus

contributes to assessing further the environmental and human health impacts of burning coal-

waste materials.

The principal components of the work are: (1) collecting samples from burning areas of

solid coal-waste piles (CWP) in Brazil; (2) investigating a potential method for estimating

emissions of nanominerals and ultrafine particles, based on direct measurements and

emphasizing the importance of electron microscope investigations; (3) identifying any

potentially toxic by-products from spontaneous combustion and the possible effects on human

health from nanominerals and ultrafine particles; (4) providing the scientific community with

initial order-of magnitude nanomineral emission estimates from Brazilian coal- fire zones.


102

Many sulfate minerals (gypsum, mascagnite, letovicite, barite, jarosite, and iron sulfate);

elemental sulfur; and other S–Cl–N–H, Hg, As, Pb, and Se compounds are currently detected

in researched coal fires. The blocks assemblage of CWPM ranged in color from white

(kaolinite, gypsum, and barite) to yellow-brown and red (oxidation of high pyrite resulting

ultrafine cubic jarosite pseudomorph and nanohematite crystals) and a relatively low amount

of amorphous Si–Al–Fe–Ti–Zr nanospheres. Native sulfur in spontaneous CWPM

combustion occurs as bright yellow micro/nanocrystalline botryoidal crusts. In addition,

several members of the MgSO4∙nH2O series, epsomite, hexahydrite, and pickeringite, were

identified by XRD, Raman, HR-TEM, and FE-SEM. Dehydration of epsomite to hexahydrite

is strongly dependent on the relative humidity. In the present case, the relative abundance of

these two phases may be expected to be quite variable, depending on the ambient conditions

in the field or the analytical process.

The utilization of XRD, FE-SEM/EDS, and HR-TEM provided detailed identification and

characterization of nanoparticles, agglomerates, and mineral phases formed from burning

Brazilian coal-cleaning rejects, and permitted identification of the potential effects of such

particles on the environment and human health. Both cubic and dendritic crystal habits of

salammoniac were observed, along with sulfates (gypsum and jarosite), and Fe-minerals. The

cubic form of jarosite suggests that it is a pseudomorph after pyrite. Dehydration of jarosite

can lead to the formation of less hydrous Fe-sulfates and hematite. Hematite, with some Cr in

the mineral structure, was noted in association with jarosite. In addition, HR-TEM studies

revealed the presence of fullerene carbons and multi-walled carbon nanotubes that contain

some potentially hazardous elements with varying degrees of crystallinity. This suggests that

the particles experienced a variety of high-temperature thermal histories. Future work will

include studying the thermodynamics and by-products of combustion, estimating emissions

from fires associated with coals of different rank, and examining the potential environmental

and health impacts on residential communities near the fires. This information will be

beneficial in understanding the potential human health and environment impacts of coal fires,

the importance on national and global scales of nanoparticles and toxicants from coal fires,

and the understanding of environmental controls on coal fires and related emissions.

However, only scientific, technological, economic, and political collaboration will lead to

solutions associated with various coal-fire problems on a global scale.


103

Coal-petrography and mineralogical studies

of the Çardak coal deposit (SW Turkey)

R.G. Oskay1, A.İ. Karayiğit

2, K. Christanis

1

1University of Patras, Department of Geology, Rio-Patras, Greece; [email protected]

2Hacettepe University, Department of Geological Engineering, Ankara, Turkey

Coal deposits formed under various conditions and in various geological times, are widely

spread over Turkey. The most significant deposits are of Tertiary, especially Neogene age.

During Pliocene times the palaeoenviromental conditions used to be favourable for peat-

formation in the territory, resulting in large reserves (7 Gt). This study aims to determine coal-

petrographical and mineralogical features of samples from the Çardak coal deposit in south-

western Turkey.

Huminite is the dominant maceral group (up to 92 vol.%, on mineral matter free; mmf)

basis consisting mostly of detrohuminite (up to 46 vol.%, mmf). Gelohuminite (up to 15

vol.%, mmf) is also common. The inertinite group, mainly inertodetrinite, appears in variable

amounts (up to 10 vol.%, mmf). Liptinite macerals are common and variable in quantity (up

to 14 vol.%). The mean random reflectance of huminite is about 0.28%. The identified

minerals in the lignite samples are quartz, pyrite, clay minerals (illite-smectite group),

feldspars, calcite, and aragonite. Most of the minerals determined applying X-ray

diffractometry, are also identified under the coal-petrography microscope, i.e. framboidal

(common type) and massive pyrite, clay minerals, quartz and carbonates.

Coal facies indices (moderate Gelification Index and Ground Water Index), as well as the

presence of framboidal pyrite, indicate wet, slightly anoxic conditions and relatively stable

water level during peat accumulation. Carbonate minerals (calcite and aragonite) and shell

fragments result in calcium-rich coal. Also the presence of mollusc shell fragments indicates

that the water level was above the peatland surface. Moderate detrohuminite content could be

related to reed-sedge vegetation, although moderate Tissue Preservation and Vegetation

Indices and high telohuminite content point to woody peat-forming vegetation. Therefore

mixed vegetation might have contributed to peat formation.


104

Petrographic characteristics of Karapınar-Ayrancı Lignite

(Konya, Central Turkey)

R.G. Oskay1, M. Salman

2, K. Christanis

1, M. Taka

2, H. İnaner

3

1Department of Geology, University of Patras, Rio-Patras, Greece; [email protected]

2General Directorate of Mineral Research and Exploration (MTA), Ankara, Turkey

3Department of Geological Engineering, Dokuz Eylül University, İzmir, Turkey

As a result of collision between the Arabian and the Anatolian plates (Middle Miocene to

Quaternary) sedimentary basins were formed and volcanism was activated in Central

Anatolia. These sedimentary basins host coal-bearing sedimentary sequences with important

coal reserves. The Karapınar-Ayrancı deposit is the most significant one due to its big

reserves (1.8 Gt). The basement rock is a Jurassic-Cretaceous marine limestone. The basin

filling consists of Miocene lacustrine and Pliocene coal-bearing sediments that are overlain by

Upper Pliocene-Quaternary lacustrine and fluvial sediments and volcanic rocks. Coal-

petrology studies were carried out on 29 core samples from two boreholes drilled in the north-

eastern part of the deposit. Matrix and mineral-rich lithotypes are common, char-rich coal also

occurs. In the studied lignite samples huminite macerals (up to 98 vol.%, on mineral matter

free basis; mmf) dominate. Detrohuminite is the most common maceral sub-group (up to 82

vol.%, mmf); telohuminite sub-group varies from 5 to 38 vol.%, mmf). Inertinite, mainly

fusinite and inertodetrinite, shows a great variety (up to 21 vol.%, on mmf basis). Liptinite,

commonly liptodetrinite, occurs in lower concentrations than the other groups (up to 13

vol.%, mmf). Inorganic constituents, namely clay minerals, carbonates, as well as framboidal

or euhedral pyrites, are common (up to 29 vol.%). Even though the dominance of

detrohuminite can be related with reed-sedge vegetation, the variable telohuminite quantities,

as well as the moderate tissue preservation and vegetation indices might be related to changes

in vegetation (dominance of herbaceous plants to mixed herbaceous and woody vegetation)

during peat formation. Low to moderate ground water influence and gelification indices, as

well as alternation between matrix and mineral-rich lithotypes could be related to water level

fluctuation. The predominance of herbaceous vegetation, along with high water table, resulted

in the fragmentation of the plant material and the predominance of detrohuminite. On the

other hand, high intertinite contents might indicate low water levels and thus, slightly oxic

conditions during peat accumulation. Fusinite and semi-fusinite along with char-rich lithotype

point to wild fires on and/or around the palaeomire. Also the occurrence of syngenetic

(framboidal) pyrite is related to anoxic conditions. The Karapınar-Ayrancı lignite formed in a

reed-sedge mire with subordinate contribution of woody vegetation under slightly anoxic

limno-telmatic conditions.


