Comparative study on Perfluoro(2-methyl-3-oxahexanoic) acid removal by quaternary ammonium functionalized silica gel and granular activated carbon from batch and column experiments and molecular simulation-based interpretation

Jin-Kyu Kang; Min-Gyeong Kim; Song-Bae Kim; Sanghyun Jeong; Jeong-Eun Oh

doi:10.1016/j.scitotenv.2024.171753

Comparative study on Perfluoro(2-methyl-3-oxahexanoic) acid removal by quaternary ammonium functionalized silica gel and granular activated carbon from batch and column experiments and molecular simulation-based interpretation

Sci Total Environ. 2024 May 20:926:171753. doi: 10.1016/j.scitotenv.2024.171753. Epub 2024 Mar 22.

Authors

Jin-Kyu Kang¹, Min-Gyeong Kim², Song-Bae Kim³, Sanghyun Jeong², Jeong-Eun Oh⁴

Affiliations

¹ Department of Marine Environmental Engineering, Gyeongsang National University, Gyeongsangnam-do 53064, Republic of Korea.
² Department of Civil and Environmental Engineering, Pusan National University, Busan 46241, Republic of Korea.
³ Water Environmental Systems and Deep Learning Laboratory, Seoul National University, Seoul 08826, Republic of Korea.
⁴ Department of Marine Environmental Engineering, Gyeongsang National University, Gyeongsangnam-do 53064, Republic of Korea; Department of Civil and Environmental Engineering, Pusan National University, Busan 46241, Republic of Korea. Electronic address: jeoh@pusan.ac.kr.

PMID: 38522552
DOI: 10.1016/j.scitotenv.2024.171753

Abstract

Removing perfluoro(2-methyl-3-oxahexanoic) acid (HFPO-DA) in water treatment is hindered by its hydrophobicity and negative charge. Two adsorbents, quaternary-ammonium-functionalized silica gel (Qgel), specifically designed for anionic hydrophobic compounds, and conventional granular activated carbon (GAC) were investigated for HFPO-DA removal. ANOVA results (p ≪ 0.001) revealed significant effects on initial concentration, contact time, and adsorbent type. Langmuir model-derived capacities were 285.019 and 144.461 mg/g for Qgel and GAC, respectively, with Qgel exhibiting higher capacity irrespective of pH. In column experiments, selective removal of HFPO-DA removal with Qgel was observed; specifically, in the presence of NaCl, the breakthrough time was extended by 10 h from 26 to 36 h. Meanwhile, the addition of NaCl decreased the breakthrough time from 32 to 14 h for GAC. However, in the presence of carbamazepine, neither of the adsorbents significantly changed the breakthrough time for HFPO-DA. Molecular simulations were also used to compare the adsorption energies and determine the preferential interactions of HFPO-DA and salts or other chemicals with Qgel and GAC. Molecular simulations compared adsorption energies, revealing preferential interactions with Qgel and GAC. Notably, HFPO-DA adsorption energy on GAC surpassed other ions during coexistence. Specifically, with Cl^- concentrations from 1 to 10 times, Qgel showed lower adsorption energy for HFPO-DA (-62.50 ± 5.44 eV) than Cl^- (-52.89 ± 2.59 eV), a significant difference (p = 0.036). Conversely, GAC exhibited comparable or higher adsorption energy for HFPO-DA (-18.33 ± 40.38 eV) than Cl- (-32.36 ± 29.89 eV), with no significant difference (p = 0.175). This suggests heightened selectivity of Qgel for HFPO-DA removal compared to GAC. Consequently, our study positions Qgel as a promising alternative for effective HFPO-DA removal, contributing uniquely to the field. Additionally, our exploration of molecular simulations in predicting micropollutant removal adds novelty to our study.

Keywords: Adsorption; Adsorption energy; Gen-X; HFPO-DA; Quaternized silica gel; Selective removal.