Molecular and Geochemical Tracers for the Precise Apportionment of Hydrocarbon Spills from Vessels in Critical Coastal Habitats

Authors

  • Yin Yu

    China Waterborne Transport Research Institute, Beijing 100088, China

  • Fang Zhou

    China Waterborne Transport Research Institute, Beijing 100088, China

  • Xiaoguang You

    China Waterborne Transport Research Institute, Beijing 100088, China

  • Shiyue Wang

    China Waterborne Transport Research Institute, Beijing 100088, China

DOI:

https://doi.org/10.30564/jees.v8i5.13259
Received: 13 February 2026 | Revised: 26 April 2026 | Accepted: 2 May 2026 | Published Online: 14 May 2026

Abstract

The danger of hydrocarbon spills from vessels presents long-term threats to vital coastal environments, such as mangroves, salt marshes, seagrass meadows, coral reef-related shorelines, and ecological sensitivity is coupled with maritime activities. The accurate source apportionment is necessary to perform impact assessment, remediation prioritization and regulatory enforcement, but it is still hard to achieve because of the complex source mixtures and fast post-release weathering. This is a review of molecular and geochemical tracer techniques to determine and apportion ship-produced hydrocarbons in coastal systems. We assess the forensic usefulness of diagnostic biomarkers (hopanes, steranes), n-alkanes and isoprenoids, polycyclic aromatic hydrocarbons, and explore the effects of evaporation, dissolution, photo-oxidation, and biodegradation on molecular fingerprints and their effect on interpretation. They are complementary geochemical evidence, such as stable carbon and hydrogen isotopes (δ13C, δD), radiocarbon limits separating fossil and modern carbon, and elemental indications and evidence of marine fuel and lubricants, including trace metals. The combinations of multi-tracer evidence and chemometric techniques and mixing models, with highlighting built-in discrimination between refined fuels, solving overlapping sources, and quantifying the uncertainty of the situation in complex coastal environments are mentioned. Lastly, we cover new directions of future development, such as high-resolution mass spectrometry, analysis of compound-specific isotopes, and machine learning, and the requirement of standardized protocols and libraries of weathered marine fuels. In combination, these developments can enhance defensible attribution of murderous tanker pollution and uphold protection of susceptible shoreline ecosystems.

Keywords:

Hydrocarbon Forensics; Vessel Spills; Biomarkers; Compound-Specific Isotopes; Coastal Sediments

References

[1] Ansari, Z.A., Matondkar, S.G.P., 2014. Anthropogenic activities including pollution and contamination of coastal marine environment. Journal of Ecophysiology and Occupational Health. 14(1/2), 71–78.

[2] Barbier, E.B., Hacker, S.D., Kennedy, C., et al., 2011. The value of estuarine and coastal ecosystem services. Ecological Monographs. 81(2), 169–193.

[3] Rogowska, J., Namieśnik, J., 2010. Environmental implications of oil spills from shipping accidents. Reviews of Environmental Contamination and Toxicology. 206, 95–114.

[4] Navare, J., 2001. Marine Oil Spill Incidents from Sea-Going Tankers: An Idiographic Exploration of the Spill Effects on Structure, Culture and Behaviour in Risk and Collective Incident Management [PhD Thesis]. University of Southampton: Southampton, UK.

[5] Renken, H., 2010. Global Trends in Ship-Sourced Marine Pollution. In Proceedings of Oil in the Sea Conference, Hamburg, Germany, 17–19 November 2010.

[6] Asare, E.A., Abdul-Wahab, D., Asamoah, A., et al., 2024. Source apportionment of hydrocarbons in Ghana's coastal sediments: Utilizing hydrocarbons ratios and advanced statistical methods. Water, Air, & Soil Pollution. 235(12), 823.

[7] Wagener, A.d.L.R., Falcão, A.P., Farias, C.O., et al., 2019. Distribution and source apportionment of hydrocarbons in sediments of oil-producing continental margin: A fuzzy logic approach. Environmental Science and Pollution Research. 26(17), 17032–17044.

[8] Wise, S.A., Rodgers, R.P., Reddy, C.M., et al., 2023. Advances in chemical analysis of oil spills since the Deepwater Horizon disaster. Critical Reviews in Analytical Chemistry. 53(8), 1638–1697.

[9] Okparanma, R.N., Mouazen, A.M., 2013. Determination of total petroleum hydrocarbon (TPH) and polycyclic aromatic hydrocarbon (PAH) in soils: A review of spectroscopic and nonspectroscopic techniques. Applied Spectroscopy Reviews. 48(6), 458–486.

[10] Filewood, T., Kwok, H., Brunswick, P., et al., 2022. Advancement in oil forensics through the addition of polycyclic aromatic sulfur heterocycles as biomarkers in diagnostic ratios. Journal of Hazardous Materials. 435, 129027.