105

Mineral matter and trace elements in the Karapınar-Ayrancı lignite

(Konya, Central Turkey)

R.G. Oskay1, M. Salman

2, M. Taka

2, K. Christanis

1, H. Inaner

3

1Department of Geology, University of Patras, Rio-Patras, Greece; [email protected]

2General Directorate of Mineral Research and Exploration (MTA), Ankara, Turkey

3Department of Geological Engineering, Dokuz Eylül University, Turkey

The Karapınar-Ayrancı coal deposit (south-Central Turkey) hosts the second biggest lignite

deposit (1.8 Gt) of Turkey. As it is planned to be exploited for power generation,

understanding the mineralogical and elemental composition is important for technological and

environmental aspects. This paper presents preliminary results on mineralogical and

geochemical composition of the lignite samples and their ash residues from one borehole at

NE part of the deposit. The samples display high ash yield (average 37.30%; on dry basis),

high volatile matter content (average 74.00%; on daf basis), high total S (up to 11.68%, daf)

and H contents (up to 10.35%, daf). The identified minerals in the bulk lignite samples are

quartz, clay minerals (illite, kaolinite/chlorite and smectite), mica, halite, feldspar, calcite,

pyrite, bassanite/gypsum. Most of the minerals, i.e. framboidal (common type) and euhedral

pyrite, clay minerals, quartz and carbonates, are also identified under the microscope.

Minerals and other inorganic constituents in coal have different reaction pathways during

combustion, thus the identified minerals in ash residues at 750°C vary strongly.

Quartz/cristobalite, forsterite, feldspar, akermanite, gehlenite, illite/mica, haematite, Ca-

ferrites, lime, anhydrite, and rarely dolomite are identified in the ash. Factor analysis on

geochemical data shows that the elements have intermediate affinities; except of Ag, Al, Cu,

Li, V, and Ni. Also the HAPs such As, Be, Cr, Co, Pb, Mn, and Ni are determined in the

studied samples; however, their contents are below the world and Turkish feeding coal

average values. Beside, high total S content will cause environmental and technological

problems (e.g. acid drainage at a dumping site or boiler corrosion), although the presence of

calcite in lignite and anhydrite in ash indicate that sulphur contained is bound by carbonates

during combustion; hence wet scrubber could be effective as a desulphurization technique. On

the other hand, the presence of lime, haematite and Ca-ferrites in ash will cause slagging and

fouling problems in the boilers. Applying reasonable exploitation planning, appropriate

beneficiation techniques and choosing suitable boiler system, technological and

environmental impacts of lignite from Karapınar-Ayrancı deposit could be successfully faced.


106

Monitoring progress of combustion under oxy-fuel atmosphere of coals

and charcoals of similar volatile matter content by microscopy techniques

J.G. Pohlmann1,2

, E. Osório1, A.C.F. Vilela

1, M.A. Diez

2, A.G. Borrego

2

1Iron and Steelmaking Laboratory (LASID), UFRGS, PO Box 15021, 91501-970, Porto Alegre, Brazil; ++ 55 51

3308 7074; [email protected] 2Instituto Nacional del Carbón (INCAR-CSIC). Francisco Pintado Fe, 26, 33011 Oviedo, Spain

Pulverized coal is widely used to be burned in boilers for power generation or as a source of

heat and reducing gases in the ironmaking process whereas charcoal is a promising fuel to

partially replace it because of its renewable origin and neutrality in CO2 emissions (Norgate

and Langberg 2009). Oxy-fuel combustion technology consists of burning the fuel in a N2-

free atmosphere, which is replaced by a CO2-rich gas facilitating the subsequent capture of

CO2. Both incorporation of biomass in the process and oxy-fuel combustion can be combined

for a greater abatement in industrial processes. Biomass is known to be more reactive than

coal under similar combustion conditions (Kastanaki and Vamvuka 1996) but its low density,

low calorific value and high hygroscopic character typically prevents a wider incorporation

into operating industrial processes. Densification of biomass reduces its volatile matter

content, increases its calorific value and facilitates the handling of the material by

approaching its characteristics to those of the fuel to be replaced (Arias et al. 2008). In this

context two fuels with similar volatile matter content (~23%), one being a medium volatile

bituminous coal (CRA) and the other one the fines generated during industrial charcoal

production from eucalyptus (CCF), have been selected for this study in order to follow the

transformation occurring during their combustion under oxy-fuel atmosphere with increasing

oxygen content.

The CRA coal has a vitrinite reflectance of 1.23% and an inertinite content of 47%, mostly

teloinertinite having an average reflectance of 1.88%. CCF has higher reflectance (Rr=2.27%)

and higher scatter in the readings than the coal (standard deviation of 1.3 vs. 0.4%), but

similar modal values around Rr=1.7%. Combustion of pulverized samples (36-80µm) at 2.5, 5

and 10% O2 in CO2 has been carried out in a Drop Tube Furnace (DTF) at 1300 ºC. Optical

microscopy analysis was performed on the samples as well as test of reactivity to CO2 in

thermobalance and specific surface area measurements by adsorption isotherms.

As expected, char conversions increased with oxygen content in the DTF and were

significantly higher for the charcoal than for the coal for similar oxygen concentrations.

Figure 1 shows the appearance of the chars obtained under different O2/CO2 conditions. Coal

chars yielded generally cenospheric particles with abundant secondary porosity within the

walls. Vitrinite transformed to form anisotropic domains in swollen particles whereas a

significant part of the inertinite remained unfused generating massive isotropic particles. The

high degree of association between the vitrinite and inertinite in the coal results in common

mixed particles containing material derived from both components. CCF chars consisted of

mostly isotropic particles, some of them with massive and compact appearance and some

formed by cell-walls with empty channels as also observed in fusinite. During the combustion



107

tests some of the massive particles developed devolatilization vacuoles. Higher conversions

lead to smaller particles in the coal chars and to the collapse of the most delicate particles with

cellular structure, being concentrated in the most combusted chars the massive and larger

particles. Combustion progressed in the coal chars through the boundaries of the anisotropic

domains whereas in the charcoal chars the surfaces of the particles were finely spotted.

Specific surface area of both fuels significantly increased in the reactor with CCF chars

reaching significantly higher surface areas of both mesopores (BET) and micropores (CO2-

DR) than the CRA chars. In both cases micropore surface areas were higher than those of

mesopores. Both mesopore and micropore specific surface areas firstly increased with

conversion and then decreased for the most burned chars in CCF chars, whereas a continuous

increase in mesopores and decrease in micropores is observed in the coal chars. The specific

surface areas control the reactivity to CO2 results, being the coal chars, with much anisotropic

material, less reactive than the isotropic CCF chars.

Fig. 1. Optical microscopy images of chars under different O2/CO2 atmospheres.

Acknowledgement: This work has been financed through a bilateral Spain-Brazil project PIB2010BZ-

00418/CNPq 560839/2010-3 and the Brazilian Coal Net. The assistance of Dr. D. Álvarez from INCAR in the

preparation of the chars is gratefully acknowledged.

References

Norgate T. Langberg D. 2009 - Environmental and Economic Aspects of Charcoal Use in Steelmaking. ISIJ

International, 49, 4: 587-595.

