Phthalates are recognized as emerging environmental contaminants and are classified as endocrine-disrupting chemicals, as they can induce various toxic effects in organisms and interfere with hormonal functions in biological systems, thereby posing significant health risks. In this study, contamination of environmental matrices with phthalate residues—including water, agricultural soils, and grapes—was investigated. In addition, the sorption behavior of dibutyl phthalate (DBP) and di-(2-ethylhexyl phthalate (DEHP) from aqueous solutions onto biochars derived from apple residues and functionalized with metal oxides (Fe 3 O 4 and NiO), green-synthesized using plant extracts from Urtica dioica L. with the aim of their preliminary application in environmental remediation and the reduction of food-chain contamination risks. Several experimental series were conducted, including the determination of the sorption capacity of the biochars as a function of pH (3 - 9), characterization of adsorption isotherms at three temperatures (288 K, 298 K, and 308 K), and the thermodynamic parameters of adsorption. The experimental data were interpreted using the Langmuir and the Freundlich isotherm models. Furthermore, the thermodynamic parameters of the DBP sorption process onto the biochars, namely Gibbs free energy (Δ G 0 ), enthalpy (Δ H 0 ), and entropy (Δ S 0 ), were calculated.
Gore, A.C., La Merrill, M., Patisaul, H. and Sargis, R.M. (2024) Endocrine Disrupting Chemicals: Threats to Human Health. Endocrine Society and International Pollutants Elimination Network. https://www.endocrine.org
Den Hond, E., Tournaye, H., De Sutter, P., Ombelet, W., Baeyens, W., Covaci, A., et al. (2015) Human Exposure to Endocrine Disrupting Chemicals and Fertility: A Case-Control Study in Male Subfertility Patients. Environment International , 84, 154-160. https://doi.org/10.1016/j.envint.2015.07.017
Muñoz, J.P. (2025) The Impact of Endocrine-Disrupting Chemicals on Stem Cells: Mechanisms and Implications for Human Health. Journal of Environmental Sciences , 147, 294-309. https://doi.org/10.1016/j.jes.2023.11.015
Huang, L., Zhu, X., Zhou, S., Cheng, Z., Shi, K., Zhang, C., et al. (2021) Phthalic Acid Esters: Natural Sources and Biological Activities. Toxins , 13, Article 495. https://doi.org/10.3390/toxins13070495
Hahladakis, J.N., Velis, C.A., Weber, R., Iacovidou, E. and Purnell, P. (2018) An Overview of Chemical Additives Present in Plastics: Migration, Release, Fate and Environmental Impact during Their Use, Disposal and Recycling. Journal of Hazardous Materials , 344, 179-199. https://doi.org/10.1016/j.jhazmat.2017.10.014
Giuliani, A., Zuccarini, M., Cichelli, A., Khan, H. and Reale, M. (2020) Critical Review on the Presence of Phthalates in Food and Evidence of Their Biological Impact. International Journal of Environmental Research and Public Health , 17, Article 5655. https://doi.org/10.3390/ijerph17165655
Defranceschi, M., Ribera, D. and Doly, L. (2015) Substances émergentes, polluants émergents dans les déchets: Le cas des phthalates. Etude RECORD n˚13-0151/1A, Rapport final, 137 p. https://record-net.org/media/etudes/184/public/rapport/rapport-record13-0151-1a.pdf
Wang, L., Yuan, T., Kwa, Y.C. and Jong, M. (2025) Chronic Exposure to Phthalates in Drinking Water: The Implications on Public Health. Current Opinion in Environmental Science & Health , 44, Article ID: 100602. https://doi.org/10.1016/j.coesh.2025.100602
Okpara, K.E., Phoungthong, K., Agbozu, I., Edwin-Isotu, E. and Techato, K. (2022) Phthalate Esters in Tap Water, Southern Thailand: Daily Exposure and Cumulative Health Risk in Infants, Lactating Mothers, Pregnant and Nonpregnant Women. International Journal of Environmental Research and Public Health , 19, Article 2187. https://doi.org/10.3390/ijerph19042187
Farhadi, M., Sepahvand, A., Beiranvand, B. and Soleimani, F. (2025) Phthalate Concentrations in Drinking Water in WPRO Regions: A Systematic Review and Meta-analysis. Desalination and Water Treatment , 322, Article ID: 101217. https://doi.org/10.1016/j.dwt.2025.101217
Huggins, T.M., Haeger, A., Biffinger, J.C. and Ren, Z.J. (2016) Granular Biochar Compared with Activated Carbon for Wastewater Treatment and Resource Recovery. Water Research , 94, 225-232. https://doi.org/10.1016/j.watres.2016.02.059
Wang, S., Zhang, H., Wang, J., Hou, H., Du, C., Ma, P., et al. (2021) Application of Biochar for Wastewater Treatment. In: Thapar Kapoor, R., Treichel, H. and Shah, M.P., Eds., Biochar and its Application in Bioremediation , Springer, 67-90. https://doi.org/10.1007/978-981-16-4059-9_4
Julinová, M. and Slavík, R. (2012) Removal of Phthalates from Aqueous Solution by Different Adsorbents: A Short Review. Journal of Environmental Management , 94, 13-24. https://doi.org/10.1016/j.jenvman.2011.09.006
Lehmann, J. and Joseph, S. (2015) Biochar for Environmental Management: An introduction. In: Lehmann, J. and Joseph, S., Eds., Biochar for Environmental Management , Routledge, 33-46.