[11] Stout, S., Wang, Z. (Eds.), 2016. Standard Handbook Oil Spill Environmental Forensics: Fingerprinting and Source Identification. Academic Press: Cambridge, MA, USA.

[12] Upadhayay, H.R., Semmens, B.X., Stock, B.C., et al., 2017. Methodological perspectives on the application of compound-specific stable isotope fingerprinting for sediment source apportionment. Journal of Soils and Sediments. 17(6), 1537–1553.

[13] Lizaga, I., Latorre, B., Gaspar, L., et al., 2022. Combined use of geochemistry and compound-specific stable isotopes for sediment fingerprinting and tracing. Science of the Total Environment. 832, 154834.

[14] Philp, R.P., 2007. The emergence of stable isotopes in environmental and forensic geochemistry studies: A review. Environmental Chemistry Letters. 5(2), 57–66.

[15] Zhang, Y., Xian, B., Sun, W., et al., 2024. The environmental hazards and treatment of ship’s domestic sewage. Toxics. 12(11), 826.

[16] Zhou, P., Chen, C., Ye, J., et al., 2015. Combining molecular fingerprints with multidimensional scaling analyses to identify the source of spilled oil from highly similar suspected oils. Marine Pollution Bulletin. 93(1–2), 121–129.

[17] Betti, M., Boisson, F., Eriksson, M., et al., 2011. Isotope analysis for marine environmental studies. International Journal of Mass Spectrometry. 307(1–3), 192–199.

[18] Christensen, J.H., Tomasi, G., 2007. Practical aspects of chemometrics for oil spill fingerprinting. Journal of Chromatography A. 1169(1–2), 1–22.

[19] Galil, B.S., 2006. Shipwrecked–shipping impacts on the biota of the Mediterranean Sea. In: Davenport, J., Davenport, J.L. (Eds). The Ecology of Transportation: Managing Mobility for the Environment. Springer: Dordrecht, The Netherlands. pp. 39–69.

[20] Uhler, A.D., Stout, S.A., Douglas, G.S., et al., 2016. Chemical character of marine heavy fuel oils and lubricants. In: Stout, S.A., Wang, Z. (Eds). Standard Handbook Oil Spill Environmental Forensics: Fingerprinting and Source Identification. Elsevier: Cambridge, MA, USA. pp. 641–683.

[21] Gounder, R.M., 2019. Introductory chapter: Heavy crude oil processing—An overview. In Processing of Heavy Crude Oils-Challenges and Opportunities. IntechOpen: London, UK.

[22] Corbett, J.J., Winebrake, J.J., 2008. Emissions tradeoffs among alternative marine fuels: Total fuel cycle analysis of residual oil, marine gas oil, and marine diesel oil. Journal of the Air & Waste Management Association. 58(4), 538–542.

[23] Tornero, V., Hanke, G., 2016. Chemical contaminants entering the marine environment from sea-based sources: A review with a focus on European seas. Marine Pollution Bulletin. 112(1–2), 17–38.

[24] Cahoon, D.R., McKee, K.L., Morris, J.T., 2021. How plants influence resilience of salt marsh and mangrove wetlands to sea-level rise. Estuaries and Coasts. 44(4), 883–898.

[25] Culbertson, J.B., Valiela, I., Pickart, M., et al., 2008. Long-term consequences of residual petroleum on salt marsh grass. Journal of Applied Ecology. 45(4), 1284–1292.

[26] Bastos, L.P.H., da Costa Cavalcante, D., Alferes, C.L.F., et al., 2022. Fingerprinting an oil spill event (August of 2021) in the oceanic Fernando de Noronha archipelago using biomarkers and stable carbon isotopes. Marine Pollution Bulletin. 186, 114316.

[27] Tarr, M.A., Zito, P., Overton, E.B., et al., 2016. Weathering of oil spilled in the marine environment. Oceanography. 29(3), 126–135.

[28] Gouthami, K., Mallikarjunaswamy, A.M.M., Bhargava, R.N., et al., 2023. Microbial biodegradation and biotransformation of petroleum hydrocarbons: Progress, prospects, and challenges. In: Kumar, V., Bilal, M., Romanholo, L.F. (Eds.). Genomics Approach to Bioremediation: Principles, Tools, and Emerging Technologies. John Wiley & Sons, Inc.: Hoboken, NJ, USA. pp. 229–247.

[29] Arndt, S., Jørgensen, B.B., LaRowe, D., et al., 2013. Quantifying the degradation of organic matter in marine sediments: A review and synthesis. Earth-Science Reviews. 123, 53–86.