Kastanaki E. Vamvuka D. 2006 - A comparative reactivity and kinetic study on the combustion of coal–biomass

char blends. Fuel, 85: 1186-1193.

Arias B., Pevida C., Fermoso J., Plaza M. G., Rubiera F., Pis J.J. 2008 - Influence of torrefaction on the

grindability and reactivity of woody biomass. Fuel Processing Technology, 89: 169-175.


108

Microscopical characterization of carbon materials derived from coal and

petroleum and their interaction phenomena on making steel electrodes,

anodes and cathodes blocks

G. Predeanu1, C. Panaitescu

1, M. Balanescu

1, G. Bieg

2, A. Gómez Borrego

3, M.A. Diez

3,

B. Kwiecińska4, M. Marques

5, M. Mastalerz

6, M. Misz-Kennan

7, S. Pusz

8, I. Suárez Ruiz

3,

S. Rodriguez5, A.K. Singh

9, A. Varma

10, A. Zdravkov

11, D. Životić

12

1University Politehnica Bucharest, Bucharest, Romania

2Mikroskopische Untersuchungen, Haltern am See, Germany

3Instituto Nacional del Carbón (INCAR-CSIC) Oviedo, Spain

4AGH University of Science and Technology, Kraków, Poland

5Universidade do Porto, Porto, Portugal

6Indiana University, Indiana Geological Survey, Indiana, USA

7University of Silesia Sosnowiec, Poland

8Polish Academy of Sciences, Gliwice, Poland

9TATA Iron & Steel Comp. Ltd, Jamshedpur, India

10Indian School of Mines, Dhanbad, India

11University of Mining and Geology “St. Ivan Rilski”, Sofia, Bulgaria

12University of Belgrade, Belgrade, Serbia

Introduction

The Microscopy of Carbon Materials Working Group of Commission III of the International

Committee for Coal and Organic Petrology was established to investigate the efficiency of

microscopical methods to the study of carbon materials derived from coal and petroleum, with an

emphasis on quality control of raw materials either on different technological stages, in order to

evaluate the physical-chemical properties of the parent, intermediary, and final products.

The WG is focused to consolidating and completing the existent methods developed for carbon

materials structural and textural characterization: (i) Describe of the optical appearance of the

carbon textures and identify the morphological differences as: optical texture and shape, optical

type and size; (ii) Use the previouse exercises classification scheme to distinguish between

different classes considered both for the optical texture (isotropic/anisotropic), and shape, optical

type (punctiform, mosaic, fiber, ribbon, domain) and size; (iii) Evaluate the origin of optical

texture and the porosity development.

Experimental

A very simple classification scheme was used, in which the criteria to distinguish between

different classes considered both the optical texture, type and size, origin and the porosity

development. The results were evaluated on 4 levels: (i) optical texture (isotropic or anisotropic);

(ii) optical type and size (punctiform, mosaic, fiber, ribbon, domain); (iii) origin of the inclusions;

(iv) all levels together. The exercises consisted on 372 fields in black and white pictures. The

criteria proposed for the classifications of optical appearance of mesophase during thermal

evolution to semicoke and coke were according to the terminology belonging to the ASTM D

5061/1997, Microscopical determination of volume percent of textural components in

metallurgical coke.


109

Results and discussions

The activities developed were focused to: (2009) Identify the petrographic textures representing

the structural organization of the organic matter corresponding to solid carbon precursors, as:

coal-tar pitch coke, petroleum coke, calcinated anthracite; (2010) Identify the mesophase

formation from the isotropic aromatic parent liquid to an anisotropic solid texture (nucleation,

coalescing, mesophase coalescing final stage) of coal-tar pitches: binder pitch (type A) and

impregnating pitch (type C) currently used as matrix precursors of many carbon materials;

describe the evolution of optical characteristics of pitches during heating up to 480, 500, 800 and

1000oC that influences their preparation within the production industrial steps; (2011) Identify of

the morphological differences occurred between the three different samples of steel electrodes

used: baked electrodes, re-baked electrodes and graphitized electrodes and the interaction

phenomena between calcinated petroleum coke and binders: binder pitch and impregnating pitch;

(2013) Identify of the morphological differences occurred in the anodes and cathodes blocks used

in aluminum industry which petrographic composition depends on the grain size distribution of

the blended solids (petroleum coke, anthracite and the quality of the binding material (pitch).

A B C D

Fig. 1. Photomicrographs of needle calcinated petroleum coke (A), mesophase formation in impregnation pitch

(B), anisotropic calcinated anthracite (C), graphitized petroleum coke (D) 500X, glycerin imm.

Fig.2. Average level of agreement of each analyst during participation in 2009-2011 ICCP CM WG

Conclusions

It has been realized in a good agreement between the 15 active participants who attended about all

the exercises.


110

Characterization and petrographic composition of ash and slag from

the Turceni coal-fired power plant, South-West Romania

G. Predeanu1, C. Panaitescu

2, L.G. Popescu

1

1University “Constantin Brancusi” of Targu Jiu, 30 Calea Eroilor, Targu Jiu, Gorj County, Romania

[email protected]; [email protected] 2University “Politehnica” Bucharest, 1 Polizu St. Bucharest, Romania [email protected]

Introduction

A variety of combustion waste products are generated during burning lignite in power plants.

They exhibit complex composition depending mostly on coal type and technological

processes used. The aim of the present study is the chemical and petrographic characterization

of some lignite combustion residues, ash and slag sampled from the storage deposit of the

Ceplea Valley belonging to the Turceni power plant historical dump, covering an area of

approx. 50 ha, and in which the accumulated amount is of approx. 20 million tons.

The physical-chemical composition of ash and slag depends on physical-chemical

composition of parent coals and of a series of particular factors, as are the rank and

petrographic composition (Levandowski, Kalkreuth 2009; Moreno et al. 2005; Suárez-Ruiz et

al. 2008; Panaitescu et al. 2008). Knowledge of the properties of coal ashes is an important

parameter also due to the fact that ash and slag deposits may create environmental problems

through leaching of toxic substances, in decisions on their industrial use and in evaluation of

their environmental impacts.

Experimental

Laboratory measurements of X-ray fluorescence (XRF) have confirmed that, in terms of

chemical composition the ash from the Ceplea Valley deposit matches the oxidic class SiO2 -

Al2O3 - Fe2O3 - CaO, being from this point of view relatively similar to feldspathic calcareous

clays, partially calcined (weakly burned firebrick): 40-50% SiO2, 16-21% Al2O3, 8-9% Fe2O3,

9-14% CaO, 1.5-3% Na2O+K2O (Abagiu et al. 2013).

Results and discussions

Low rank of lignite is represented by the increased proportion of wood components, in

particular of those structured (textinite), and the presence of attrinite and densinite,

corpohuminite and gelinite components (Table 1). Behavior of organic and mineral matter

during combustion is shown in photomicrographs of Fig.1.

Table 1. Structural composition of lignite, % vol (Predenau et al. 2013)





111

Pet

rog

rap

hic

com

po

nen

t

Tex

tin

ite

(ro

un

d c

ells

)

Tex

tin

ite

(elo

ng

ated

cell

s)

To

tal

stru

ctu

red

wo

od

en m

ater

ial

Ulm

init

e

Org

anic

w

oo

den

mat

eria

l

Att

rin

ite

+ d

ensi

nit

e

Co

rpo

hu

min

ite

Gel

init

e

Lip

tin

ite

Iner

tin

ite

To

tal

org

anic

mat

ter

Cla

y m

iner

als

Fer

rou

s m

iner

als

To

tal

min

eral

mat

ter

To

tal

org

anic

+

min

eral

mat

ter

% 0.5 27.2 27.7 20.5 48.2 2.5 6.7 13.3 1.0 0.5 72.2 24.0 3.8 27.8 100.0

a b c d

Fig. 1. Photomicrographs of ash and slag, reflected light, glycerin immersion, 500X: a) inertinite tissue, b)

carbominerite and pirite, c) textinite and fungi, d) mineral oxides.

