Gas chromatographic-mass spectrometric investigation of n-alkanes and carboxylic acids in bottom sediments of the northern Caspian Sea


Gas chromatography–mass spectrometry
oxonium ions

How to Cite

Kenzhegaliev, A., Zhumagaliev, S., Kenzhegalieva, D., & Orazbayev, B. (2018). Gas chromatographic-mass spectrometric investigation of n-alkanes and carboxylic acids in bottom sediments of the northern Caspian Sea. Geologos, 24(1), 69–78.


Prior to the start of experimental oil production in the Kashagan field (northern part of the Caspian Sea), n-alkanes and carboxylic acids contained in samples obtained from bottom sediments in the area of artificial island “D” were investigated by gas chromatography–mass spectrometry. Concentrations of 10 n-alkanes (composed of C10-C13, C15-C20) and 11 carboxylic acids (composed of C6-C12, C14-C16) were identified and measured. Concentrations of individual alkanes and carboxylic acids in bottom sediments of the various samples varied between 0.001 ÷ 0.88 μg/g and 0.001 ÷ 1.94 μg/g, respectively. Mass spectra, in particular the M+ molecular ion peak and the most intense peaks of fragment ions, are given. The present study illustrates the stability of molecular ions to electronic ionisation and the main fragment ions to the total ion current and shows that the initial fragmentation of alkanes implies radical cleavage of C2H5 rather than CH3. All aliphatic monocarboxylic acids studied were characterised by McLafferty rearrangement leading to the formation of F4 cation-radical with m/z 60 and F3 cation-radical with m/z 88 in the case of ethylhexanoic acid. The formation of oxonium ions presents another important aspect of acid fragmentation. Using mass numbers of oxonium ions and rearrangement ions allows determination of the substitution character in α- and β- C atoms. The essence of our approach is to estimate the infiltration of hydrocarbon fluids from the enclosing formation into sea water, comprising an analysis of derivatives of organic compounds in bottom sediments. Thus, concentrations of derived organic molecules can serve as a basis for estimates of the depth at which hydrocarbon fluids leak, i.e., to serve as an auxiliary technique in the search for hydrocarbon deposits and to repair well leaks.


Aeppli, C., Nelson, R.K., Radović, J.R., Carmichael, C.A., Valentine, D.L. & Reddy, C.M., 2014. Recalcitrance and degradation of petroleum biomarkers upon abiotic and biotic natural weathering of Deepwater Horizon oil. Environmental Science & Technology 48, 6726–6734.

Bonini, M., Tassi, F., Akper, A., Feyzullayev, A., Chingiz, S., Aliyev, C., Capecchiacci, F. & Minissale, A., 2013. Deep gases discharged from mud volcanoes of Azerbaijan: New geochemical evidence. Marine and Petroleum Geology 43, 450–463.

Boonyatumanond, R., Wattayakorn, G., Togo, A. & Takada, H., 2006. Distribution and origins of polycyclic aromatic hydrocarbons (PAHs) in riverine, estuarine, and marine sediments in Thailand. Marine Pollution Bulletin 52, 942–956.

Chen, S.-C, Hsu, S.-K., Wang, Y., Chung, S.-H., Tsai, C.-H., Liu, C.-S., Lin, H.S. & Lee Y.-W., 2014. Distribution and characters of the mud diapirs and mud volcanoes off southwest Taiwan. Journal of Asian Earth Sciences 92, 201–214.

De Hoffmann, E. & Stroobant, V., 2007. Mass Spectrometry. Principles and Applications. Third Edition. John Wiley and Sons, Ltd. England. 3–26

Etiope, G., Feyzullayev, A., Baciu, C.L. & Milkov, A.V., 2004. Methane emission from mud volcanoes in eastern Azerbaijan. Geology 32, 465–468.

Fernandes, L., Garg, A. & Borole, D.V., 2014. Amino acid biogeochemistry and bacterial contribution to sediment organic matter along the western margin of the Bay of Bengal. Deep-Sea Research I: Oceanographic Research Papers 83, 81–92.

Feyzullayev, A.A., 2012. Mud volcanoes in the South Caspian basin: nature and estimated depth of its products. Natural Science 4, 445–453.

Feyzullayev, A.A., Tagiyev, M. & Lerche, I., 2015. On the origin of hydrocarbons in the main Lower Pliocene reservoirs of the South Caspian Basin, Azerbaijan. Energy Exploration and Exploitation 33, 1–13.

