Rabindra Raj Giri

Degradation of common pharmaceuticals and personal care products in mixed solutions by advanced oxidation techniques

Widespread detection of pharmaceutical compounds in water environment has been a serious concern recently, while conventional sewage treatments are ineffective for their elimination. But, advanced oxidation techniques are very promising to remove varieties of organic contaminants in water. This research aims to elucidate oxidation potentials of sixteen commonly used pharmaceutical compounds in mixed solutions by seven advanced oxidation techniques in laboratory batch experiments. The removal profiles exhibited four distinct patterns: a) easily degradable by all seven techniques, b) not easily degradable by all seven techniques, c) easily degradable by ozone-based techniques, but not by ultraviolet radiation-based techniques and d) easily degradable by ultraviolet radiation-based techniques, but not by ozone-based techniques. Ozone-based techniques rather than ultraviolet radiation-based techniques were very powerful for simultaneous removal of the compounds efficiently. Moreover, ozonation combined with ultraviolet radiation was the most appropriate technique for simultaneous removal of the tested compounds efficiently. Increased ozone dissolution and decomposition with ozone-based techniques did not always enhance the compounds’ removal. Physicochemical properties of the compounds and solution pH also presumably played an important role on the removal which merits further attention.

A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution.

More efficient oxidation methods are needed to degrade especially newly emerging recalcitrant organic contaminants at low concentrations in the water environment. Reduced photonic efficiency of immobilized TiO2 is a major challenge in TiO2-assisted advanced oxidation processes (AOP). Mineralization of 2,4-dichllorophenoxyacetic acid (2,4-D) in low aqueous solution by O3/UV/TiO2 using the worlds first high-strength TiO2 fiber was investigated and compared with O3, UV/TiO2, and O3/TiO2 in laboratory batch experiments. The 2,4-D degradation and total organic carbon (TOC) removal followed pseudo first-order reaction kinetic, while their rates in O3/UV/TiO2 were respectively about 1.5 and 2.4 times larger than the summation of the values in 03 and UV/TiO2. The O3/UV/TiO2 was characterized by few aromatics with very low abundance, fast disappearance of aliphatics and more than 95% dechlorination. The discrepancies in organic carbon mass balance among the intermediates and 2,4-D were attributed mainly to few apparently major unidentified intermediates. The significantly enhanced 2,4-D mineralization in O3/UV/TiO2 was attributed to increased ozone dissolution followed by its decomposition, and reduced electron-hole recombination in presence of dissolved ozone resulting in a large number of hydroxyl radical (*OH) generation from more than one parallel path. The removal efficiencies of the systems can further be enhanced by optimizing design parameters, and O3/UV/TiO2 with the TiO2 fiber is promising to mineralize recalcitrant organic contaminants in water at low concentrations.

Heterogeneous photocatalytic ozonation of 2,4-D in dilute aqueous solution with TiO2 fiber

Photocatalytic ozonation (O(3)/UV/TiO2) is an emerging oxidation method for recalcitrant organic contaminants in water. However, immobilised TiO2 catalysts suffer from reduced photonic efficiency. Therefore, TiO2 catalysts with excellent mechanical and thermal properties and enhanced photonic efficiencies are sought. This paper aimed to elucidate the mineralisation of low concentration 2,4-D (45.0 microM) by O(3)/UV/TiO2 using the worlds first high-strength TiO2 fibre in laboratory batch experiments. 2,4-D degradation and TOC removal followed pseudo first-order reaction kinetic. The removal rates for 2,4-D and TOC in O(3)/UV/TiO2 were 1.5 and 2.4-fold larger than the summation of the values for ozonation (O3)) and photocatalysis (UV/TiO2), respectively. O(3)/UV/TiO2 was characterised by few aromatic intermediates with low abundance, fast degradations of aliphatic intermediates and dechlorination as a major step. The significantly enhanced 2,4-D mineralisation in O(3)/UV/TiO2 was attributed to increased ozone dissolution and decomposition, and reduced electron-hole recombination resulting in large number of hydroxyl radical (*OH) formation from more than one parallel path. The discrepancies in the organic carbon mass budget were attributed to few apparently major unidentified intermediates, while chlorine mass balance was reasonably acceptable. The mineralisation efficiency of O(3)/UV/TiO2 with the TiO2 fibre can further be enhanced by optimisation of experimental design parameters. The new TiO2 fibre is very promising to overcome the problem of reduced efficiency of TiO2 catalyst in an immobilised state.