Conclusions

The paper presents the petrographic analyses carried out with the goal of identifying the

behavior of organic and mineral material of lignite of Oltenia basin during combustion.

The results of this study provide information which can be applied throughout power plant

operation and for environmental impact studies.

Acknowledgements. The present research has been carried out through the LIFE10 ENV/RO/729 Project.

References

Abagiu T., Volceanov E., Predeanu G., Zăman F., Popescu L. G., Slăvescu V. 2013 - Physical-chemical

characteristics of some industrial wastes arguments for their use in the field of building materials

manufacturing. 13th

Int. GeoConference SGEM 2013, Albena 17-23 June, in press.

Levandowski J., Kalkreuth W. 2009 - International Journal of Coal Geology, 77: 269-281.

Moreno N., Querol X., Andre J.M., Stanton K., Towler M., Nugteren H. et al. 2005 - Fuel, 84: 1351–1363.

Panaitescu C., Predeanu G., Miu M. 2008 - 60-th ICCP Meeting, 25th Meeting of TSOP, Oviedo, Spain.

Predeanu G., Abagiu T., A.,, Popescu L. G., Cruceru M. 2013 - Evaluation of structural changes that occur

during the combustion of coal of Oltenia basin at turceni power plant. 13th

Int. GeoConference SGEM 2013,

Albena 17-23 June, in press.

Suárez-Ruiz I., Valentim B., Bouzinos A., Flores D., Gómez Borrego A., Kalaitzidis S. Predeanu G. et al. 2008 -

The Society of Organic Petrology (TSOP) Newsletter, 25, 3: 10-13.


112

Qualitative improvement of xylite by mechanical preparation

G. Predeanu1, O.V. Scorţariu

2, C. Panaitescu

3

1Metallurgical Research Institute, Mehadia St. 39, Sector 6, 060543 Bucharest, Romania

2Energy Complex Oltenia, Branch Mining Division Targu Jiu, T. Vladimirescu St. 1-15, 210143 Tîrgu Jiu,

Gorj County, Romania 3University Politehnica, Bucharest, Polizu St. 1, Sector 1, 011061, Bucharest, Romania

Introduction

This paper presents the results obtained at pilot level of preparation (by crushing and

volumetric classifying) of xylite, for obtaining structural unchanged varieties sizes suitable for

experiments to obtain charcoal and activated carbon (Predenau et al. 2005; Predenau,

Panaitescu 2007). The experiments were performed to improve the xylite quality recovered

from the Oltenia lignite basin, by mechanical preparation. The study analyzes the most

important parameters that involves the selective grinding of a representative amount of 15.7

tone xylite (moisture, mineral content, botanic origin), using an industrial equipment (a

hammer-crusher of 50 tone/h) and the yields and quality of the fractions obtained on passing

through 30, 20, and 10 mm sieves. The key objectives of this study are: (1) to establish yields

and quality of the fractions obtained by processing a representative amount of xylite (2) to

reveal the occurrence, selection methods and preliminary assessment of the xylite reserves

necessary for designing a capacity for commercial-scale processing installation. It was proved

that selective crushing and sieving is a very effective technique to obtain > 80% yields of

xylite fractions over 10 mm, used for charcoal and activated carbon making. Selected xylite

fractions were characterized by analytical methods, including optical microscopy.

Experimental

The study is based on about 35 tones of xylite hand picked from Lupoaia open pit mine (coal

seam VIII, Motru Coalfield) and transported by railway, to the raw material deposit. In order

to perform xylite mechanical processing by crushing and sizing, the sample was stored on a

concrete covered platform, to decrease the total moisture content from 45-50% (deposit total

moisture) up to 20-25%, with positive influence on the energy consumption during

pyrogenation stage. At the end of the storage period, the whole xylite amount was transferred

to the coal preparation unit, belonging to the Motru thermal power plant UAATA of 6 MW/h.

The preparation flowsheet included: the underground storage bunker (capacity of 5 tone);

scoope elevator; hammer-crusher of 50 tone/h capacity; conveyor belt no.1; intermediary

bunker; conveyor belt no.2; vibrating sieve (with a capacity of 5 to/h) with round meshes of

10, 20 and 30 mm. After the first passing through the crushing equipment, xylite was sorted to

grain sizes using 10, 20 and 30 mm sieves (phase I).

The unsieved fraction on the 30 mm sieve, having a coarse-robust, wooden or fibrous

aspect, was weighed and separately deposited for further crushing (phases II and III).


113

Results and discussion

The petrographic researches of the fractions obtained by crushing and screening demonstrated

a preferential repartition of the macerals by grain size categories depending of their natural

grindability is shown in Fig.1. The large scale experiments confirmed the previous results

concerning the quantitative structural aspects of the organic and mineral composition, as

follows: increasing of structured wooden material to the large grain sizes: 71.2% (+30 mm)

and 69.5% (20-30 mm); increasing of total wooden to the large fractions: 86.6% (+30 mm)

and 78.2% (20-30 mm); mineral mass is accumulated mostly in the fine fraction: 10.5% (10-

20 mm) as in coarse fraction 5.0% vol. (+30 mm) due to preferential distribution of clay

minerals in structurated material and high crushing capacity of carbagilite.

a b c

Fig. 1. Photomicrographs of some petrographic constituents in xylite fractions, reflected light, oil immersion,

250x: a) Cellulose impregnation (dark grey); b) Fissured gelinite with mono-, bi- and pluricellular funginite

(white); c) Textinite with pressed round cells and small mineral impregnation.

Conclusions

In the present investigation was demonstrated the positive effect of mechanical preparation of

xylite samples by crushing and sizing to be used for char and activated carbon making. The

results are extremly encouraging from the quality of size fractions obtained taking into

account the xylite amount that was processed, and the mechanical preparation performed on

an industrial flowsheet.

References

Predeanu G., Vacarciuc I., Scorţariu O., Hanu D. 2005 - LIFE 02 ENV /RO/46, Final report EnvACTCARB,

Special Issue, www.icem.ro/life1/SiteLife/index.html.

Predeanu G., Panaitescu C. 2007 - Petrographical evaluation of xylite activated carbon. Int. J. Coal Geol. 71:

542-553.

http://www.icem.ro/life1/SiteLife/index.html


114

Vitrinite Thermal Maturation Profiles and Comparative Study for Five

Yukon Petroleum Exploration Wells

J.C. Reyes, S. Saad, L.S. Lane

Geological Survey of Canada 3303 33rd

St. NW Calgary, Alberta, Canada, T2L 2A7; 1- 403 292-7120;

[email protected]

Eagle Plain Basin is one of eight prospective basins in the Yukon identified as having

significant oil and gas potential. To date, more than 34 wells have been drilled in the basin,

many of which show evidence of the presence of conventional oil and gas. An understanding

of these multifaceted petroleum systems is imperative for present and future development in

the area. In this study, quantitative vitrinite reflectance and qualitative analyses of dispersed

organic matter (DOM) from five petroleum exploration wells in Eagle Plain, north-Central

Yukon were summarized in order to determine thermal maturity profiles in Silurian to Upper

Cretaceous strata throughout the basin. These five wells are representative of eight wells that

are summarized in a soon-to-be released GSC Open File Report (Open File 7056). This study

integrates data from previous work by Link and Bustin (1989) as well as recent analyses from

the Geo-Mapping for Energy and Minerals (GEM) Yukon Basins Project, a four year project

aimed at upgrading geoscience knowledge of Yukon’s sedimentary basins.