Gay, A., Nakano, Y., Gilhooly, W., Berndt, C., Heeschen, K., Suzuki, N., Saegusa, S., Nakagawa, F., Tsunogai, U., Jiang, S.Y. & Lopez, M., 2011. Geophysical and geochemical evidence of large scale fluid flow within shallow sediments in the eastern Gulf of Mexico, offshore Louisiana. Geofluids 11, 34–47.

Hedges, J.I. & Keil, R.G., 1995. Sedimentary organic matter preservation: An assessment and speculative synthesis. Marine Chemistry 49, 81–115.

Kaiser, K. & Benner, R., 2009. Biochemical composition and size distribution of organic matter at the Pacific and Atlantic time-series stations. Marine Chemistry 113, 63–77.

Kallmeyer, J., Pockalny, R., Adhikari, R.R., Smith, D.C. & D’Hondt, S., 2012. Global distribution of microbial abundance and biomass in subseafloor sediment. Proceedings of the National Academy of Sciences of the United States of America 109, 16213–16216.

Kan, J., Hanson, T.E., Ginter, J.M., Wang, K. & Chen, F., 2005. Metaproteomic analysis of Chesapeake Bay bacterial communities. Saline Systems 1, 1–13.

Kemp, W., 1991. Infrared spectroscopy. In: Organic Spectroscopy. Macmillan Education, 19–99.

Khoroshko, L.O., Takhistov, V.V., Petrova, V., Viktorovskii, I.V., Lahtipera, M. & Paasivirta, J., 2004. Mass spectrometric identification of alicyclic polysulfide’s in sediments of the Eastern Gulf of Finland, I. European Journal of Mass Spectrometry 10, 731–736.

Kroonenberg, S.B., Simmons, M.D., Alekseevski, N.I., Aliyeva, E., Allen, M.B., Aybulator, D.N. & Hoogendoorn, R. M., 2005. Two deltas, two basins, one river, one sea. The modern Volga Delta as an analogue of the Neogene Productive Series, South Caspian Basin. [In:] River Deltas – Concepts, Models, and Examples. SEPM Special Publication 83, 231–256.

Kovats, E., 1958. Gas-Chromatographische Charakterisierung organischer Verbindungen. Teil 1: Retentions indices aliphatischer Halogenide, Alkohole, Aidehyde und Ketone. Helvetica Chimica Acta 41, 1915–1932.

Lyons, T.W., 1997. Sulfur isotopic trends and pathways of iron sulfide formation in upper Holocene sediments of the anoxic Black Sea. Geochimica et Cosmochimica Acta 61, 3367–3382.

Lyons, T.W. & Berner, R.A., 1992. Carbon–sulfur–iron systematics of the uppermost deep-water sediments of the Black Sea. Chemical Geology 99, 1–27.

McLafferty, F.W., 1959. Mass Spectrometric Analysis. Molecular Rearrangements. Analytical Chemistry 31, 82–87.

McLafferty, F.W., 1963. Mass Spectrometry of Organic Ions. Academic Press, New York, 481 pp.

Middelburg, J.J. & Meysman, F.J.R., 2007. Burial at Sea. Science 316, 1294–1294.

Mirza, R., Mohammadi, M., Ali Dadolahi, S., Safahieh, A., Savari, A. & Hajeb, P., 2012. Polycyclic Aromatic Hydrocarbons in Seawater, Sediment, and Rock Oyster Saccostrea cucullata from the Northern Part of the Persian Gulf (Bushehr Province). Water, Air & Soil Pollution 223, 189–198.

Monazami Tehrani, G., Halim, S.H., Hashim, R., Tavakoly, S.B., Savari, A. & Khani, J.R., 2013. Distribution of total petroleum hydrocarbons and polycyclic aromatic hydrocarbons in Musa Bay sediments (Northwest of the Persian Gulf). Environment Protection Engineering 39, 5–22.

Moore, E.K., Harvey, H.R., Faux, J.F., Goodlett, D.R. & Nunn, B.L., 2014. Protein recycling in the Bering Sea algal incubations. Marine Ecology Progress Series 515, 45–59.

Muramoto, J.A., Honjo, S., Fry, B., Hay, B.J., Howarth, R.W. & Cisne, J.L., 1991. Sulfur, iron and organic carbon fluxes in the Black Sea-sulfur isotopic evidence for origin of sulfur fluxes. Deep-Sea Research I: Oceanographic Research Papers 38, 1151–1187.