[30] Iqbal, J., Overton, E.B., Gisclair, D., 2008. Polycyclic aromatic hydrocarbons in Louisiana rivers and coastal environments: Source fingerprinting and forensic analysis. Environmental Forensics. 9(1), 63–74.

[31] Jukić, A., 2013. Petroleum Refining and Petrochemical Processes. University of Zagreb: Zagreb, Croatia. Available from: https://www.fkit.unizg.hr/_download/repository/PRPP_2013_Crude_oil_composition.pdf

[32] dos Santos Fernandes, R.M.A., 2018. Risk Management of Coastal Pollution from Oil Spills Supported by Operational Numerical Modelling [PhD Thesis].Universidade De Lisboa: Lisboa, Portugal.

[33] Wang, Z., Stout, S. (Eds.), 2010. Oil Spill Environmental Forensics: Fingerprinting and Source Identification. Elsevier: Boston, MA, USA.

[34] Simoneit, B.R.T., 2004. Biomarkers (molecular fossils) as geochemical indicators of life. Advances in Space Research. 33(8), 1255–1261.

[35] Brocks, J.J., Summons, R., 2005. Sedimentary hydrocarbons, biomarkers for early life. In Treatise on Geochemistry, Volume 8: Biogeochemistry. Elsevire: Amsterdam, The Netherlands. pp. 63–115.

[36] Huizinga, B.J., Tannenbaum, E., Kaplan, I.R., 1987. The role of minerals in the thermal alteration of organic matter—IV. Generation of n-alkanes, acyclic isoprenoids, and alkenes in laboratory experiments. Geochimica et Cosmochimica Acta. 51(5), 1083–1097.

[37] Yin, F., Gao, C., Song, Z., et al., 2022. Chemical signatures of polycyclic aromatic hydrocarbons in the emissions from in situ oil burns. Marine Pollution Bulletin. 183, 114033.

[38] Farrell-Jones, J., 2003. Petroleum Hydrocarbons and Polyaromatic Hydrocarbons. In: Thompson, K.C., Nathanail, C.P. (Eds.). Chemical Analysis of Contaminated Land. Wiley-Blackwell: Hoboken, NJ, USA. pp. 132–176.

[39] Saha, M., Togo, A., Mizukawa, K., et al., 2009. Sources of sedimentary PAHs in tropical Asian waters: Differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance. Marine Pollution Bulletin. 58(2), 189–200.

[40] Salata, A.B.A.d.M., Pereira, M.G.S., de Lima, I.F.S., et al., 2025. Impact of environmental weathering on the chemical composition of spilled oils in a real case in Brazil. Coasts. 5(4), 49.

[41] Haseeba, K.P., Vethamony, P., Veerasingam, S., et al., 2025. A comprehensive review of oil residues in the world oceans: Types, characteristics, sources and distribution. Marine Pollution Bulletin. 217, 118106.

[42] Syakti, A.D., 2016. Molecular diagnostic ratios to assess the apportionment of petroleum hydrocarbons contamination in marine sediment. Molekul. 11(2), 208–219.

[43] Kaplan, I.R., Galperin, Y., Lu, S.-T., et al., 1997. Forensic environmental geochemistry: Differentiation of fuel-types, their sources and release time. Organic Geochemistry. 27(5–6), 289–317.

[44] Li, Y., Xiong, Y., Yang, W., et al., 2009. Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills. Marine Pollution Bulletin. 58(1), 114–117.

[45] Pond, K.L., Huang, Y., Wang, Y., et al., 2002. Hydrogen isotopic composition of individual n-alkanes as an intrinsic tracer for bioremediation and source identification of petroleum contamination. Environmental Science & Technology. 36(4), 724–728.

[46] Rosenheim, B.E., Pendergraft, M.A., Flowers, G.C., et al., 2016. Employing extant stable carbon isotope data in Gulf of Mexico sedimentary organic matter for oil spill studies. Deep Sea Research Part II: Topical Studies in Oceanography. 129, 249–258.

[47] White, H.K., Reddy, C.M., Eglinton, T.I., 2008. Radiocarbon-based assessment of fossil fuel-derived contaminant associations in sediments. Environmental Science & Technology. 42(15), 5428–5434.

[48] Wakeham, S.G., McNichol, A.P., 2014. Transfer of organic carbon through marine water columns to sediments–insights from stable and radiocarbon isotopes of lipid biomarkers. Biogeosciences. 11(23), 6895–6914.

[49] Celo, V., Dabek-Zlotorzynska, E., McCurdy, M., 2015. Chemical characterization of exhaust emissions from selected Canadian marine vessels: The case of trace metals and lanthanoids. Environmental Science & Technology. 49(8), 5220–5226.

[50] Eichler, P., Müller, M., Rohmann, C., et al., 2017. Lubricating oil as a major constituent of ship exhaust particles. Environmental Science & Technology Letters. 4(2), 54–58.

