Decontamination of water co-polluted by copper, toluene and tetrahydrofuran using lauric acid

Abstract

Co-contamination by organic solvents (e.g., toluene and tetrahydrofuran) and metal ions (e.g., Cu²⁺) is common in industrial wastewater and in industrial sites. This manuscript describes the separation of THF from water in the absence of copper ions, as well as the treatment of water co-polluted with either THF and copper, or toluene and copper. Tetrahydrofuran (THF) and water are freely miscible in the absence of lauric acid. Lauric acid separates the two solvents, as demonstrated by proton nuclear magnetic resonance (¹H NMR) and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR). The purity of the water phase separated from 3:7 (v/v) THF:water mixtures using 1 M lauric acid is ≈87%v/v. Synchrotron small angle X-Ray scattering (SAXS) indicates that lauric acid forms reverse micelles in THF, which swell in the presence of water (to host water in their interior) and ultimately lead to two free phases: 1) THF-rich and 2) water-rich. Deprotonated lauric acid (laurate ions) also induces the migration of Cu²⁺ ions in either THF (following separation from water) or in toluene (immiscible in water), enabling their removal from water. Laurate ions and copper ions likely interact through physical interactions (e.g., electrostatic interactions) rather than chemical bonds, as shown by ATR-FTIR. Inductively coupled plasma-optical emission spectrometry (ICP-OES) demonstrates up to 60% removal of Cu²⁺ ions from water co-polluted by CuSO₄ or CuCl₂ and toluene. While lauric acid emulsifies water and toluene in the absence of copper ions, copper salts destabilize emulsions. This is beneficial, to avoid that copper ions are re-entrained in the water phase alongside with toluene, following their migration in the toluene phase. The effect of copper ions on emulsion stability is explained based on the decreased interfacial activity and compressional rigidity of interfacial films, probed using a Langmuir trough. In wastewater treatment, lauric acid (a powder) can be mixed directly in the polluted water. In the context of groundwater remediation, lauric acid can be solubilized in canola oil to enable its injection to treat aquifers co-polluted by organic solvents and Cu²⁺. In this application, injectable filters obtained by injecting cationic hydroxyethylcellulose (HEC +) would impede the flow of toluene and copper ions partitioned in it, protecting downstream receptors. Co-contaminants can be subsequently extracted upstream of the filters (using pumping wells), to enable their simultaneous removal from aquifers.