Color removal and disinfection with UV/H2O2 system for wastewater reclamation and reuse

K.H. Ahn, K.Y. Park, S.K. Maeng, K.G. Song, K.P. Kim, S.H. Lee and J.H. Kweon*
Water and Environment and Remediation Research Center, Korea Institute of Science and Technology, P.O. BOX 131, Cheongyang, Seoul 130-650, Korea (E-mail: smaeng@kist.re.kr) * Department of Environmental Engineering, Kunkuk University, Hwayang-dong 1, Gwangin-gu, Seoul, 143-701, Korea Abstract Reuse of wastewater efuents from secondary treatment processes in municipal wastewater treatment plants has been issued because of substantial volumes of relatively clean waters. The major components of criteria for wastewater reclamations are color, organic matter, and pathogens. An advanced oxidation process with low-pressure ultraviolet and hydrogen peroxide addition (UV/H2O2 system) has been employed for removal of the major components in the criteria for reuse of wastewater. Sand lter pretreatment was applied to remove turbidity and to improve performance of UV irradiation. The results showed that total coliforms were effectively inactivated by the UV irradiation alone with the contact time of 30 minutes but color was remained. The addition of H2O2 signicantly improved the removal of color and dissolved organic matter in the same contact time. Keywords Hydrogen peroxide; secondary efuent; UV; water reuse

Water Science and Technology: Water Supply Vol 5 No 1 pp 5157 IWA Publishing 2005

Introduction

Korea has a mean annual precipitation of 1,274 mm, which is 1.3 times the worlds average. However, difficulties still exist in maintaining reliable water supply systems because of the substantial seasonal and geographical variation of water precipitation. Rapid growth in economics and population in urban areas further increases the water demand per capita. The water demand is expected to exceed the water supply by 2 109 m3 in 2011 and 3 109 m3 in 2020 in Korea (The Ministry of Construction and Transportation, 2001). Therefore, application of the reclamation of wastewater in Korea has been extensively investigated in past 20 years. The earliest planned reclamation was to reuse process waters, instead of wastewater discharge, for cleaning water and cooling water in 1980. The wastewater collected from washstands, water baths, and building cleaning has been reclaimed for toilet flushing, cooling water, and process water in a company since 1984. In the late 1980s, the reclamation expanded its application to domestic and sewage wastewaters. Tremendous increases of the reclamation plants of domestic and sewage wastewater occurred in the early 1990s, which is reflected in the recent status of reclamation as shown in Table 1. Approximately 1.0 105 m3/day of reclaimed water was reused for beneficial purposes in 2001. While the reclamation of wastewater was implemented in 99 on-site individual buildings, little attempt has been made to use effluents from publicly owned wastewater treatment plants in Korea. Only 2.9% of wastewater effluents are reused, and the applications are limited to cleaning individual buildings, landscape irrigation, and cooling tower water. The reuse of the wastewater effluents is likely considered as a reliable water resource since effluents from the wastewater treatment plants are produced in sufficiently large amounts, i.e., approximately 2 107 m3 per day. As alternative water resources, the Ministry of Environment in Korea is promoting to reuse over 10% of secondary effluents or wastewater treatment plant effluents from 2010 (MOE, 2003).

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Table 1 Installation of domestic wastewater reuse plants during past 20 years in Korea
Years 19801985 19851990 19901995 19952000 2001

Numbers of installed plants Reclaimed wastewater (m3/day)

2 12,400

4 14,300

15 53,930

61 82,501

68 104,781

To reuse wastewater treatment plant effluents, it is required to meet water quality criteria in Korea (Table 2). Previous research indicated that organic matter (measured as chemical oxidation demand, COD, or biochemical oxidation demand, BOD) concentrations in wastewater treatment plant effluents from 95% of domestic wastewater treatment plants were sufficiently low to meet water quality criteria for reuse (Ahn et al., 2002). The most problematic water qualities for reuse are color and pathogens in the wastewater effluents. Therefore, an ultraviolet (UV) process with hydrogen peroxide (H2O2) addition was proposed to treat wastewater effluent for reuse. The UV systems have shown excellent performance in the removal of pathogens and have also been recommended as a disinfection process for the reclaimed water by Ministry of Environment in Korea. The addition of H2O2 to the UV system has shown improvement in removal of organic contents and hazardous materials including dye wastewater and humic substances (Ince, 1999; Wang et al., 2000). Some researchers also investigated the removal of dissolved organic matter in the wastewater effluents by the UV/H2O2 systems (Wang et al., 2001). However, little research has been performed on the removal of color along with the removal of organic matter. In this research, low-pressure UV lamp was used for the removal of pathogens, soluble organic matter, and especially, color. The wastewater effluents from the Gwangju municipal wastewater treatment plant were used as an influent for the system.
Methods
Experimental apparatus and operation

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A schematic diagram of the UV/H2O2 system is shown in Figure 1. Sand filtration as pretreatment was installed to eliminate effects of turbidity on the irradiation efficiencies for removal of color and organic matter. The hydrogen peroxide was completely mixed before the UV chamber. A low-pressure lamp was applied for economic reasons. The contact time of the system was determined with the influent flow rate into the chamber. The key parameters of the used low-pressure lamp system are summarized in Table 3. The nominal average UV intensity was approximately calculated with one-point source summation method. The UV transmittance at 253.7 nm was 68% for the influent of this system.
Table 2 Criteria of water quality for reuse in Korea
Parameters Toilet ushing Agricultural irrigation Landscape irrigation Other non-potable reuse*

Total Coliforms Chlorine residual Appearance Turbidity BOD Odor pH Color CODMn ***

ND** > 0.2 mg/L < 2 NTU < 10 mg/L 5.8~8.5 < 20 Pt-Co unit < 20 mg/L

ND** ND** No unpleasantness to users < 2 NTU < 2 NTU < 10 mg/L < 10 mg/L No unpleasantness to users 5.8~8.5 5.8~8.5 < 20 mg/L < 20 mg/L

ND** > 0.2 mg/L < 2 NTU < 10 mg/L 5.8~8.5 <20 Pt-Co unit < 20 mg/L

* Examples of non-potable reuse: car washing, building maintenance, ** ND: not detected, *** Potassium permanganate (KMnO4) was used as an oxidant, instead of potassium dichromate (K2Cr2O7) for measurement of COD (Kim, 1989)

K.H. Ahn et al.