Neretin, N., Bottcher, M.E. & Volkov, I.I., 1998. The stable sulfur isotopic composition of sulfur species in the Black Sea water column. Mineralogical Magazine 62A, 1075–1076.

Nesvizhskii, A.I., Keller, A., Kolker, E. & Aebersold, R., 2003. A statistical model for identifying proteins by tandem mass spectrometry. Analytical Chemistry 75, 4646–4658.

Ogar, N.P., Mutysheva, G.K. & Little, D.I., 2014. Environmental Monitoring of the North-Eastern Caspian Sea in Development of Oil Fields (Findings of Agip KCO Environmental Surveys), Almaty, 6–11.

Oguri, K., Harada, N. & Tadai, O., 2012. Excess 21°Pb and 137 Cs concentrations, mass accumulation rates, and sedimentary processes on the Bering Sea continental shelf. Deep-Sea Research II: Topical Studies in Oceanography 61–64, 193–204.

Planke, S., Svensen, H., Hovland, M., Banks, D.A. & Jamtveit, B., 2003. Mud and fluid migration in active mud volcanoes in Azerbaijan. Geo-Marine Letters 23, 258-268.

Rau, G.H., Sullivan, C.W. & Gordon, L.I., 1991. δ 13C and δ 15N variations in Weddell Sea particulate organic matter. Marine Chemistry 35, 355–369.

Ronchi, P., Ortenzi, A., Borromeo, O. & Zempolich, W.G., 2010. Depositional setting and diagenetic processes and their impact on the reservoir quality in the late Visean–Bashkirian Kashagan carbonate platform (Pre-Caspian Basin, Kazakhstan). AAPG Bulletin 94, 1313–1348.

Sowell, S.M., Wilhelm, L.J., Norbeck, A.D., Lipton, M.S., Nicora, C.D., Barofsky, D.F., Carlson, C.A., Smith, R.D. & Giovanonni, S.J., 2009. Transport functions dominate the SAR11 metaproteome at low-nutrient extremes in the Sargasso Sea. ISME Journal 3, 93-105.

Stein, S., Mirokhin, D., Tchekhovskoi, D., Mallard, G., Mikaia, A., Zaikin, V. & Clifton, C., 2002. The NIST mass spectral search program for the NIST/EPA/NIH mass spectra library. Standard Reference Data Program of the National Institute of Standards and Technology. Gaithersburg.

Sweeney, R.E. & Kaplan, I.R., 1980. Stable isotope composition of dissolved sulfate and hydrogen sulfide in the Black Sea. Marine Chemistry 9, 145–152.

Villinski, J.C., Dunbar, R.B. & Mucciarone, D.A., 2000. Carbon 13 / Carbon 12 ratios of sedimentary organic matter from the Ross Sea, Antarctica: A record of phytoplankton bloom dynamics. Journal of Geophysical Research 105, 14163–14172.

Waldhier, M.C., Dettmer, K., Gruber, M.A. & Oefner, P.J., 2010. Comparison of derivatization and chromatographic methods for GC–MS analysis of amino acid enantiomers in physiological samples. Journal of Chromatography B 878, 1103–1112.

Wijsman, J.W.M., Middelburg, J.J. & Heip, C.H.R., 2001. Reactive iron in Black Sea sediments: implications for iron cycling. Marine Geology 172, 167–180.

Zhumagaliev, S.Zh., Kenzhegaliev, A., Kenzhegalieva, D.A. & Orazbayev, B.B., 2013. The mass-spectra and the features of the fragmentation of organic sulfur compounds in the sediments of the northern part of the Caspian Sea. News of the Academy of Sciences of the Republic of Kazakhstan. Series Chemistry and Technology 2, 17–24 (in Russian).

Zhumagaliev, S.Zh., Kenzhegaliev, A., Kenzhegalieva, D.A. & Orazbayev, B.B., 2014. Mass-spectrometric identification of elemental sulfur and some alkylthiophenes in the sediments of the northern part of the Caspian Sea. News of the Academy of Sciences of the Republic of Kazakhstan. Series Chemistry and Technology 1 (403), 25–29 (in Russian).

Zonneveld, K.A.F., Versteegh, G.J.M., Kasten, S., Eglinton, T.I., Emeis, K.C., Huguet, C., Koch, B.P., de Lange, G.J., de Leeuw, J.W. & Middelburg, J.J., 2010. Selective preservation of organic matter in marine environments; processes and impact on the sedimentary record. Biogeosciences 7, 483–511.