115

Evaluation of Cretaceous coals from western India

through petrographical and geochemical parameters

B.D. Singh1, S. Mahesh

1, S. Paul

2, A. Singh

1, S. Dutta

2

1Organic Petrology Group, Birbal Sahni Institute of Palaeobotany, 53 University Road, Lucknow-226 007;

[email protected] 2Department of Earth Sciences, Indian Institute of Technology Bombay, Powai, Mumbai-136 119

The Early Cretaceous coal deposit in the Thangad area of the Surendranagar district (Gujarat

State) is associated with the Than Formation of the Saurashtra Basin. The data generated on

organic composition (macerals), mineral matter contents, rank, total organic carbon (TOC),

biomarkers, etc. of the deposits of Thangad, through petrographic and geochemical studies,

are utilized to characterize these western Indian coals for their optimal utilization. The

quantitative estimation of macerals indicates that the coals are rich in vitrinite macerals (39-

57%) followed by inertinite (9-33%) and liptinite (2-16%) macerals. Among the vitrinite

group of macerals, telovitrinite (collotelinite + telinite) is dominant in these coals followed by

detrovitrinite (collodetrinite + vitrodetrinite). The liptinites are chiefly constituted by

liptodetrinite and bituminite. Semifusinite/ fusinite and inertodetrinite represent the inertinite

group. The coals have moderate to high contents (8-36%) of associated mineral matters

represented mainly by clastic minerals and pyrite (10-12%). The rank, determined through

vitrinite reflectance measurements (Rr mean values: 0.86-1.05%), indicates that the studied

coals are of high-volatile bituminous A stage.

The saturated hydrocarbon in the studied samples is characterized by C14 to C32 n-alkanes

with a unimodal distributional pattern. Isoprenoids pristane to phytane ratio varies from 1.1 to

2.8. The major diterpenoids in the samples are 19-norisopimarene, labdane,

sandaracopimarane and unknown C18 and C19 diterpenoids. Presence of these diterpanes

suggests the terrigenous land plants (as also indicated by Phytane/n-C18 vs Pristane/n-C17

plot), more precisely conifers were the contributor to the precursor organic matter. Absence of

extended tricyclic terpanes series and the association of C19 and C20 tricyclic terpanes with

conifer derived diterpenoids indicate that these compounds were derived from the higher

plants. Rock-Eval Tmax and vitrinite reflectance data indicate that the studied coals have fall in

the catagenetic zone of hydrocarbon generation. The TOC content (20-60%) and presence of

Type III/II kerogen suggest that the coal-bearing sequence has the potential to generate both

oil and gaseous hydrocarbons.



116

Structure and reactivity of pyrolitic carbon

collected from the coke oven chamber

Ł. Smędowski

Institute for Chemical Processing of Coal, 1 Zamkowa St., 41-803 Zabrze; +48 32 271 0041-355;

[email protected]

Carbon deposits, called by cokemakers as ‘graphites’, form as a result of thermal cracking of

tars and gas hydrocarbons that are released during industrial coking of coal charge (Zymla

and Honnart 2007). There are a lot of papers where the mechanisms of deposits’ forming are

described (Mianowski et al. 2006; Zymla and Honnart 2007). In this work the knowledge

about carbon deposits that consist mainly of pyrolitic carbon was fill up with the results of

studies on their structure. The aim of this work is to characterize structure and reactivity of

pyrolitic carbon collected from the coke oven chamber.

Four samples of carbon deposits were collected from different parts of coke oven chamber,

e.g.: form the oven wall (dep. 1), from the oven door (dep.2), oven roof (dep.3), ascension

pipe (dep.4). This chamber works in ArcellorMittal Poland – division Zdzieszowice coking

plant. Samples were studied with use of: Raman spectroscopy (RS) and X-ray diffraction

(XRD). Basing on analysis of XRD and Raman spectra sets of structural parameters were

determined for each sample and the quantitative characterization of carbon deposits structural

ordering was done. Furthermore, it was found that structure of pyrolitic carbon depends on

thermal conditions that took place while carbon deposits were formed. Basic parameters of

the deposits studied are presented in Table 1. It can be seen that the moisture and ash contents

are similar for all samples studied while the volatiles and carbon contents change with the

temperature in chamber – the dep.1 sample that formed in the highest temperature the is most

devolatilized and mainly consist of carbon while the dep.4 sample (formed in the lowest

temperature) has quite high content of volatiles and low content of carbon.

Table 1. Basic characteristics of samples studied.

dep.1 dep.2 dep.3 dep.4

Moisture content, Ma, % 0.1 0.2 0.6 0.8

Ash content, Ad, % 1.5 3.3 2.4 4.5

Volatiles content, Vdaf

, % 0.23 0.28 1.42 8.15

Carbon content, Cdaf

, % 97.6 96.2 94.2 92.9

Values of the structural parameters of pyrolitic carbons are presented in Table 2. It can be

seen that the crystal stacking and interlayer spacing changes in similar order as the volatiles

and carbon contents and differs from 7,83 to 3,10 nm and from 0,345 to 0,352 nm

respectively. However, there is an deviation from this trend for both the Raman parameters.

The ID1/IG as well as AD3+D4/Aall reach the lowest values for the dep.3 sample, collected from

the oven roof. The ID1/IG parameter corresponds to the lateral size of the crystalites, La, while

AD3+D4/Aall corresponds to the amounts of amourphous and very poor ordered carbon in the



117

structure of the material (Ferrari and Robertson 2000). Both of these parameters correspond to

the reactivity of the structure with depends on the amounts of disordered carbon atoms as well

as on the accesibility to the carbon atoms that form aromatic layers of pyrolitic carbon. If the

lateral size of crystalizes is small and there is a lot of disordered material than reactivity of

such material is relatively high. The potentially higher reactivity of the dep.3 sample is an

important conclusion for cokemakers because the pyrolitic carbon is unwanted material in the

coke oven chamber, especially on its roof because the presence of ‘graphite’ in high amounts

can seriously disturb technological operations performed durng production of coke. The most

popular method of the deposits removal is their burning off. For that reason, conlusion

presented in this work seems to be interesting for the cokemakers, because it indicates that the

smaller amounts of oxygen can be used for the burning off the deposits on the roof than in the

case of the ovens wall and door.

Table 2. Values of structural parameters of samples studied.

dep.1 dep.2 dep.3 dep.4

Lc, nm 7.83 3.55 3.32 3.10

d002, nm 0.345 0.347 0.350 0.352

ID1/IG 2.25 2.18 1.62 1.93

AD3+D4/Aall 0.24 0.26 0.43 0.28

Notation: Lc – crystal stacking (XRD), d002 – interlayer spacing (XRD), ID1/IG – ratio of D1 and G bands

intensities (RS), AD3+D4/Aall – ratio of D3+D4 bands area to the sumaric area of all bands (Raman).

Acknowledgements: This study was financed under the Smart Coking Plant R&D Project (Innovative Economy

Programme (POIG), Contract no 01.01.02.-24-017/08).

References

Ferrari A.C., Robertson J. 2000 - Interpretation of Raman spectra of disordered and amorphous carbon, Physical

Review B - Condensed Matter and Materials Physics. 61: 14095-14107.