Downie, A., Crosky, A. and Munroe, P. (2012) Physical Properties of Biochar. In: Lehmann, J. and Joseph, S., Eds., Biochar for Environmental Management , Routledge, 45-64.
Ahmad, M., Rajapaksha, A.U., Lim, J.E., Zhang, M., Bolan, N., Mohan, D., et al. (2014) Biochar as a Sorbent for Contaminant Management in Soil and Water: A Review. Chemosphere , 99, 19-33. https://doi.org/10.1016/j.chemosphere.2013.10.071
Tan, X., Liu, Y., Gu, Y., Xu, Y., Zeng, G., Hu, X., et al. (2016) Biochar-Based Nano-Composites for the Decontamination of Wastewater: A Review. Bioresource Technology , 212, 318-333. https://doi.org/10.1016/j.biortech.2016.04.093
Bocșa, M., Lung, I., Tata, T., Opriș, O., Stegarescu, A., Kacso, I., et al. (2025) Sustainable Biochar Derived from Apple Wastes and Enhanced with Metal Oxides Green Synthesized for Water Purification by Adsorption. Discover Materials , 5, Article No. 279. https://doi.org/10.1007/s43939-025-00473-7
de Oliveira, T.F., Cagnon, B., Fauduet, H., Licheron, M. and Chedeville, O. (2012) Removal of Diethyl Phthalate from Aqueous Media by Adsorption on Different Activated Carbons: Kinetic and Isotherm Studies. Separation Science and Technology , 47, 1139-1148. https://doi.org/10.1080/01496395.2011.645184
Scopetani, C., Pellinen, J. and Selonen, S. (2024) Phthalates and Other Organic Chemicals in Agricultural Soils after Use of Different Types of Conventional and Biodegradable Plastics. Environmental Research , 255, Article ID: 119177. https://doi.org/10.1016/j.envres.2024.119177
Li, H., Liu, H., Liu, Z., Su, H., Simayi, S. and Liu, G. (2025) Distribution Features and Health Risk Assessment of Phthalate Pollutants in Facility Soil and Agricultural Products in Xinjiang, China. Agronomy , 15, Article 821. https://doi.org/10.3390/agronomy15040821
Topdas, E.F. (2023) Potential Toxic Phthalates and Heavy Metals Contamination in Vinegars and Human Health Risk Assessment. Journal of Food Composition and Analysis , 122, Article ID: 105491. https://doi.org/10.1016/j.jfca.2023.105491
Benito, S. (2019) The Management of Compounds That Influence Human Health in Modern Winemaking from an HACCP Point of View. Fermentation , 5, Article 33. https://doi.org/10.3390/fermentation5020033
Hou, H., Min, Y., Liu, X., Wang, P., Zhou, Z. and Liu, D. (2021) Occurrence and Migration of Phthalates in Adhesive Materials to Fruits and Vegetables. Journal of Hazardous Materials , 418, Article ID: 126277. https://doi.org/10.1016/j.jhazmat.2021.126277
Zhang, M. and Hou, J. (2025) Phthalate Contamination in Food: Occurrence, Health Risks, Biomarkers for Detection, and Mitigation Strategies to Enhance Food Safety. Journal of Agricultural and Food Chemistry , 73, 13178-13194. https://doi.org/10.1021/acs.jafc.5c02394
Jun, B., Kim, Y., Han, J., Yoon, Y., Kim, J. and Park, C.M. (2019) Preparation of Activated Biochar-Supported Magnetite Composite for Adsorption of Polychlorinated Phenols from Aqueous Solutions. Water , 11, Article 1899. https://doi.org/10.3390/w11091899
Zhou, Y., Zhao, B., Wang, L., Li, T., Ye, H., Li, S., et al. (2022) Adsorption of Phthalate Acid Esters by Activated Carbon: The Overlooked Role of the Ethanol Content. Foods , 11, Article 2114. https://doi.org/10.3390/foods11142114
Hamdaoui, O. and Naffrechoux, E. (2007) Modeling of Adsorption Isotherms of Phenol and Chlorophenols onto Granular Activated Carbonpart II. Models with More than Two Parameters. Journal of Hazardous Materials , 147, 401-411. https://doi.org/10.1016/j.jhazmat.2007.01.023
Liu, Y. (2009) Is the Free Energy Change of Adsorption Correctly Calculated? Journal of Chemical & Engineering Data , 54, 1981-1985. https://doi.org/10.1021/je800661q
Değermenci, G.D., Değermenci, N., Ayvaoğlu, V., Durmaz, E., Çakır, D. and Akan, E. (2019) Adsorption of Reactive Dyes on Lignocellulosic Waste; Characterization, Equilibrium, Kinetic and Thermodynamic Studies. Journal of Cleaner Production , 225, 1220-1229. https://doi.org/10.1016/j.jclepro.2019.03.260
Zhou, X., Yu, X., Maimaitiniyazi, R., Zhang, X. and Qu, Q. (2024) Discussion on the Thermodynamic Calculation and Adsorption Spontaneity Re Ofudje et al. (2023). Heliyon , 10, e28188. https://doi.org/10.1016/j.heliyon.2024.e28188