Hydrogen peroxide (H 2 O 2 ) in the range of several tens to several hundreds of micromoles per liter is usually added to the process water in advanced oxidation processes (AOPs). In this study, a spectrophotometric method using copper(II) ion and 2,9-dimethyl-1,10-phenanthroline (DMP) for measuring H 2 O 2 concentration was compared with other methods [i.e., spectrophotometric methods using titanium oxalate and N,N-diethyl-p-phenylenediamine (DPD) and a fluorometric method using p-hydroxyphenyl acetic acid (POHPAA)]. Particular attention was paid to sensitivities and effects of coexisting substances. The most sensitive method was the fluorometric method, followed in order by DPD, DMP, and the titanium oxalate colorimetric method; their detection limits in 1-cm cells were 0.16, 0.77, 0.80, and 29 µM, respectively. Therefore, the DMP method was found to be reasonably sensitive when applied to AOPs. Also, the DMP reagent is commercially available, and the absorbance of Cu(DMP) 2 + , a reaction product of the DMP method, was not affected by reaction time. In the DMP method, copper(II)-DMP complexes react with humic acid, and colored chemicals are produced. However, the slopes of the calibration curves of H 2 O 2 containing up to 10 mg of C L -1 from humic acid did not change significantly as compared to that in ultrapure water. The effect of chlorine on the DMP method was not observed up to at least 23 µM (0.8 mg of Cl L -1 ) of free chlorine, although the DPD and fluorometric methods are known to be interfered by chlorine. From this study, it was concluded that the DMP method is suitable to be used in AOPs.

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O3/vacuum ultraviolet (VUV, ultraviolet radiation by a low pressure mercury lamp at 185 and 254 nm), O3/H2O2 and VUV processes rapidly decomposed organophosphoric acid triesters (OPEs) dissolved in distilled water as compared to simple ozonation. The O3/VUV process was the fastest of the three advanced oxidation processes (AOPs) for the decomposition of 1 mg/l of OPEs in pH 7.5 phosphate buffer solution (0.5 mM). However the difference between the pseudo-first-order rate constants of the O3/VUV and O3/H2O2 processes decreased in the condition of increasing OPEsw concentration, and the efficiencies of the two processes were almost the same at an initial concentration of 20 mg/l. Contrary to results in distilled water, in an effluent from a solid waste landfill site, the O3/H2O2 process was the fastest. This is manily due to the absorption of VUV radiation by nitrate ion. WE confirmed that nitrate ion of more than a few mg/l strongly interfered with the generation of hydroxyl (OH) radicals from VUV radiation while the O3/H2O2 process was not affected. The use of an ESR-spin trapping technique revealed that AOPs generated more OH radicals than ozonation alone, and the detection of hydrogen atom confirmed that VUV radiation directly generated OH radicals from water.

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The effect of co-existing compounds on the decompositions of three target compounds (i.e., 1,2,4-trichlorobenzene (TCB), 1,4-dioxane, and 17β-estradiol) using the ozone/hydrogen peroxide (O3/H2O2) process was investigated. Their reactivities toward HO• are assumed to be of the order of 109 /M · s. The decomposition rate of TCB was much higher during the O3/H2O2 process than during ozonation in the presence of bicarbonate ion, an inhibitor of radical chain reactions. 17β-Estradiol, a highly reactive target compound toward ozone, was decomposed at lower ozone dose than TCB and 1,4-dioxane, lowly reactive target compounds toward ozone, in the presence of humic acid. The reactivities of the co-existing compounds toward HO• were significantly related to the treatment efficiency of TCB when their concentrations as TOC were similar. The effect of humic acid, fulvic acid, and glucose, target compounds highly reactive toward HO•, on the decomposition of TCB was similar regardless of co-existing compounds. On the other hand, significantly lower effect of acetate and oxalate ions, target compounds lowly reactive toward HO•, on the decomposition of TCB was observed. Ozone dose required for the decomposition of TCB was inversely proportional to TCB concentration when HO• generated was greatly scavengedby co-existing compounds. On the other hand, ozone dose required for the decomposition of TCB was less affected by TCB concentration when HO• generated was used effectively for the decomposition of TCB.