PMID- 36564692 OWN - NLM STAT- MEDLINE DCOM- 20230329 LR - 20240228 IS - 1614-7499 (Electronic) IS - 0944-1344 (Print) IS - 0944-1344 (Linking) VI - 30 IP - 13 DP - 2023 Mar TI - Adsorption of the hydrophobic organic pollutant hexachlorobenzene to phyllosilicate minerals. PG - 36824-36837 LID - 10.1007/s11356-022-24818-4 [doi] AB - Hexachlorobenzene (HCB), a representative of hydrophobic organic chemicals (HOC), belongs to the group of persistent organic pollutants (POPs) that can have harmful effects on humans and other biota. Sorption processes in soils and sediments largely determine the fate of HCB and the risks arising from the compound in the environment. In this context, especially HOC-organic matter interactions are intensively studied, whereas knowledge of HOC adsorption to mineral phases (e.g., clay minerals) is comparatively limited. In this work, we performed batch adsorption experiments of HCB on a set of twelve phyllosilicate mineral sorbents that comprised several smectites, kaolinite, hectorite, chlorite, vermiculite, and illite. The effect of charge and size of exchangeable cations on HCB adsorption was studied using the source clay montmorillonite STx-1b after treatment with nine types of alkali (M(+): Li, K, Na, Rb, Cs) and alkaline earth metal cations (M(2+): Mg, Ca, Sr, Ba). Molecular modeling simulations based on density functional theory (DFT) calculations to reveal the effect of different cations on the adsorption energy in a selected HCB-clay mineral system accompanied this study. Results for HCB adsorption to minerals showed a large variation of solid-liquid adsorption constants K(d) over four orders of magnitude (log K(d) 0.9-3.3). Experiments with cation-modified montmorillonite resulted in increasing HCB adsorption with decreasing hydrated radii of exchangeable cations (log K(d) 1.3-3.8 for M(+) and 1.3-1.4 for M(2+)). DFT calculations predicted (gas phase) adsorption energies (- 76 to - 24 kJ mol(-1) for M(+) and - 96 to - 71 kJ mol(-1) for M(2+)) showing a good correlation with K(d) values for M(2+)-modified montmorillonite, whereas a discrepancy was observed for M(+)-modified montmorillonite. Supported by further calculations, this indicated that the solvent effect plays a relevant role in the adsorption process. Our results provide insight into the influence of minerals on HOC adsorption using HCB as an example and support the relevance of minerals for the environmental fate of HOCs such as for long-term source/sink phenomena in soils and sediments. CI - (c) 2022. The Author(s). FAU - Bohm, Leonard AU - Bohm L AUID- ORCID: 0000-0002-3435-5956 AD - Institute of Soil Science and Soil Conservation, Research Centre for BioSystems, Land Use and Nutrition (iFZ), Justus Liebig University Giessen, Heinrich-Buff-Ring 26, 35392, Giessen, Germany. leonard.boehm@umwelt.uni-giessen.de. FAU - Grancic, Peter AU - Grancic P AD - Institute for Soil Research, Department of Forest and Soil Sciences, University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, 1190, Vienna, Austria. FAU - Scholtzova, Eva AU - Scholtzova E AD - Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska Cesta 9, 845 36, Bratislava 45, Slovakia. FAU - Heyde, Benjamin Justus AU - Heyde BJ AD - Institute of Soil Science and Soil Conservation, Research Centre for BioSystems, Land Use and Nutrition (iFZ), Justus Liebig University Giessen, Heinrich-Buff-Ring 26, 35392, Giessen, Germany. FAU - During, Rolf-Alexander AU - During RA AD - Institute of Soil Science and Soil Conservation, Research Centre for BioSystems, Land Use and Nutrition (iFZ), Justus Liebig University Giessen, Heinrich-Buff-Ring 26, 35392, Giessen, Germany. FAU - Siemens, Jan AU - Siemens J AD - Institute of Soil Science and Soil Conservation, Research Centre for BioSystems, Land Use and Nutrition (iFZ), Justus Liebig University Giessen, Heinrich-Buff-Ring 26, 35392, Giessen, Germany. FAU - Gerzabek, Martin H AU - Gerzabek MH AUID- ORCID: 0000-0002-3307-8416 AD - Institute for Soil Research, Department of Forest and Soil Sciences, University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, 1190, Vienna, Austria. FAU - Tunega, Daniel AU - Tunega D AD - Institute for Soil Research, Department of Forest and Soil Sciences, University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, 1190, Vienna, Austria. LA - eng GR - 443637168/Deutsche Forschungsgemeinschaft/ GR - BO5388/1-1/Deutsche Forschungsgemeinschaft/ GR - I 4876-N/Austrian Science Fund/ GR - 2/0021/19/Vedecka Grantova Agentura MSVVaS SR a SAV/ PT - Journal Article DEP - 20221223 PL - Germany TA - Environ Sci Pollut Res Int JT - Environmental science and pollution research international JID - 9441769 RN - T1FAD4SS2M (Clay) RN - 4Z87H0LKUY (Hexachlorobenzene) RN - 1302-78-9 (Bentonite) RN - 0 (Environmental Pollutants) RN - 0 (Soil Pollutants) RN - 0 (Aluminum Silicates) RN - 0 (Minerals) RN - 0 (Soil) RN - 0 (Organic Chemicals) RN - 0 (Cations) SB - IM MH - Humans MH - Clay MH - Hexachlorobenzene/chemistry MH - Bentonite/chemistry MH - *Environmental Pollutants MH - Adsorption MH - *Soil Pollutants/analysis MH - Aluminum Silicates/chemistry MH - Minerals/chemistry MH - Soil/chemistry MH - Organic Chemicals/chemistry MH - Cations/chemistry PMC - PMC10039842 OTO - NOTNLM OT - Cations OT - Clay minerals OT - Environmental fate OT - Halogenated aromatic hydrocarbons OT - Hydration enthalpy OT - Molecular simulations OT - Montmorillonite OT - Persistent organic pollutants (POP) COIS- The authors declare no competing interests. EDAT- 2022/12/24 06:00 MHDA- 2023/03/29 06:05 PMCR- 2022/12/23 CRDT- 2022/12/23 23:44 PHST- 2022/10/04 00:00 [received] PHST- 2022/12/13 00:00 [accepted] PHST- 2023/03/29 06:05 [medline] PHST- 2022/12/24 06:00 [pubmed] PHST- 2022/12/23 23:44 [entrez] PHST- 2022/12/23 00:00 [pmc-release] AID - 10.1007/s11356-022-24818-4 [pii] AID - 24818 [pii] AID - 10.1007/s11356-022-24818-4 [doi] PST - ppublish SO - Environ Sci Pollut Res Int. 2023 Mar;30(13):36824-36837. doi: 10.1007/s11356-022-24818-4. Epub 2022 Dec 23.