Polycyclic aromatic hydrocarbons in two sedimentary environments of the Tertiary Krepoljin coal basin


  • Gordana Devic University of Belgrade, IHTM
  • Marija Pergal University of Belgrade, IHTM, Center of Chemistry
  • Miodrag Pergal




illite-montmorillonitic environment, calcitic environment , polycyclic aromatic hydrocarbons, gas chromatography with triple quad detector, multivariate statistical technique


In the present study, statistical correlation analysis and multivariate statistical techniques (PCA/FA) were employed to investigate polycyclic aromatic hydrocarbons (PAHs) in sediments, such as illite-montmorillonite (IM) and calcite (Ct), from two sedimentary environments of the Tertiary Krepoljin brown coal basin in Serbia. The coal and sediment layers were formed in fresh-water bogs during the Lower Miocene period. The total amount of extractable PAHs was determined by gas chromatography with a triple quad mass detector (GC-MS-MS), and it ranged from 449 to 10585 μg l−1 in all sediments. Eight of the total 16 PAHs, which ranged from 175.17 to 658.42 μg l−1, include benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, which are regarded as potentially carcinogenic, indicating a higher possibility of adverse ecological effects. Medium molecular-weight (MMW) PAHs were found to be predominant in all sediments. PAH concentrations are affected by several factors, such as carbon content, H/C mole ratio, and (less significant) O/C mole ratio. The non-existence of a correlation between the N/C ratio and other parameters indicates unspecific changes which accompany the original organic matter. The lower-sulfur Ct sediment samples were found to have a higher PAH content than higher sulfur IM samples, leading to the conclusion that the PAH content of sediments may be related to the depositional environment.


(1) Radke, M.; Wollisch, H.; Teichmüller, M., Generation and distribution of aromatic hydrocarbons in coals of low rank. Org. Geochem. 1990, 15, 539–563.


(2) Achten, C.; Hofmann, T., Native polycyclic aromatic hydrocarbons (PAH) in coals – a hardly recognized source of environmental contamination. Sci. Total Envi-ron. 2009, 407, 2461–2473.


(3) Dameng, L.; Zhihua, L.; Yunyong, L., Distribution and occurrence of polycyclic aromatic hydrocarbons from coal combustion and coking and its impact on the environ-ment. Energy Procedia. 2011, 5, 734–741. https://doi.org/:10.1016/j.egypro.2011.03.129

(4) Laumann, S.; Micić, V.; Kruge, A. M.; Achten, C.; Sachsenhofer, R. F.; Schwarzbauer, J.; Hofmann, T., Variations in concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in coals related to the coal rank and origin. Environ. Pollut. 2011, 159, 2690–2697.


(5) Baran, A.; Tarnawski, M.; Urbański, K.; Pawlas, A.; Spalek, I., Concentration, sources and risk assessment of PAHs in bottom sediments. Environ Sci Pollut Res. 2017, 24, 23180–23195.


(6) Lawal, A., Polycyclic aromatic hydrocarbons. A review, Cogent Environmental Science 2017, 3, 1–89. https://doi.org/10.1080/23311843.2017.13398417

(7) Ciesielczuk, J.; Fabiańska, M. J.; Misz-Kennan, M.; Jura, D.; Filipiak, P.; Matuszewska, A., The disappearance of coal seams recorded in associated gangue rocks in the SW part of the Upper Silesian Coal Basin, Poland. Minerals. 2021, 11, 1–30.


(8) Xue, J.; Liu, G. J.; Niu, Z. Y.; Chou, C. L.; Qi, C.; Zheng, L. G.; Zhang, H. Y., Factors that influence the ex-traction of polycyclic aromatic hydrocarbons from coal. Energy Fuels. 2007, 21, 881–890.


(9) Stout, S. A.; Emsbo-Mattingly, S., Concentration and character of PAHs and other hydrocarbons in coals of varying rank – Implications for environmental studies of soils and sediments containing particulate coal. Org. Geo-chem. 2008, 39, 801–819.


(10) Wang, L.; Liu, G.; Zhang, J.; Chou, C. L.; Liu, J., Abun-dances of polycyclic aromatic hydrocarbons (PAHs) in 14 Chinese and American coals and their relation to coal rank and weathering. Energy Fuels. 2010, 24, 6061–6066. https://doi.org/10.1021/ef1010622

(11) Ward, C. R. Analysis and significance of mineral matter in coal seams. Int. J. Coal Geol. 2002 50, 135–168.

(12) Ketzer, M.; Holz, M.; Morad, S. Al-Aasm, S., Sequence stratigraphic distribution of diagenetic alterations in coal-bearing, paralic sandstones: evidence from the Rio Bonito formation (early Permian), southern Brazil. 2003. https://doi.org/10.1046/j.1365-3091.2003.00586.x

(13) Liu, L;. Liu, Q.; Li, Y., Occurrence of iron in the minerals of carboniferous coal gangue of the Pingshuo open-pit mine, North China. Clays Clay Miner. 2022. 70, 695–711.


(14) Yuan, L.; Huang, W.; Jiu, B.; Sun, Q.; Che, Q., Modes of occurrence and origin of minerals in Permian coals from the Huainan Coalfield, Anhui, China. Minerals. 2022 10, 399. https://doi.org/10.3390/min10050399

(15) Ciesielczuk, J.; Górka, M.; Fabiańska, M. J.; Misz-Kennan, M.; Jura, D., The influence of heating on the carbon isotope composition, organic geochemistry and petrology of coal from the Upper Silesian Coal Basin (Poland): An experimental and field study. International Journal of Coal Geology 2021 241, 103749. https://doi.org/10.1016/j.coal.2021.103749

(16) Dević, G., An Assessment of the chemical characteristics of early diagenetic processes in a geologically well-defined brown coal basin. Energy Sources, Part A: Re-covery, Utilization, and Environmental Effects, 2015, 37, 2559–2566.