Mianowski A., Bigda R., Zymla V. 2006 - Study on kinetics of combustion of brick-shaped carbonaceous

materials. Journal of Thermal Analysis and Calorimetry 84: 563 – 574.

Zymla V., Honnart F. 2007 - Coke oven carbon deposits growth and their burning off, ISIJ international, 2007,

10: 1422 - 1431.

http://www.scopus.com/authid/detail.url?authorId=54415476900&eid=2-s2.0-0242603790

http://www.scopus.com/authid/detail.url?authorId=7404532552&eid=2-s2.0-0242603790

http://www.scopus.com/source/sourceInfo.url?sourceId=11000153773&origin=recordpage

http://www.scopus.com/source/sourceInfo.url?sourceId=11000153773&origin=recordpage


118

Organic petrology and geochemistry of the Oligocene source rocks

in the Glina Depression (Croatia)

D. Španić, T. Troskot-Čorbić

INA-Industrija nafte d.d., E&P Research Laboratory Department, Zagreb, Croatia, [email protected]

The outcrop samples from four locations of the Oligocene source rocks from Glina

Depression in the Croatian part of Internal Dinarides were geochemically and petrologically

analyzed and typified. Glina Depression occupies the southwestern portion of the Pannonian

basin and is situated at its margin south from the petroleum productive Sava depression unit.

External or Karst Dinarides represent carbonate platform which exists from the Jurassic to

the Middle Eocene, while Internal Dinarides correspond to contemporaneous periplatform

carbonate flysch interlayered with distal pelagic sediments of the Tethys Sea. At the Eocene-

Oligocene boundary, plate tectonic activity caused destruction of the western part of the

Tethys Sea, which resulted in the appearance of the Mediterranean Basin in the south and the

intracontinental euxinic Paratethys Basin in the north.

Present-day Internal Dinarides corresponds to southern margin of the Paratethys. Glina

Depression was probably restricted lagoon with brackish influences and periodically suboxic

to anoxic bottom conditions.

Dark laminated carbonaceous shales have organic carbon in the range from 2.03 to 13.61

%. Rock Eval pyrolysis indicates kerogen type I-II with consequently good to excellent

potential for hydrocarbon generation (HI= 331-946 mg HC/g TOC; S2= 6.71-128.78 mg

HC/g rock). Pyrolytic maturity parameters show diagenetic stage in thermal evolution

(Tmax= 428-438°C, PI= 0.01-0.06).

Microscopic examinations and stable carbon isotope analyses on kerogen concentrates, as

well as gas chromatographic analyses of the alkane fraction of extractable organic matter

revealed two types of organic facies:

1. Strong yellow fluorescing bituminite (amorphous organic matter) without any traces of

structured macerals. Thermal alteration indices, estimated on isolated amorphous

organic matter, are 2- (0.35-0.45 VR). Stable carbon isotope analyses give values from -

28.61 to - 31.08 δ13CPDB. Gas chromatographic analyses show dominance of C18-C24

normal alkanes and Pr/Ph ratio <0.8, which is evidence for algal origin of organic

matter and anoxic environment of deposition.

2. Moderate yellow-orange to orange-brown fluorescing bituminite with traces of yellow

fluorescing alginite (Botryococcus), liptodetrinite and up to 20 % vitrinite (huminite).

Vitrinite reflectance values are from 0.33-0.49 % VR. This type of kerogen is richer in

heavy stable carbon isotope (-25.16 to -27.22 δ13CPDB) in comparison with former

type of organic facies. In the gas chromatograms dominate odd alkanes in the range

C25-C31 and Pr/Ph ratio is over 1, which means high terrestrial organic matter input

and suboxic to oxic environment of deposition.


119

Study on morphology, structure and composition

of thermally altered coal and biomass

I. Sýkorová, M. Havelcová, Z. Weishauptová, H. Trejtnarová, J. Blažek

Institute of Rock Structure and Mechanics AS CR,v.v.i. V Holešovičkách 41, 182 09 Praha 8, Czech Republic;

+420 266009 280; [email protected]

Products of thermal degradation of fossil fuels and vegetation formed in nature and human

life embody very interesting carbonaceous materials. They can represent raw materials for

electricity production, preferably from renewable energy sources, for other industrial

purposes, e.g. steel and chemical industry, and for ecological applications, e.g. preparation of

sorbents for treatment of sewage, gasses. The relatively resistant carbonaceous residues

remaining after incomplete combustion of fossil fuels and vegetation can contribute

significantly to the carbon content in soil in recent, and in sediments in the past. On the other

hand the carbonaceous compounds and solid products can cause problems in the environment

and health.

The first part of the solution of the grant project (No. 13-18482S of the Czech Science

Foundation Research Grants) was focused on the study of changes in morphology, structure

and composition of thermally degraded coal and biomass due to two basic processes of

incomplete combustion in air and reduction atmosphere. The attention was paid to ecological

aspects expressed by “black carbon” (BC) and PAHs production.

Six original raw materials of various rank: bituminous coal (the Czech Part of the Upper

Silesian Basin), lignite (the Tertiary Sokolov Basin), peat from the Krásno peat bog in

western Bohemia, and biomass (oak and spruce wood and grain of the wheat) were subjected

to char production. Raw materials were heated to temperatures of 350, 450, 600, 800oC in a

muffle furnace in the air and nitrogen atmosphere. Produced chars as the raw materials were

divided into samples for petrographic, sorption and chemical analyses.

The results showed significant effects of increased temperature and atmosphere on mass

loss, reflectance values, petrological composition, porous characteristics, elemental and

hydrocarbon composition. Mass losses increased up to 66% during the exposure of coal

samples to temperatures of 25 – 600oC in the air atmosphere and up to 39% in the nitrogen

atmosphere. Maximal mass losses up to 89% were found in chars from peat and plant

materials at 350oC in the air and up to 72% in the nitrogen atmosphere. Random reflectance,

porous character of chars, and portion of fine fragments primarily of soot particles lower than

1µm produced from all raw materials increased rapidly in the air atmosphere but final

reflectance at 800 oC is lower (Rr = 3.9- 5.7%) than that of the chars from the nitrogen

atmosphere (Rr = 4.1 – 6.8%).

The changes in random reflectance observed with the increasing extent of thermal

alteration were consistent with decreasing- hydrogen content, increasing - carbon content and

volumes, and surface area of micropores. All studied raw materials have developed

microporous texture with volume of micropores from 0.0248 to 0.0406cm3/g, and surface area



120

of micropores between 63 and 113m2/g. The highest values of micropores volumes above

0.1300cm3/g and surface area of micropores above 400m

2/g were determined in chars

produced from plant materials. The parameter characteristic energy E plays a fundamental

role in the characterization of carbons. It rapidly increases in chars produced in air atmosphere

particularly in chars from lignite.

Random reflectance correlated well with H/C atomic ratios and BC values obtained by

chemo-thermal oxidation method. The highest BC values in raw materials were found in

lignite (0.32%wt BC) and in chars from bituminous coal (3.29% wt BC). The results show

that BC forms only small percentage of the total organic carbon in produced chars.

By the use of Py-GC/MS compounds were identified in the chars that were found also in

the raw materials and represent their remnants (phenol, benzofuran, indene, naphthalene and

their alkyl derivatives). However, there were also found compounds developed during

material alteration or rather originating from aromatic structures from which they were

released during Py-GC/MS. BC, formed by the incomplete combustion of fossil fuels,

biofuels, and biomass, is a broad range of combustion products, from slightly charred forms

of low condensation degree to the most condensed and graphitic forms of carbon. Formed at

lower temperatures, BC consists mainly of smaller clusters of condensed carbon, and the

identified compounds correspond to this imperfect structure (quinoline, biphenylene,

methylbiphenyles, dibenzofuran). The condensed aromatic network was formed at higher

temperature and the number and intensity of components in pyrograms decreased.

