Effects of electrolytes and fractionated dissolved organic matter on selective adsorption of pharmaceuticals on terephthalic acid-based metal-organic frameworks

Dujduan Sompornpailin; Chalita Ratanatawanate; Natthawadee Chantanavorakunchai; Patiparn Punyapalakul

doi:10.1016/j.envres.2020.110335

Effects of electrolytes and fractionated dissolved organic matter on selective adsorption of pharmaceuticals on terephthalic acid-based metal-organic frameworks

Environ Res. 2021 May:196:110335. doi: 10.1016/j.envres.2020.110335. Epub 2020 Oct 16.

Authors

Dujduan Sompornpailin¹, Chalita Ratanatawanate², Natthawadee Chantanavorakunchai³, Patiparn Punyapalakul⁴

Affiliations

¹ International Postgraduate Programs in Hazardous Substance and Environmental Management, Graduate School, Chulalongkorn University, Bangkok, 10330, Thailand; Center of Excellence on Hazardous Substance Management, Chulalongkorn University, Bangkok, 10330, Thailand.
² National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120, Thailand; Research Network of NANOTEC - CU on Environment, Bangkok, 10330, Thailand.
³ Department of Environmental Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, 10330, Thailand.
⁴ Center of Excellence on Hazardous Substance Management, Chulalongkorn University, Bangkok, 10330, Thailand; Department of Environmental Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, 10330, Thailand; Research Unit Control of Emerging Micropollutants in Environment, Chulalongkorn University, Bangkok, 10330, Thailand; Research Network of NANOTEC - CU on Environment, Bangkok, 10330, Thailand. Electronic address: patiparn.p@chula.ac.th.

PMID: 33075356
DOI: 10.1016/j.envres.2020.110335

Abstract

In this study, we investigated the synergetic effects of coexisting electrolytes and dissolved organic matter (DOM) on Carbamazepine (CBZ) and Ciprofloxacin (CIP) adsorption on the 1D flexible structure of MIL-53(Al) and 3D rigid structure of UiO-66(Zr). The effects of electrolytes on the adsorption of CBZ and CIP on 1D flexible framework of MIL-53(Al) were more significant than those observed from the 3D framework of UiO-66(Zr). The presence of sulfate, nitrate, and phosphate anions indicates high potential to promote the adsorption of CBZ and CIP onto MIL-53(Al) and UiO-66(Zr) because of the decrease of solubility and strengthening of electrostatic interactions by substitution of oxo-anions at the metal complex node via covalent bonding. The lower hydration energy of the potassium ion enhanced CBZ adsorption on MIL-53(Al), while the higher hydration energy of calcium and magnesium ions reduced the adsorption capacity of CBZ and CIP on MIL-53(Al) and UiO-66(Zr). CBZ interacted with fractionated humic acid better than CIP. High-density carboxylic and aromatic functional groups on humic acid ensured that only humic acid larger than 1KDa was adsorbed by MIL-53(Al). Tryptophan-like and humic acid-like DOM were both detected in real hospital effluent, and their effects on CIP and CBZ adsorption onto MIL-53(Al) were investigated. The presence of tryptophan did not affect CBZ adsorption on MIL-53(Al) (except when coexisting with calcium ions). Conversely, tryptophan interfered with CIP adsorption. The presence of humic acid lower than 1KDa promoted the adsorption of CBZ and CIP by increasing the breathing effect of MIL-53(Al)'s 1D flexible framework. The presence of humic acid with molecular size greater than 1KDa enhanced both CBZ and CIP adsorption via a multilayer adsorption mechanism.

Keywords: Adsorption; Dissolved organic matter; Electrolyte; Metal-organic framework; Pharmaceutical residue.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Adsorption
Metal-Organic Frameworks*
Pharmaceutical Preparations*
Phthalic Acids*

Substances

Metal-Organic Frameworks
Pharmaceutical Preparations
Phthalic Acids
terephthalic acid