Water matrix effect on UV photodegradation of perfluorooctanoic acid

The widespread detection of perfluorinated compounds (PFCs) in the water environment has been a concern for the last several years, while effluents from wastewater treatment facilities are the major sources of these compounds. Even advanced oxidation technologies (AOTs) are not useful for mineralization of the compounds due to their very high stability. Photochemical techniques using particularly vacuum UV (VUV) have been found to be very promising in this regard. But the use of VUV in UV-based AOTs has still not progressed much. Moreover, the impact of water quality on PFCs photomineralization is unknown. This investigation aimed to assess photomineralization potentials of perfluorooctanoic acid (PFOA) in ultrapure water (UPW), tap water (TW), surface water and treated wastewater effluent using a reactor setup enabling maximum utilization of VUV emission of low pressure lamp in laboratory batch experiments. Neya River water (NRW) and the Nakahama Wastewater Treatment Plant Effluent (NWWTPE) represented surface water and treated wastewater effluent respectively. Also, tests were carried out in 50% diluted NRW and NWWTPE. PFOA photomineralization in terms of PFOA removal, defluorination and total organic carbon (TOC) removal are discussed. The usefulness of the method for PFOA mineralization in organic-rich wastewaters, and further research needs are also highlighted.

Significance of water quality and radiation wavelength for UV photolysis of PhCs in simulated mixed solutions

Ultraviolet (UV) photolysis of sixteen pharmaceutical compounds (PhCs) in mixed solutions with four types of water and two sets of UV radiation was investigated. UVC (254 nm) photolysis was ineffective at eliminating a large number of PhCs while a big number of them were refractory. However, vacuum UV (VUV: 185 nm + 254 nm) photolysis in the same experimental conditions eliminated the PhCs almost completely. The eliminations in ultrapure water (UPW), tap water (TW) and Neya River water (NRW) and their organic/inorganic contents were inversely correlated, which was more evident in VUV photolysis. Natural organic matter (NOM) in NRW did not have an impact in indirect photolysis, but effluent organic matter (EfOM) in secondary-treated effluent (NWTPE) enhanced indirect photolysis, which was more evident in VUV photolysis underlining the point that radiation wavelength/intensity can be a limiting factor in organic-rich waters. Moreover, VUV photolysis was far superior (90% mineralization) to UVC photolysis (10% mineralization) for PhCs mineralization. The greatly enhanced elimination and mineralization efficiencies observed for VUV photolysis were attributed to accelerated direct photolysis with 185 nm wavelength and indirect photolysis involving ·OH. The results demonstrated efficacy of VUV photolysis in wastewater treatment and its potential use as a tertiary treatment.

Efficacies of UVC and VUV photolysis for mineralization of pharmaceutical compounds in mixed aqueous solution

AbstractThe usefulness of ultraviolet-C (UVC: 254 nm) and vacuum UV (VUV: 185 +  254 nm) photolysis for elimination and mineralization of four selected pharmaceutical compounds (PhCs) in mixed aqueous solution were tested in laboratory batch experiments. UVC photolysis was unable to eliminate moderate and refractory PhCs. Moreover, it was not at all useful for mineralization of the PhCs (<10% TOC removal, 30 min reaction) and longer reaction period (i.e. 60 min) had no significant positive impact on the mineralization efficiency. On the other hand, VUV photolysis eliminated the PhCs almost completely in a short reaction period irrespective of their nature, and 90% mineralization was achieved in an hour. The greatly enhanced elimination and mineralization efficiencies for VUV photolysis were attributed to accelerated direct and indirect photolysis reactions. Based on the results, it was concluded that VUV photolysis was very promising over UVC photolysis for mineralization of PhCs in mixed aqueous solution...

Volume Reduction of Municipal Solid Wastes Contaminated with Radioactive Cesium by Ferrocyanide Coprecipitation Technique

Municipal solid wastes (MSW) with elevated concentrations of radioactive cesium (rad-Cs hereafter) have been generated in some areas of Japan in the aftermath of the Fukushima Daiichi Nuclear Power Plant (F1 hereafter) accident. Both recycling and final disposal of the contaminated MSW have become a difficult problem in the affected areas, resulting in accumulation of treated residues in the treatment facilities.

Low-pressure reverse osmosis membrane separation of non-fluorinated and perfluorinated organic compounds in water

AbstractThe purpose of this study is to compare retention characteristics of perfluorinated organic compounds (PFCs) and similar-structured non-fluorinated organic compounds (NFCs) by new generation low-pressure reverse osmosis (LPRO) membranes based on physicochemical properties of the compounds and the results of bench-scale membrane efficiency batch tests as the first-step screening. Molecular weight (MW), molecular size, and hydrophobicity of the compounds greatly influence their retentions by loose and low-desalting membranes than those by tight and high-desalting membranes. The retentions in general increased with increasing MW and molecular length (ML). The retentions are explained more reliably by using both MW and molecular width/height parameters. The roles of MW and ML on the retentions could not be differentiated, since MW increases almost linearly with ML. The NFCs are more easily rejected than the PFCs by the membranes most probably due to hydrophobic adsorption of the PFCs to membranes lead...