Eurasian Journal of Soil Science

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants that pose significant environmental and health risks due to their widespread distribution and carcinogenic properties. Developing efficient and environmentally friendly extraction methods for PAHs from complex matrices like bottom sediments is essential for advancing pollution monitoring and mitigation efforts. The influence of temperature and time parameters of water in a subcritical state on the extraction of widespread, contrasting in physicochemical properties polycyclic aromatic hydrocarbons (PAHs) from bottom sediment samples of the Lena River with varying initial pollutant content was studied. It was shown that the optimal extraction parameters for naphthalene are 240°C for 20 minutes, for phenanthrene and fluoranthene – 240°C for 30 minutes, for benzo(a)pyrene – 250°C for 30 minutes, and for benzo(g,h,i)perylene – 260°C for 40 minutes. Under these conditions, the proportion of extracted PAHs varies from 76% to 85%. A comparison was conducted of widely used PAH extraction methods based on the use of toxic solvents from standard techniques. It was established that the efficiency of extraction methods can be ranked as follows: ultrasound extraction > subcritical extraction > saponification method. In this case, the value of the PAH extraction coefficient during subcritical extraction was 1.23-1.29, during saponification - 1.35 and 1.34, and during the ultrasonic extraction method - 1.10 and 1.08.

Keywords

Polycyclic aromatic hydrocarbons, organic pollutants, bottom sediments, pollution, naphthalene, phenanthrene, benzo(a)pyrene, extraction method, high-performance liquid chromatography.

References

<p>ATSDR, 1995. Toxicological profile for polycyclic aromatic hydrocarbons. Agency for Toxic Substances and Disease Registry. U.S. Department of Health and Human Services. Washington DC. Available at [Access date: 15.07.2024]:&nbsp; https://wwwn.cdc.gov/tsp/ToxProfiles/ToxProfiles.aspx?id=122&amp;tid=25</p>

<p>ATSDR, 2020. Minimal risk levels (MRLs) list. Agency for Toxic Substances and Disease Registry. U.S. Department of Health and Human Services. Washington DC. Available at [Access date: 15.07.2024]:&nbsp; https://www.atsdr.cdc.gov/mrls/mrllist.asp#15tag&nbsp;</p>

<p>Buchman, M.F., 2008.&nbsp; NOAA Screening Quick Reference Tables, NOAA OR&amp;R Report 08-1, Seattle WA, Office of Response and Restoriation Division, Administration, 34p. Available at [Access date: 15.07.2024]: https://repository.library.noaa.gov/view/noaa/9327</p>

<p>Chaplygin, V., Dudnikova, T., Mandzhieva, S., Minkina, T., Barakhov, A., Nevidomskaya, D., Rajput, V.D., Litvinov, Yu., Burachevskaya, M., Chernikova, N., Nazarenko, O., Barbashev, A., Sushkova, S., 2023. A 10-year ecological monitoring of soils and Triticum aestivum in the impact zone of a power station. <em>Agriculture</em> 13(3): 722.</p>

<p>Diagboya, P.N., Olu-Owolabi, B.I., Dikio, E.D., Adebowale, K.O., 2018. Concentration-dependent and simultaneous sorption and desorption of pyrene and fluorene on major soil minerals in sub-Saharan Africa. <em>Applied Clay Science</em> 153: 257&ndash;264.</p>

<p>Dudnikova, T., Minkina, T., Sushkova, S., Barbashev, A., Antonenko, E., Konstantinova, E., Shuvaev, E., Nevidomskaya, D., Ivantsov, A., Bakoeva, G., Gorbunova, M., 2023a. Background content of polycyclic aromatic hydrocarbons during monitoring of natural and anthropogenically transformed landscapes in the coastal area soils. <em>Water</em> 15: 2424.</p>

<p>Dudnikova, T., Sushkova, S., Minkina, T., Barbashev, A., Ferreira, C.S.S., Antonenko, E., Shuvaev, E., Bakoeva, G., 2023b. Main factors in polycyclic aromatic hydrocarbons accumulations in the long-term technogenic contaminated soil. <em>Eurasian Journal of Soil Science</em> 12: 282&ndash;289.</p>

<p>Fedorenko, A.G., Chernikova, N., Minkina, T., Sushkova, S., Dudnikova, T., Antonenko, E., Fedorenk,o G., Bauer, T., Mandzhieva, S., Barbashev, A., 2021. Effects of benzo [a] pyrene toxicity on morphology and ultrastructure of Hordeum sativum. <em>Environmental Geochemistry and Health</em> 43: 1551&ndash;1562.</p>