[51] Moldanová, J., Fridell, E., Popovicheva, O., et al., 2009. Characterisation of particulate matter and gaseous emissions from a large ship diesel engine. Atmospheric Environment. 43(16), 2632–2641.

[52] Li, Y., Liu, Y., Jiang, D., et al., 2018. Effects of weathering process on the stable carbon isotope compositions of polycyclic aromatic hydrocarbons of fuel oils and crude oils. Marine Pollution Bulletin. 133, 852–860.

[53] Miller, J.R., 2013. Forensic assessment of metal contaminated rivers in the 21st century using geochemical and isotopic tracers. Minerals. 3(2), 192–246.

[54] D’Antonio, M., Di Renzo, V., Arienzo, I., et al., 2022. Isotopic analysis techniques applied to forensics: New frontiers of isotope geochemistry. In: Mercurio, M., Langella, A., Di Maggio, R.M., et al. (Eds.). Mineralogical Analysis Applied to Forensics: A Guidance on Mineralogical Techniques and Their Application to the Forensic Field. Springer: Cham, Switzerland. pp. 251–290.

[55] McCallum, P., Filewood, T., Sawitsky, J., et al., 2023. Enhancement of oil forensic methodology through the addition of polycyclic aromatic nitrogen heterocycle biomarkers for diagnostic ratios. Environmental Monitoring and Assessment. 195(3), 416.

[56] Martins, L.L., Pereira, V.B., Nascimento, A.P., et al., 2024. Forensic geochemistry reveals international ship dumping as a source of new oil spill in Brazil's coastline (Bahia) in late 2023. Environmental Science & Technology. 58(21), 9328–9338.

[57] Christensen, J.H., Tomasi, G., 2016. A multivariate approach to oil hydrocarbon fingerprinting and spill source identification. In: Stout, S.A., Wang, Z. (Eds). Standard Handbook Oil Spill Environmental Forensics: Fingerprinting and Source Identification. Elsevier: Cambridge, MA, USA. pp. 747–788.

[58] Hajihosseinlou, M., Maghsoudi, A., Ghezelbash, R., 2024. Geochemical anomaly detection and pattern recognition: A combined study of the Apriori algorithm, principal component analysis, and spectral clustering. Minerals. 14(12), 1202.

[59] Peters, K.E., Walters, C.C., Moldowan, J.M., 2007. The Biomarker Guide: Volume 2: Biomarkers and Isotopes in Petroleum Systems and Earth History, 2nd ed. Cambridge University Press: Cambridge, UK.

[60] Owens, E.H., Taylor, E., Parker, H.A., 2016. Spill site characterization in environmental forensic investigations. In: Stout, S.A., Wang, Z. (Eds). Standard Handbook Oil Spill Environmental Forensics: Fingerprinting and Source Identification. Elsevier: Cambridge, MA, USA. pp. 1–24.

[61] Li, T., Sun, G., Yang, C., et al., 2019. Source apportionment and source-to-sink transport of major and trace elements in coastal sediments: Combining positive matrix factorization and sediment trend analysis. Science of the Total Environment. 651, 344–356.

[62] Alao, J.O., Saqr, A.M., Ayejoto, D.A., et al., 2025. Environmental impacts of hydrocarbon contaminants and associated potential public health risks. Journal of Hazardous Materials Advances. 19, 100853.

[63] Anejionu, O.C.D., Ahiarammunnah, P.-A.N., Nri-ezedi, C.J., 2015. Hydrocarbon pollution in the Niger Delta: Geographies of impacts and appraisal of lapses in extant legal framework. Resources Policy. 45, 65–77.

[64] Kruge, M.A., Lara-Gonzalo, A., Gallego, J.L.R., 2020. Environmental forensics of complexly contaminated sites: A complimentary fingerprinting approach. Environmental Pollution. 263, 114645.

[65] Radovic, J.R., Silva, R.C., 2024. Ultrahigh-resolution mass spectrometry advances for biogeochemical analysis: From seafloor sediments to petroleum and marine oil spills. Journal of the American Society for Mass Spectrometry. 36(1), 7–33.

[66] Ya, M., Wu, Y., Wang, X., et al., 2022. The importance of compound-specific radiocarbon analysis in source identification of polycyclic aromatic hydrocarbons: A critical review. Critical Reviews in Environmental Science and Technology. 52(6), 937–978.

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How to Cite

Yu, Y., Zhou, F., You, X., & Wang, S. (2026). Molecular and Geochemical Tracers for the Precise Apportionment of Hydrocarbon Spills from Vessels in Critical Coastal Habitats. Journal of Environmental & Earth Sciences, 8(5), 169–184. https://doi.org/10.30564/jees.v8i5.13259