The composition of chars was dependent on the used conditions and indicated that

incomplete combustion leads to the formation of aromatic structures and regions.

Compounds typical for the BC presence were identified and there were no essential

differences in compound compositions between the two used environments.


121

Organic facies of the Upper Jurassic sediments

in the Poštak Mountain, Croatia

T.Troskot-Čorbić1, D. Španić

1INA-Industrija nafte d.d., E&P Research Laboratory Department, Zagreb, Croatia;

[email protected]

Carbonate deposits of the Karst (External) Dinarides ranging from the Lower Jurassic to

Cretaceous were formed on the Adriatic Carbonate Platform (AdCP). The Late Jurassic

megafacies of “limestones with cherts” was deposited within tectonically formed

intraplatform troughs which had temporary or continuous connection to the open sea. During

recent investigations the most complete succession of Kimmeridgian deeper marine deposits

has been documented at the slopes of Poštak Mt. New informal stratigraphic unit Poštak is

proposed composed of three members: Rastičevo, Dimići and Lemeš.

The objective of this study is detailed organic geochemical characterization of the Dimići

member in Poštak Mt.

Standard organic geochemistry analyses were performed on more than 100 outcrops. An

integral interpretation of this data was made in the sense of comprehensive organic facies

study in order to define organic matter types, source rocks and their generative potential as

well as genetic correlations.

Based on the integration of analytical data organic facies AB/B (after Jones 1987) it is

recognized as follows: Organic facies AB/B is characterized with high organic matter content,

excellent hydrocarbon potential and high transformation ratio. Type II kerogen dominates in

the organic-rich laminated limestones. Occasionally, the type I kerogen is present as well.

Organic facies AB/B is of marine, algal-bacterial origin. According to microsolubility and

strong yellow to yellow-orange fluorescence effect, organic matter is a mixture of algal,

bacterially degraded kerogen and migrated bitumen. Bitumen reflectance is in the range from

0.15 to 0.30% Ro (asphaltite group). Organic facies AB/B is characterized with high organic

sulfur content (from 6 to 10%). Stable carbon isotope values are in range from 1 3

C -27.79

to -24.65‰ in kerogen and from -29.53 to -25.55‰ in bitumen. Correlation is mainly

positive. These values are frequent in the Jurassic rocks and they are generally attributed to

the specific algal and bacterial lipids, as well as to the developed water anoxia.

The Upper Jurassic fine-grained, laminated limestones have an excellent generation

potential and represent very good to excellent oil-prone source rocks.

Organic matter content is in range from 0.35 and 11.9%, in average 2.97% TOC).

Petroleum potential is from good to excellent (between 1.17 and 67.00 mg HC/g rock, in

average 18.25 mg HC/g rock). Amorphous organic matter gradually changes from lamalginite

to bituminite I and finally to organo-bituminous-mineral groundmass, i.e. to matrix

bituminite. Solid bitumen is incorporated in all structural types. Phytoplankton is represented

by prasinophycean phycomata and dinoflagellate cysts. Throughout the geological columns



122

quantitative variations in cyanobacterial and liptinite/liptodetrinite content are

microscopically observed. Variations in C27 and C29 regular sterane were documented as well.

These dark organic-rich laminated limestones (mudstones) with cherts form the older part

of Lemeš trough deposits. Organic matter was deposited in deeper trough of the Adriatic

Carbonate Platform. Deposition occurred in the low energy environment within intraplatform

trough. Water stratification and bottom waters euxinia were occasionally disturbed by inflow

of the open sea water masses.

The laminated organic matter in a form of lamalginite was deposited in calm, stable

environment with developed water mass stratification, under oxygen–depleted conditions. In

relatively disturbed unstable conditions organic matter deposited as lamalginite became

decomposed and bacterially degraded which led to a gradual transition into bituminite I and

finally into organo-bituminous-mineral groundmass, matrix bituminite.

According to maturity parameters (Tmax, PI, TAI, fluorescence color, vitrinite reflectance,

bitumen reflectance, biomarker maturity parameters M/H, 22S/(22S+22R), Rc, Rm(MDR),

20S/(20S+20R), Ts/Tm), the organic facies AB/B generally reach onset of oil

generation.

High percentages of organic-bonded sulfur confirm that organic matter formation took

place in the marine, carbonate environment with contemporaneous sulfur incorporation into a

kerogen macromolecule structure. This kind of organic facies enabled hydrocarbon generation

at lower degree of thermal transformation. Consequently, the total bitumen yields are high.

The extractable fractions are dominated by resins and asphaltenes which reflect these specific

organic facies enriched in sulfur, but also some degradation effects due to the atmospheric

influence. Gas chromatograms of alkane fraction of bitumen show predominance of n-alkane

in lower molecular range, domination of phytane over pristane and n-alkane over iso-alkane,

respectively. These profiles are typical for bitumen of algal-bacterial origin and anoxic

(reducing) depositional environment and correspondent to the defined maturity level. Source

rock extracts and bitumens or bituminous coatings show high degree of similarity which

indicates short migration paths. Migrabitumen, which fill fissures, cavities and pores in the

rocks, is classified as the natural asphalt. That bitumen is product of early generation from

sulfur and organic rich kerogen. In the absence of the cap rocks, bitumen reached the surface,

and was degraded and transformed from primary viscous liquid into a solid bitumen.


123

Spectral fluorescence variability of pollen and spores

from peat-forming plants

J. Urbanczyk1, M.A. Fernandez Casado

2, T.E. Díez

2, A.G. Borrego

1

1Instituto Nacional del Carbón (INCAR-CSIC). Aptdo. 73, 33080 Oviedo, Spain;

[email protected] 2BOS Department. University of Oviedo. Catedrático Rodrigo Uría s/n, 33006 Oviedo, Spain

Fluorescence is the ability of the organic compounds to produce visible light when irradiated

with short wavelength light. The fluorescence properties of liptinite macerals are widely used

to assess the maturity of source rocks (Teichmüller and Wolff, 1977). They also have shown

to vary with the degree of alteration (Michelsen and Kohrasani, 1990). In extremely immature

sediments as is the case of peat, the fluorescence properties of the different components are

strongly influenced by their botanical characteristics such as species, taxon and state of

preservation of the material (van Gijzel, 1967) and has been applied to follow environmental

changes (Yeloff and Hunt, 2005). In this context this study aims to a characterization of

fluorescence spectra of pollen and spores of peat-forming plants in order to assess the intrinsic

variability within a single taxon. This is the first step of a wider study on the factors affecting

fluorescing properties in peat.

Pollen and spores of up to 26 different species of fresh peat-forming plants have been

spread over a glass as typically done for palynological preparations. An incident light optical

microscope with oil immersion objective has been used to collect the fluorescence spectra in

range of 420-750 nm using UV excitation. The spectra have been corrected for the optical

system using a quartz iodine lamp (Baranger et al., 1991). For each species at least 10 spectra

were collected on different grains to obtain average spectra to be compared.