<p>GOST 17.4.4.02-84; Methods of sampling and preparation of samples for chemical, bacteriological, helminthological analysis. Standartiform, Moscow, Russia. p. 8. [n Russian]</p>

<p>IARC, 2020. List of classifications, volumes 1-123. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Lyon: International Agency for Research on Cancer. Available at [Access date: 15.07.2024]: https://monographs.iarc.fr/list-of-classifications-volumes/</p>

<p>Islam, M.N., Park, H.S., Park, J.H., 2015. Extraction of diesel from contaminated soil using subcritical water. <em>Environmental Earth Sciences</em> 74: 3059&ndash;3066.</p>

<p>Latawiec, A.E., Reid, B.J., 2010. Sequential extraction of polycyclic aromatic hydrocarbons using subcritical water. <em>Chemosphere</em> 78(8): 1042&ndash;1048.</p>

<p>Lau, E.V., Gan, S., Ng, H.K., 2010. Extraction techniques for polycyclic aromatic hydrocarbons in soils. <em>International Journal of Analytical Chemistry</em> 1: 398381.</p>

<p>Liang, X., Zhu, L., Zhuang, S., 2016. Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions. <em>Journal of Soils and Sediments</em> 16: 1509-1518.</p>

<p>Macdonald, D.D., Carr, R.S., Calder, F.D., Long, E.R., Ingersoll, C.G., 1996. Development and evaluation of sediment quality guidelines for Florida coastal waters. <em>Ecotoxicology</em> 5: 253&ndash;278.</p>

<p>Marvin, C.H., Berthiaume, A., Burniston, D.A., Chibwe, L., Dove, A., Evans, M., Hewitt, M., Hodson, P., Muir, D.C.G., Parott, J.L., Thomas, P.J., Tomy, T., 2021. Polycyclic aromatic compounds in the Canadian Environment: Aquatic and terrestrial environments. <em>Environmental Pollution</em> 285: 117442.</p>

<p>MU 1424076, 1976. Methodical instructions and control for sampling from environmental objects and their preparation for subsequent determination of carcinogenic PAHs. M., p. [in Russian]</p>

<p>Poole, S.K., Dean, T.A., Oudsema, J.W., Poole, C.F., 1990. Sample preparation for chromatographic separations: an overview. <em>Analytica Chimica Acta</em> 236: 3&ndash;42.</p>

<p>Rabodonirina, S., NET, S., Ouddane, B., Merhaby, D., Dumoulin, D., Popescu, T., Ravelonandro, P., 2015. Distribution of persistent organic pollutants (PAHs, Me-PAHs, PCBs) in dissolved, particulate and sedimentary phases in freshwater systems. <em>Environmental Pollution</em> 206: 38&ndash;48.</p>

<p>RD 52.10.556-95. Methodical instructions. Determination of pollutants in samples of marine bottom sediments and suspensions. Roshydromet, State Oceanographic Institute, 1996. 49 p. [in Russian]</p>

<p>Ren, X., Zeng, G., Tang, L., Wang, J., Wan, J., Liu, Y., Yu, J., Yi, H., Ye, S., Deng, R., Sorption, transport and biodegradation&ndash;an insight into bioavailability of persistent organic pollutants in soil. <em>Science of the Total Environment</em> 610-611: 1154&ndash;1163.</p>

<p>Rhodes, A.H., Riding, M.J., McAllister, L.E., Lee, K., Semple, K.T., 2012. Influence of activated charcoal on desorption kinetics and biodegradation of phenanthrene in soil. <em>Environmental Science and Technology</em> 46(22): 12445&ndash;12451.</p>

<p>Sojinu, O.S., Wang, J.Z., Sonibare, O.O., Zeng, E.Y., 2010. Polycyclic aromatic hydrocarbons in sediments and soils from oil exploration areas of the Niger Delta, Nigeria. <em>Journal of Hazardous Materials</em> 174(1-3): 641&ndash;647.</p>

<p>Song, Y.F., Jing, X., Fleischmann, S., Wilke, B.M., 2002. Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments. <em>Chemosphere</em> 48(9): 993&ndash;1001.</p>

<p>Sushkova, S., Dudnikova, T., Minkina, T., Barbashev, A., Antonenko, E., Shuvaev, E., Nemtseva, A., 2024. Investigating the possibility of using subcritical water for extracting polycyclic aromatic hydrocarbons from soils of the dry-steppe zone. <em>Eurasian Journal of Soil Science</em> 13(3): 224&ndash;233.</p>

