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

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.

Trypan blue removal from water with zein sorbents and laccase.

ABSTRACT: Zein-based materials were used to remove Trypan blue from water under flow conditions and in batch tests. In flow tests, zein dissolved at pH = 13 was injected in sand columns and subsequently coagulated with CaCl2, to create an adsorbent filter which removed over 99% of Trypan blue. Batch tests were conducted using zein powder, zein dissolved at pH = 13 and coagulated with CaCl2, Fe2Cl3 or citric acid, and zein dissolved in ethanol and then coagulated with water. The highest Trypan blue removal was achieved with zein powder (4000 mg Trypan blue/kg sorbent, as determined through spectrophotometry), followed by zein coagulated with Fe2Cl3 (500 mg Trypan blue/kg sorbent) and with other salts (140 mg Trypan blue/kg sorbent). Differences in the sorption efficiency are attributed to differences in the surface area. The sorption isotherm of Trypan blue onto zein-based sorbents was a Type II isotherm, suggesting physisorption. Desorption of Trypan blue was limited when zein-based coagulated sorbents were immersed in pure water. Trypan blue could be degraded by free laccase in water, as determined through spectrophotometry and electrospray ionization mass spectroscopy (ESI-MS). Trypan blue could also be degraded by laccase when zein-based laccase-containing sorbents were prepared at pH = 10, using Fe2Cl3 as coagulant. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s42452-020-04107-w.

Selective solvent filters for non-aqueous phase liquid separation from water.

Injectable filters permeable to water but impermeable to non-polar solvents were developed to contain non-aqueous phase liquids (NAPL) in contaminated aquifers, hence protecting downstream receptors during NAPL remediation. Filters were produced by injecting aqueous solutions of 0.01% chitosan, hydroxyethylcellulose and quaternized hydroxyethylcellulose into sand columns, followed by rinsing with water. Polymer sorption onto silica was verified using a quartz-crystal microbalance with dissipation monitoring. Fluorescence and gas chromatography mass spectroscopy showed low ppm range concentrations of non-polar solvents (e.g., hexane and toluene) in water eluted from the filters (in the absence of emulsifiers). The contact angles between polymer-coated surfaces and hexane or toluene were > 90°, indicating surface oleophobicity. Organic, polar solvents (e.g. tetrahydrofuran and tetrachloroethylene, TCE) were not separated from water. The contact angles between polymer-coated surfaces and TCE was also > 90°. However, the contact area with polymer coated surfaces was greater for TCE than non-polar solvents, suggesting higher affinity between TCE and the surfaces. Emulsifiers can be used to facilitate NAPL extraction from aquifers. Emulsion separation efficiency depended on the emulsifier used. Emulsions were not separated with classical surfactants (e.g. Tween 20 and oleic acid) or alkaline zein solutions. Partial emulsion separation was achieved with humic acids and zein particles.