(17) Devic, G.; Popovic, Z., Biomarker and micropetrographic investigations of coal from the Krepoljin brown coal basin serbia. Inter. J. Coal Geol. 2013, 105, 48–59. https://doi.org/10.1016/j.coal.2012.11.010

(18) Kruge, M. A., Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds. Int. J. Coal Geol. 2000, 43, 27–51.


(19) Howarth, R. J.; Garrett, R. G., Statistical analysis and data display at the Geochemical Prospecting Research Centre and Applied Geochemistry Research Group, Imperial College, London. Geochemistry Exploration Environment Analysis, 2010, 10, 289.


(20) Herojeet, R.; Rishi, M.; Lata, R.; Sharma, R., Application of environmetrics statistical models and water quality in-dex for groundwater quality characterization of alluvial aquifer of Nalagarh Valley, Himachal Pradesh, India. Sustainable Water Resources Management. 2016 2, 39. https://doi.org/10.1007/s40899-015-0039-y

(21) Liu, C. W.; Lin, K. H.; Kuo, Y. M., Application of factor analysis in the assessment of groundwater quality in a blackfoot disease area in Taiwan. Sci. Total Environ. 2013, 442, 77–89.


(22) Ugochukwu, U. C.; Onuorah, L.; Okwu-Delunzu, V. U.; Odinkonigbo, U. E.; Onuora, O. H., Effects of power sta-tion and abattoir on PAH input into sediments of Oji Riv-er: ecological and human health exposure risks. Environ. Monit. Assess. 2019, 191, 775–779.


(23) Kalf, D. F.; Crommentuijn, T.; Van de Plassche, T. E. J., Environmental quality objectives for 10 polycyclic aro-matic hydrocarbons (PAHs). Ecotoxicology and Envi-ronmental Safety, 1997, 36, 89–97.


(24) Stout, S. A.; Uhler, A. D.; McCarthy, K. J.; Emsbo-Mattingly, S., Chemical Fingerprinting of Hydrocarbons. In Introduction to Environmental Forensics; Academic Press, San Diego, 2002, pp. 137–260.

(25) Laumann, S.; Micić, V.; Kruge, M. A.; Achten, C.; Sach-senhofer, R. F.; Schwarzbauer, J.; Hofmann, T., Variations in concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in coals related to the coal rank and origin. Environ. Poll. 2011, 59, 2690–2697.


(26) Fang, R.; Li, M.; Wang, T. G.; Zhang, L.; Shi, S., Identi-fication and distribution of pyrene, methylpyrenes and their isomers in rock extracts and crude oils. Org. Geo-chem. 2015, 83–84, 65–76.


(27) Verma, S. K.; Masto, R. E.; Gautam, S.; Choudhury, D. P.; Ram, L. C.; Maiti, S. K.; Maity, S., Investigations on PAHs and trace elements in coal and its combustion resi-dues from a power plant. Fuel. 2015, 162, 138–147. https://doi.org/10.1016/j.fuel.2015.09.005

(28) Praus, P., Principal component weighted index for wastewater quality monitoring. Water. 2019, 11, 2–13. https://doi.org/10.3390/w11112376

(29) Yao, P.; Zhao, B.; Bianchi, T.; Guo, S.; Zhao, Z.; Li, M. Remineralization of sedimentary organic carbon in mud deposits of the Changjiang Estuary and adjacent shelf: Implications for carbon preservation and authigenic min-eral formation. Continental Shelf Res. 2014, 91, 1–11. https://doi.org/:10.1016/j.csr.2014.08.010

(30) Bojakowska I.; Sokołowska, G., Polycyclic aromatic hydrocarbons in materials of burned peatlands. Geol. Quart, 2003, 45, 401–408.


(31) Taguchi, K.; Hasegawa, K.; Suzuki, T., The relationship between silica minerals and organic matter diagenesis: Its implication for the origin of oil. Org.Geochem. 1988, 13, 97–107.


(32) Asfahani, J.; Al-Hent, R.; Aissa, M., Identifying spec-trometric signatures of phosphate deposits and enclosing sediments in Al-Awabed area, Northern Palmyrides, Cen-tral Syria, by the use of statistical factor analysis. Appl Radiat Isot. 2006, 64, 1082–1090.


(33) Amrami, A.; Aizenshtat, Z., Mechanisms of sulfur intro-duction chemically controlled: δ34S imprint. Org. Geo-chem. 2004, 35, 1319–1336.

https://doi.org/ 10.1016/j.orggeochem.2004.06.019

(34) Tang, Y. G.; Li, R.; Wang, S., Research progress and prospects of coal petrology and coal quality in China. Int. J. Coal Sci. Technol. 2020, 7, 273–287. https://doi.org/10.1007/s40789-020-00322-3



2023-06-26 — Updated on 2023-07-01


How to Cite

Devic, G., Pergal, M., & Pergal, M. (2023). Polycyclic aromatic hydrocarbons in two sedimentary environments of the Tertiary Krepoljin coal basin. Macedonian Journal of Chemistry and Chemical Engineering, 42(1), 25–36. https://doi.org/10.20450/mjcce.2023.2552 (Original work published June 26, 2023)



Organic Chemistry