Significant differences were found between the spectra of the various species with spectral

maxima ranging from 430 to 675 nm and intensity from around 20 to over 300 arbitrary units

(Fig.1). Obtained spectra could be assigned to either bluish wavelengths or to yellowish-

orange colors. The majority of species fell on the second color group: Serratula tinctoria

(Asteraceae family) with very strong intensity followed by Equisetum palustre

(Equisetaceae), Calluna vulgaris (Ericaceae) or Salix atrocinerea (Salicaceae). Lower

intensities in that colour group showed, among others: Tilia cordata (Malvaceae), Quercus

robur (Fagaceae) and Betula pubescens. Within species with intense bluish spectra we can

mention: Narcissus asturiensis (Amaryllidaceae), Ranunculus repens (Ranunculaceae) and

Molinia caerulea (Poaceae) whereas Sphagnum sp. (Sphagnaceae) and Corylus avellana

(Betulaceae) show spectra of


124

medium to low intensities. The variability within each species has been assessed using the

standard deviation and the coefficient of variation. The standard deviations were generally

This effect can be minimized when the coefficients of variation are considered. They ranged

between 0.10 and 0.30 for most of the species and were higher in the extreme of the spectra.

Among the species with the lowest intrinsic variability Q. robur and Castanea sativa can be

mentioned, whereas the largest variability was observed for Polypodium vulgare and Erica

mackaiana. This study has shown moderate variability within a single species in a single

sample, but significant variability within different peat-forming species. Further studies are

under development to study the spectral variability of similar species in peat.

Acknowledgement: Financial support from MICINN (CGL2009-13990-C02-01/02) and a FPU fellowship from

MEC for J. Urbanczyk are gratefully acknowledged.

References

Baranger R., Martinez L., Pittion J., Pouleau J. 1991 - A new calibration procedure for fluorescence

measurements of sedimentary organic matter. Organic Geochemistry 17: 467-475.

Michelsen J.K., Khorasani G.K. 1990 - Monitoring chemical alterations of individual oil-prone macerals by

means of microscopical fluorescence spectrometry combined with multivariate data analysis. Organic

Geochemistry 15: 179-192.

Teichmuller M., Wolf M. 1977 - Application of fluorescence microscopy in coal petrology and oil exploration.

Journal of Microscopy 109: 49-73.

van Gijzel P. 1967 - Palynology and fluorescence microscopy. Review of Palaeobotany and Palynology 2:

49-79.

Yeloff D., Hunt C. 2005 - Fluorescence microscopy of pollen and spores: a tool for investigating environmental

change. Review of Palaeobotany and Palynology 133: 203-219.

Fig.1. Fluorescence spectra of pollen and spores of some peat-forming plants.


125

Organic petrology of the Aptian section in the downdip Mississippi Interior

Salt Basin, Mississippi, USA

B.J. Valentine, P.C. Hackley, A.M. Bove, C.B. Enomoto, C.D. Lohr, K.R. Scott

U.S. Geological Survey, MS 956 National Center, Reston VA 20192; [email protected] 703-648-6480

This basin analysis study investigates a thermal maturity anomaly within the downdip

Mississippi Interior Salt Basin (MISB) of southern Mississippi, USA, by examining the

organic petrology of Aptian shales (Pearsall-equivalent Rodessa and Pine Island Formations).

A stratigraphically equivalent section contains an unconventional shale gas play in the

Maverick Basin of south Texas with an estimated mean undiscovered gas resource of 8.8 TCF

(Hackley, 2012). The USGS reconnaissance conducted in 2011-2012 examined Aptian

thermal maturity across the onshore Gulf Coast Region and indicated the section was

approaching the wet gas/condensate window in the downdip MISB (Enomoto et al., 2012). A

more focused study in 2012-2013 used six core samples and forty-six high-graded cuttings

samples (depth range of 12,000-15,000 ft below surface) collected from 15 wells in the

downdip MISB for Rock-EvalTM

pyrolysis, LecoTM

TOC, and organic petrography analysis.

Geochemical screening analysis found that samples were organically lean with TOC values

between 0.01-1.21 wt.%, averaging 0.5 wt.% (n=51). S2 ranged 0.14-2.33 mg HC/g rock,

averaging 0.40, indicating little present-day hydrocarbon generative potential. More than 70%

of the S2 values were >0.2 mg HC/g rock; however, of 51 pyrolysis analyses, only 11 gave

reasonable Tmax values (~430-530°C, converting to ~0.6-2.2% Ro), possibly due to low TOC

content. Therefore, the pyrolysis approach to characterizing these high maturity-organic lean

rocks is discounted in favor of petrographic analysis (e.g., Peters, 1986).

Despite being organic-lean, all samples contained solid bitumen and inertinite with only

two samples containing fragments of vitrinite. Due to the overlap of maceral-type reflectance

ranges, macerals were identified during analysis as either secondary solid bitumen (Ro

generally <0.8 %; recently migrated and cracked oil?), primary solid bitumen (Ro generally

>0.8%; indigenous hydrocarbons matured in situ?), solid bitumen/inert (macerals could not be

identified with absolute certainty), vitrinite or inertinite.

Based on primary solid bitumen reflectance, Ro values increase regionally across the MISB

from the southeast to the northwest. Thermal maturity in the eastern half of the basin (Ro

range 1.0 to 1.25%) appears to be related to present-day burial depth, showing a gradual

increase with respect to depth. However, thermal maturity continues to increase even as the

Aptian section shallows structurally on the Adams County High towards the western margin

of the basin (Ro range 1.4 to >1.8%). Possible explanations for this thermal anomaly include

agents such as igneous activity or salt emplacement, differences in regional crustal heat flux,

or relatively greater uplift and erosion during the regional mid-Cretaceous sea level regression

and development of the mid-Cenomanian unconformity. Extensive igneous activity during the

Late Cretaceous is known to have regionally occurred in the Monroe Uplift and Jackson

Dome structures (Salvador, 1991); however, our samples are >50 km (35 mi) distant from



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known igneous activity. Salt is ruled out because samples in the eastern portion of the basin

adjacent to salt structures did not display elevated thermal maturity. Limited evaluation of

present-day bottom-hole temperatures within the area showed no distinct trends, suggesting

past/present variations in regional heat flux do not influence thermal maturity. Therefore, we

propose that significant differential uplift and erosion at the western end of the MISB could be

responsible for the thermal maturity anomaly. The cause of the uplift and igneous activity in

the region is not well understood. A possible theory involves the reactivation of an ancient

plate boundary or graben due to rapid subsidence of the Gulf of Mexico basin (Salavador,

1991). Further sampling and analysis to examine if source rocks of Oxfordian and Late

Cretaceous age within the MISB exhibit a similar east-west thermal maturity trend as found in

the Aptian section will continue in 2013-2014.

References

Hackley P.C. 2012 - Geological and geochemical characterization of the Lower Cretaceous Pearsall Formation,

Maverick Basin, south Texas, USA: a potential shale gas resource? American Association of Petroleum

Geologists Bulletin, 96, 8: 1449-1482.

Enomoto C.B., Scott K.R., Valentine B.J., Hackley P.C., Dennen K.O., Lohr C. 2012 - Preliminary evaluation of

the shale gas prospectivity of the Lower Cretaceous Pearsall Formation in the onshore Gulf Coast region,

United States. Gulf Coast Association of Geological Societies Transactions, 62: 93-115.

Peters K.E. 1986 - Guidelines for evaluating petroleum source rock using programmed pyrolosis. The American

Association of Petroleum Geologists Bulletin, 70, 3: 318-329.

Salvador A. 1991 - Origin and development of the Gulf of Mexico Basin. in Salvador, A., ed., The Gulf of

Mexico Basin (The Geology of North America, Vol. J): Boulder, CO, Geologic Society America: 389-444.

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