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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2015, Vol. 9 Issue (3) : 429-435
Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2
Eunsung KAN1,*(),Chang-Il KOH2,Kyunghyuk LEE2,Joonwun KANG2
1. Department of Molecular Bioscience and Bioengineering, University of Hawaii, Honolulu, HI 96822, USA
2. Department of Industrial Environment and Health, Yonsei University, Wonju 220-842, Korea
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In the present study, the decomposition rates of carbon tetrachloride (CCl4) and 2,4-dichlorophenol (2,4-DCP) in water by the ultraviolet (UV) light irradiation alone and H2O2/UV were experimentally investigated. The detailed experimental studies have been conducted for examining treatment capacities of the two different ultraviolet light sources (low and medium pressure Hg arc) in H2O2/UV processes. The low or medium UV lamp alone resulted in a 60%–90% decomposition of 2,4-DCP while a slight addition of H2O2 resulted in a drastic enhancement of the 2,4-DCP decomposition rate. The decomposition rate of 2,4-DCP with the medium pressure UV lamp alone was about 3–6 times greater than the low pressure UV lamp alone. In the direct photolysis of aqueous CCl4, the medium pressure UV lamp had advantage over the low pressure UV lamp because the molar extinction coefficient of CCl4 at shorter wavelength (210–220 nm) is about 20 to 50 times higher than that at 254 nm. However, adding H2O2 to the medium pressure UV lamp system rendered a negative oxidation rate because H2O2 acted as a UV absorber being competitive with CCl4 due to negligible reaction between CCl4 and OH radicals. The results from the present study indicated significant influence of the photochemical properties of the target contaminants on the photochemical treatment characteristics for designing cost-effective UV-based degradation of toxic contaminants.

Keywords H2O2/ultraviolet (UV) light      advanced oxidation      UV light irradiation      chlorinated contaminants      photochemical treatment characteristics     
Corresponding Authors: Eunsung KAN   
Online First Date: 14 March 2014    Issue Date: 30 April 2015
 Cite this article:   
Eunsung KAN,Chang-Il KOH,Kyunghyuk LEE, et al. Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2[J]. Front. Environ. Sci. Eng., 2015, 9(3): 429-435.
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Eunsung KAN
Chang-Il KOH
Kyunghyuk LEE
Joonwun KANG
Fig.1  Schematic of the photo- reactors. (a) Reactor 1 with the low pressure UV lamp, (b) Reactor 2 with the medium pressure UV lamp (P: circulation pump; C: cooler; D: drain; SP: sampling port). Please see the detailed information in Table 1
Specification of the reactors Reactor 1 Reactor 2
UV lamp low pressure Hg medium pressure Hg
electrical power per volume of a reactor /(watt·L-1) 13 150
number of lamps 1 1
material of reactor stainless steel pyrex
dimension/(inner diameter, cm × height, cm) 7 (ID) × 73 (H) 8.5 (ID) × 20 (H)
volume of reactor /L 3 1
mode of stirring recirculation magnetic stirring
Tab.1  Characteristics of the photo-reactors used for the experiments
Fig.2  Decomposition of 2,4-DCP by H2O2 with the low or medium pressure UV lamp: (a) low pressure UV with H2O2, (b) medium pressure UV with H2O2. Conditions: [2,4-DCP]0, 50 mg·L-1. The insets show the enhancement of rate constant at increasing H2O2 concentration. The enhancement is defined as [rate constant at any H2O2 concentration]/[rate constant without H2O2] in H2O2/UV processes. Please see the detailed conditions in the methods and material
Λ/nm ?/(L·mmol-1·cm-1)
H2O2 CCl4 2,4-DCP
210 133.4 98.2 500.4
220 91.3 40.7 541.0
240 36.9 3.7 471.7
254 18.5 2.1 171.4
310 2.8 5.8 21.6
Tab.2  Molar extinction coefficients of H2O2, CCl4 and 2,4-DCP
rate constant Reactor 1 Reactor 2 Reactor 2/Reactor 1
k/min-1 for UV alone 0.043 (R2 = 0.97) 0.123 (R2 = 0.97) 3.1
k′/(L·min-1·mmol-1 H2O2) for UV/H2O2 0.032 0.086 2.7
Tab.3  2,4 DCP decomposition rate by the low or medium pressure UV lamps
process RE % of 2,4-DCP operating conditions reference
UV irradiation H2O2/UV 40% in 30 min70% in 90 min85% in 10 min100% in 30 min [2,4-DCP]0, 0.46 mmol·L-1;[H2O2]0, 10 mmol·L-1; pH= 7; light intensity, 7.9×10-2 μE·cm-2·s-1 ; low pressure UV lamp (40W) [22]
UV irradiation H2O2/UV 91% in 90 min100% in 10 min [2,4-DCP]0, 0.15 mmol·L-1; [H2O2]0, 10 mmol·L-1; pH= 7; light intensity, 6.6×10-2 μE·cm-2·s-1; low pressure UV lamp (40W) [17]
UV irradiation H2O2/UV 99% in 30 min(k= 0.18 min-1)100% in 30 min(k= 0.31 min-1) [2,4-DCP]0, 0.12 mmol·L-1; [H2O2]0, 1.5 mmol·L-1; pH= 7; medium pressure UV lamp (1 kW) [23]
UV irradiation H2O2/UV 62% in 60 min83% in 120 min90% in 30 min96% in 60 min [2,4-DCP]0, 0.12 mmol·L-1; [H2O2]0, 12 mmol·L-1; pH= 7; four low pressure UV lamp (15 W for each) [24]
UV irradiation H2O2/UV 25% in 30 min90% in 175 min90% in 45 min [2,4-DCP]0, 0.4 mmol·L-1; [H2O2]0, 10 mmol·L-1; pH= 7; light intensity, 0.304 W·L-1; low pressure UV lamp (40 W) [25]
UV irradiation H2O2/UV 14% in 10 min70% in 30 min96% in 10 min99% in 30 min [2,4-DCP]0, 0.31 mmol·L-1; [H2O22]0, 10 mmol·L-1; pH= 7; light intensity: 13 W·L-1; three low pressure UV lamp this study
UV irradiation H2O2/UV 43% in 10 min97% in 30 min81% in 10 min97% in 30 min [2,4-DCP]0, 0.31 mmol·L-1; [H2O2]0, 2 mmol·L-1; pH= 7; one medium pressure UV lamp (150 W·L-1) this study
Tab.4  Summary of 2,4-DCP removal by direct photolysis and H2O2/UV processes
Fig.3  Decomposition of CCl4 by the low or medium pressure UV irradiation alone. Conditions: [CCl4]0, 10 mg·L-1; low pressure UV (Reactor 1); medium pressure UV (Reactor 2). Please see the detailed conditions in the method and material
Fig.4  Effect of H2O2 on CCl4 decomposition in H2O2/UV processes. Conditions: [CCl4]0, 10 mg·L-1; low pressure UV (Reactor 1); medium pressure UV (Reactor 2)
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