<p>Sushkova, S., Minkina, T., Mandzhieva, S., Tjurina, I., Bolotova, O., Vasilyeva, G., Orlović-Leko, P., Varduni, T., Kizilkaya, R., Akca, I., 2015. Solubility of benzo [a] pyrene and organic matter of soil in subcritical water. <em>Croatica Chemica Acta</em> 88(3): 247-253.</p>

<p>Sushkova, S., Minkina, T., Tarigholizadeh, S., Rajput, V., Fedorenko, A., Antonenko, E., Dudnikova, T., Chernikova, N., Yadav, B.K., Batukaev, A., 2021. Soil PAHs contamination effect on the cellular and subcellular organelle changes of Phragmites australis Cav. <em>Environmental Geochemistry and Health</em> 43: 2407-2421.</p>

<p>Sushkova, S.N., Vasilyeva, G.K., Minkina, T.M., Mandzhieva, S.S., Tjurina, I.G., Kolesnikov, S.I., Kizilkaya, R., Askin, T., 2014. New method for benzo [a] pyrene analysis in plant material using subcritical water extraction. <em>Journal of Geochemical Exploration</em> 144: 267-272.</p>

<p>Tsibart, A.S., Gennadiev, A.N., 2013. Polycyclic aromatic hydrocarbons in soils: sources, behavior, and indication significance (a review). <em>Eurasian Soil Science</em> 46(7): 728-741.</p>

<p>US EPA, 2007. Method 3550C. Ultrasonic Extraction. US Environmental Protection Agency. Washington, DC. Available at [Access date: 15.07.2024]: https://www.epa.gov/hw-sw846/sw-846-test-method-3550c-ultrasonic-extraction</p>

<p>US EPA, 2020. Integrated Risk Information System (IRIS). US Environmental Protection Agency. Washington, DC. Available at [Access date: 15.07.2024]: https://cfpub.epa.gov/ncea/iris_drafts/AtoZ.cfm</p>

<p>Wu, L., Sun, R., Li, Y., Sun, C., 2019. Sample preparation and analytical methods for polycyclic aromatic hydrocarbons in sediment. <em>Trends in Environmental Analytical Chemistry</em> 24: e00074.</p>

<p>Xu, L., Zhang, M., Zhu, L., 2014. Adsorption&ndash;desorption behavior of naphthalene onto CDMBA modified bentonite: Contribution of the &pi;&ndash;&pi; interaction. <em>Applied Clay Science</em> 100: 29&ndash;34.</p>

<p>Yabalak, E., Aminzai, M.T., Gizir, A.M., Yang, Y., 2024. A Review: Subcritical water extraction of organic pollutants from environmental matrices. <em>Molecules</em> 29(1): 258.</p>

<p>Zhang, Q., Liu, P., Li, S., Zhang, X., Chen, M., 2020. Progress in the analytical research methods of polycyclic aromatic hydrocarbons (PAHs). <em>Journal of Liquid Chromatography &amp; Related Technologies</em> 43(13&ndash;14): 425&ndash;444.</p>

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants that pose significant environmental and health risks due to their widespread distribution and carcinogenic properties. Developing efficient and environmentally friendly extraction methods for PAHs from complex matrices like bottom sediments is essential for advancing pollution monitoring and mitigation efforts. The influence of temperature and time parameters of water in a subcritical state on the extraction of widespread, contrasting in physicochemical properties polycyclic aromatic hydrocarbons (PAHs) from bottom sediment samples of the Lena River with varying initial pollutant content was studied. It was shown that the optimal extraction parameters for naphthalene are 240°C for 20 minutes, for phenanthrene and fluoranthene – 240°C for 30 minutes, for benzo(a)pyrene – 250°C for 30 minutes, and for benzo(g,h,i)perylene – 260°C for 40 minutes. Under these conditions, the proportion of extracted PAHs varies from 76% to 85%. A comparison was conducted of widely used PAH extraction methods based on the use of toxic solvents from standard techniques. It was established that the efficiency of extraction methods can be ranked as follows: ultrasound extraction > subcritical extraction > saponification method. In this case, the value of the PAH extraction coefficient during subcritical extraction was 1.23-1.29, during saponification - 1.35 and 1.34, and during the ultrasonic extraction method - 1.10 and 1.08.

Keywords: Polycyclic aromatic hydrocarbons, organic pollutants, bottom sediments, pollution, naphthalene, phenanthrene, benzo(a)pyrene, extraction method, high-performance liquid chromatography.

