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.

UV photolysis of perfluorooctanoic acid (PFOA) in dilute aqueous solution.

Perfluorooctanoic acid (PFOA) is very persistent in the environment and widely detected in the water environment. Only some advanced methods with extreme reaction conditions are shown to be capable of degrading the compound efficiently, and almost all the earlier investigations used very high PFOA concentrations. The compound is detected normally at very low concentrations in the water environment, while mild reaction conditions for its degradation are preferable. This article aimed to elucidate photodegradation of PFOA in dilute aqueous solutions by combined UV wavelengths (185 nm+254 nm) and 254 nm using a newly designed UV jacket. PFOA degradation was greatly enhanced with the combined wavelengths with almost one hundred percent PFOA removals in four-hour reaction. The removals were well described by the first-order reaction kinetic. The removal efficiencies and rate values significantly decreased with smaller initial PFOA concentrations. But defluorination was greatly enhanced with smaller PFOA concentrations possibly due to accelerated decomposition of fluorinated intermediates of PFOA. Formic acid and acetic acid were two tentatively identified intermediates of PFOA photolysis while the former was a major intermediate predominantly controlling solution pH during the oxidation. The results demonstrated that PFOA photolysis by the combined wavelengths with mild reaction conditions can be greatly enhanced by proper design of UV jacket and reactor system.

Oxidative degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in subcritical and supercritical waters.

Presence of chlorinated organic compounds in water bodies has become a concern among governments, health authorities and general public. Oxidation of organic compounds in water under high temperature and pressure is considered as a promising technique, but usefulness of the technique to mineralize 2,4-dichlorophenoxyacetic acid (2,4-D) is not well understood. This article aimed to elucidate degradation characteristics of 2,4-D in both subcritical and supercritical waters by laboratory batch experiments. 2,4-D degradation, total organic carbon (TOC) removal and dechlorination increased with increasing reaction time and temperature especially in subcritical waters, while dechlorination was a major step. 2,4-dichlorophenol (2,4-DCP) and acetic acid were the main degradation intermediates both in subcritical and supercritical waters. Though 2,4-D disappeared almost completely in subcritical waters near critical region ( approximately 99%), significant amounts of TOC and organic chlorine still remained as 2,4-DCP and acetic acid. But TOC removal and dechlorination were significantly enhanced ( approximately 95 and 91% respectively) in supercritical waters. Complete mineralization of 2,4-D in subcritical waters required a considerably longer reaction period, while the mineralization was almost complete within a short reaction period in supercritical waters. This is an important information of practical significance for oxidative degradation of chlorinated pesticides similar to 2,4-D.

Rejection of pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) by low pressure reverse osmosis membranes.

This paper aims to elucidate retention characteristics of some pharmaceuticals and personal care products (PPCPs), and endocrine disrupting chemicals (EDCs), by two polyamide low pressure reverse osmosis (LPRO) membranes. Feed solution pH did not have an influence on rejections of undissociated solutes, which was most likely governed by adsorption, size exclusion and diffusion simultaneously. Size exclusion was presumably dominant, especially with tight membranes (UTC-70U). Rejections of the solutes with low dipole moment (<1.0 debye) decreased with increasing octanol-water partition coefficient (K(ow)). The solutes with large K(ow) values were most likely adsorbed on membrane and subsequently passed through it resulting in larger diffusion coefficient (D(p)). The rejections decreased with increasing D(p) values irrespective of their dipole moments. Rejections of solutes with comparatively larger dipole moments might be dominated by diffusion and/or convection rather than their hydrophobicity. However, rejections of solutes with hydroxyl and carboxyl functional groups by UTC-60 increased with solution pH. More than 80% rejections were obtained for degree of dissociation (alpha)>0.5. Electrostatic repulsion played a key role for rejection of dissociated solutes, especially by loose LPRO membranes. Therefore, assessing the dissociation degree at desired pH values can be a key step to obtain an insight of rejection mechanisms by polyamide membranes.

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 world's 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.

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.

Quantification of dioxin in the sieved fraction of river sediment.

Dioxin pollution of aquatic sediments has been one of the important environmental problems in Japan. Grain size distribution and organic constituents may play important roles in dioxins contents in sediments, which have not been well investigated. This paper aims to quantify dioxins (PCDDs/Fs and co-PCBs) in sieved surface sediment fractions obtained from Kizu and Sumiyoshi Rivers in Osaka, Japan. The samples were prepared and analyzed following the 'Manual of the Survey and Measurement of Dioxins in Sediment' (Environment Agency of Japan, 2000). The results showed that TEQ concentrations of dioxins increased with decreasing grain size in sediment fractions. Sediment fractions with less than 20 microm grain size showed the highest dioxin contents. Dioxins with five and six chlorine atoms dominated other congeners in less than 20 microm fractions. The dioxin TEQ concentrations increased with total organic carbon (TOC), total carbon (TC), ignition loss (IL), total sulphur and nitrogen contents in the sediment fractions. Thus, reporting dioxin contents in sediments without considering grain size distribution may be erroneous, and conventional sedimentation and separation techniques might not be useful for treating contaminated sediments. This information can be useful for effective remediation of dioxin-contaminated sediments.