References

ATSDR, 1995. Toxicological profile for polycyclic aromatic hydrocarbons. Agency for Toxic Substances and Disease Registry. U.S. Department of Health and Human Services. Washington DC. Available at [Access date: 15.07.2024]:  https://wwwn.cdc.gov/tsp/ToxProfiles/ToxProfiles.aspx?id=122&tid=25

ATSDR, 2020. Minimal risk levels (MRLs) list. Agency for Toxic Substances and Disease Registry. U.S. Department of Health and Human Services. Washington DC. Available at [Access date: 15.07.2024]:  https://www.atsdr.cdc.gov/mrls/mrllist.asp#15tag 

Buchman, M.F., 2008.  NOAA Screening Quick Reference Tables, NOAA OR&R Report 08-1, Seattle WA, Office of Response and Restoriation Division, Administration, 34p. Available at [Access date: 15.07.2024]: https://repository.library.noaa.gov/view/noaa/9327

Chaplygin, V., Dudnikova, T., Mandzhieva, S., Minkina, T., Barakhov, A., Nevidomskaya, D., Rajput, V.D., Litvinov, Yu., Burachevskaya, M., Chernikova, N., Nazarenko, O., Barbashev, A., Sushkova, S., 2023. A 10-year ecological monitoring of soils and Triticum aestivum in the impact zone of a power station. Agriculture 13(3): 722.

Diagboya, P.N., Olu-Owolabi, B.I., Dikio, E.D., Adebowale, K.O., 2018. Concentration-dependent and simultaneous sorption and desorption of pyrene and fluorene on major soil minerals in sub-Saharan Africa. Applied Clay Science 153: 257–264.

Dudnikova, T., Minkina, T., Sushkova, S., Barbashev, A., Antonenko, E., Konstantinova, E., Shuvaev, E., Nevidomskaya, D., Ivantsov, A., Bakoeva, G., Gorbunova, M., 2023a. Background content of polycyclic aromatic hydrocarbons during monitoring of natural and anthropogenically transformed landscapes in the coastal area soils. Water 15: 2424.

Dudnikova, T., Sushkova, S., Minkina, T., Barbashev, A., Ferreira, C.S.S., Antonenko, E., Shuvaev, E., Bakoeva, G., 2023b. Main factors in polycyclic aromatic hydrocarbons accumulations in the long-term technogenic contaminated soil. Eurasian Journal of Soil Science 12: 282–289.

Fedorenko, A.G., Chernikova, N., Minkina, T., Sushkova, S., Dudnikova, T., Antonenko, E., Fedorenk,o G., Bauer, T., Mandzhieva, S., Barbashev, A., 2021. Effects of benzo [a] pyrene toxicity on morphology and ultrastructure of Hordeum sativum. Environmental Geochemistry and Health 43: 1551–1562.

GOST 17.4.4.02-84; Methods of sampling and preparation of samples for chemical, bacteriological, helminthological analysis. Standartiform, Moscow, Russia. p. 8. [n Russian]

IARC, 2020. List of classifications, volumes 1-123. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Lyon: International Agency for Research on Cancer. Available at [Access date: 15.07.2024]: https://monographs.iarc.fr/list-of-classifications-volumes/

Islam, M.N., Park, H.S., Park, J.H., 2015. Extraction of diesel from contaminated soil using subcritical water. Environmental Earth Sciences 74: 3059–3066.

Latawiec, A.E., Reid, B.J., 2010. Sequential extraction of polycyclic aromatic hydrocarbons using subcritical water. Chemosphere 78(8): 1042–1048.

Lau, E.V., Gan, S., Ng, H.K., 2010. Extraction techniques for polycyclic aromatic hydrocarbons in soils. International Journal of Analytical Chemistry 1: 398381.

Liang, X., Zhu, L., Zhuang, S., 2016. Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions. Journal of Soils and Sediments 16: 1509-1518.

Macdonald, D.D., Carr, R.S., Calder, F.D., Long, E.R., Ingersoll, C.G., 1996. Development and evaluation of sediment quality guidelines for Florida coastal waters. Ecotoxicology 5: 253–278.

Marvin, C.H., Berthiaume, A., Burniston, D.A., Chibwe, L., Dove, A., Evans, M., Hewitt, M., Hodson, P., Muir, D.C.G., Parott, J.L., Thomas, P.J., Tomy, T., 2021. Polycyclic aromatic compounds in the Canadian Environment: Aquatic and terrestrial environments. Environmental Pollution 285: 117442.

MU 1424076, 1976. Methodical instructions and control for sampling from environmental objects and their preparation for subsequent determination of carcinogenic PAHs. M., p. [in Russian]

Poole, S.K., Dean, T.A., Oudsema, J.W., Poole, C.F., 1990. Sample preparation for chromatographic separations: an overview. Analytica Chimica Acta 236: 3–42.

Rabodonirina, S., NET, S., Ouddane, B., Merhaby, D., Dumoulin, D., Popescu, T., Ravelonandro, P., 2015. Distribution of persistent organic pollutants (PAHs, Me-PAHs, PCBs) in dissolved, particulate and sedimentary phases in freshwater systems. Environmental Pollution 206: 38–48.

RD 52.10.556-95. Methodical instructions. Determination of pollutants in samples of marine bottom sediments and suspensions. Roshydromet, State Oceanographic Institute, 1996. 49 p. [in Russian]

Ren, X., Zeng, G., Tang, L., Wang, J., Wan, J., Liu, Y., Yu, J., Yi, H., Ye, S., Deng, R., Sorption, transport and biodegradation–an insight into bioavailability of persistent organic pollutants in soil. Science of the Total Environment 610-611: 1154–1163.

Rhodes, A.H., Riding, M.J., McAllister, L.E., Lee, K., Semple, K.T., 2012. Influence of activated charcoal on desorption kinetics and biodegradation of phenanthrene in soil. Environmental Science and Technology 46(22): 12445–12451.

Sojinu, O.S., Wang, J.Z., Sonibare, O.O., Zeng, E.Y., 2010. Polycyclic aromatic hydrocarbons in sediments and soils from oil exploration areas of the Niger Delta, Nigeria. Journal of Hazardous Materials 174(1-3): 641–647.

Song, Y.F., Jing, X., Fleischmann, S., Wilke, B.M., 2002. Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments. Chemosphere 48(9): 993–1001.

Sushkova, S., Dudnikova, T., Minkina, T., Barbashev, A., Antonenko, E., Shuvaev, E., Nemtseva, A., 2024. Investigating the possibility of using subcritical water for extracting polycyclic aromatic hydrocarbons from soils of the dry-steppe zone. Eurasian Journal of Soil Science 13(3): 224–233.

Sushkova, S., Minkina, T., Mandzhieva, S., Tjurina, I., Bolotova, O., Vasilyeva, G., Orlović-Leko, P., Varduni, T., Kizilkaya, R., Akca, I., 2015. Solubility of benzo [a] pyrene and organic matter of soil in subcritical water. Croatica Chemica Acta 88(3): 247-253.

Sushkova, S., Minkina, T., Tarigholizadeh, S., Rajput, V., Fedorenko, A., Antonenko, E., Dudnikova, T., Chernikova, N., Yadav, B.K., Batukaev, A., 2021. Soil PAHs contamination effect on the cellular and subcellular organelle changes of Phragmites australis Cav. Environmental Geochemistry and Health 43: 2407-2421.

Sushkova, S.N., Vasilyeva, G.K., Minkina, T.M., Mandzhieva, S.S., Tjurina, I.G., Kolesnikov, S.I., Kizilkaya, R., Askin, T., 2014. New method for benzo [a] pyrene analysis in plant material using subcritical water extraction. Journal of Geochemical Exploration 144: 267-272.

Tsibart, A.S., Gennadiev, A.N., 2013. Polycyclic aromatic hydrocarbons in soils: sources, behavior, and indication significance (a review). Eurasian Soil Science 46(7): 728-741.

US EPA, 2007. Method 3550C. Ultrasonic Extraction. US Environmental Protection Agency. Washington, DC. Available at [Access date: 15.07.2024]: https://www.epa.gov/hw-sw846/sw-846-test-method-3550c-ultrasonic-extraction

US EPA, 2020. Integrated Risk Information System (IRIS). US Environmental Protection Agency. Washington, DC. Available at [Access date: 15.07.2024]: https://cfpub.epa.gov/ncea/iris_drafts/AtoZ.cfm

Wu, L., Sun, R., Li, Y., Sun, C., 2019. Sample preparation and analytical methods for polycyclic aromatic hydrocarbons in sediment. Trends in Environmental Analytical Chemistry 24: e00074.

Xu, L., Zhang, M., Zhu, L., 2014. Adsorption–desorption behavior of naphthalene onto CDMBA modified bentonite: Contribution of the π–π interaction. Applied Clay Science 100: 29–34.

Yabalak, E., Aminzai, M.T., Gizir, A.M., Yang, Y., 2024. A Review: Subcritical water extraction of organic pollutants from environmental matrices. Molecules 29(1): 258.

Zhang, Q., Liu, P., Li, S., Zhang, X., Chen, M., 2020. Progress in the analytical research methods of polycyclic aromatic hydrocarbons (PAHs). Journal of Liquid Chromatography & Related Technologies 43(13–14): 425–444.