Figure 1 Schematic diagram of the UV/H2O2 system

The H2O2 concentrations were measured with the reflectometric method using peroxide test strips (RQflex2, Merck), which uses peroxidase to transfer peroxide oxygen to an organic redox indicator. The spectrophotometric method using Copper(II) and 2,9dimethyl-1,10-phenanthroline (DMP) was used to confirm the accuracy of the reflectometric method. Since there was a good agreement between the methods, the reflectometric method was used for simple preparations. Other liquid sample analysis was performed according to Standard Methods (APHA et al., 1998). Organic matter was analyzed based on COD and DOC.
Results and discussion
Source water characterization

The source water of the UV/H2O2 system was the effluent of the activated sludge process in Kwangju municipal wastewater treatment in Gyeonggi-do, Korea. The plant has a capacity of 20,000 m3/day and discharged into the Gyeongan stream, a branch stream of Han River. Discharged water was collected from the small well after the secondary clarifier of the activated sludge process. The composition of secondary effluent is presented in Table 4. The turbid matter concentration showed large fluctuations, sometimes higher than 5 NTU. Considering that recommended maximum concentration levels for waters for the UV disinfection is 5 NTU, a pretreatment seems necessary to reuse the wastewater effluents. Total fecal coliform concentrations are acceptable for direct discharge to the river, but quite high levels for reuse. Thus, a treatment is required to remove all detectable coliforms to
Table 3 The specication of the low-pressure UV system
Parameters Specication

Manufacturer Model Input power Output power Nominal UV density Nominal average intensity

Philips G36T5L LP Lamp 39 W 13.8 W 8.0 W/L 150 mW/cm2

Table 4 Characteristics of the secondary efuent from activated sludge process

Components Values Components Values

Turbidity (NTU) Total Coliforms (100 mL) pH Color (Pt-Co unit)

0.85.3 27.3 104 7.17.3 1433

BOD (mg/L) CODMn (mg/L) COD (mg/L) DOC (mg/L)

47 36 13.316.0 4.45.1

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reclaim the wastewater effluents. For the organic matter concentration such as COD and BOD, the effluents from the secondary treatment process meet the criteria for the reuse. The great problem for reuse is the color content in the secondary effluents. Even after the biological treatment, the color was often found over 20 Pt-Co unit. Therefore, an advanced treatment process is required to remove the color compoynds, which contain hardly biodegradable organic matter and leads the color in the secondary effluents.
K.H. Ahn et al.
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Turbidity and effects of pre-treatment

The proposed advanced treatment process, the UV irradiation alone or the UV with H2O2, was investigated for the removal of turbidity and organic matter. The results by UV alone without H2O2 are shown in Figure 2(a). As contact time was increased, concentrations of turbidity and organic matter (measured as DOC) significantly increased to the contact time of 5 minutes, and then leveled off or started to decrease. Most turbid matter in the sample was bioflocs from the secondary treatment process, i.e., activated sludge process. The increases in turbidity at the short contact time of the experiment indicated that UV irradiation was only capable to disrupt aggregates of microorganisms and release cell contents, but not to degrade them to CO2. Increases in soluble organic matter concentration with the contact times were also consistent with the idea that UV irradiation only had the very low efficiency to remove organic compounds and needed relatively long periods of contact time to convert to CO2. The advanced oxidation process with the UV and H2O2 addition was used to reduce the turbid and organic matter for reuse of the secondary effluents. Figure 2(b) shows that the addition of H2O2 was very effective to reduce DOC and turbidity in the samples. Approximately 50% of DOC and turbidity was reduced within 30 minutes of contact time. However, the turbidity was still higher than the required value for reuse, i.e., 2 NTU. Therefore, the pretreatment prior to UV contactor for the reduction of turbid matter might need to be considered for better performance in the UV/H2O2 system. Sand filtration was installed to eliminate turbidity and to improve the color removal efficiency. The sandfilter was operated with down-flow type. The water flow was varied with increasing head-loss, which comes from the accumulated deposits on the surface of the sandfilter. Backwash was performed every 48 hours based on the turbidity and flow rate measurements. Since the operation was conducted during autumn and winter season, the two-day back wash period was enough to maintain relatively good levels of water quality without any microorganism growth. It might need a frequent backwash in hot season due to significant algae concentrations in the secondary effluents. The results from the experiments with or without sand filtration are summarized in Table 3. Since the experiments were performed with secondary effluents from the real plant, the raw water characteristics were slightly fluctuated. The turbidity removal in the sand filtration was substantial, approximately 70%, whereas little effect was found in the DOC and fecal coliform concentrations. After the removal of turbidity, the color removal of UV/ H2O2 system was significantly improved, from 48% without sand filtration to 75% with sand filtration. Therefore, interference by particulates should be eliminated to obtain the maximum removal efficiency of color in the UV/H2O2 system.
Reduction of coliforms in the UV/H2O2 system

The removal of microorganisms was also investigated with the systems with or without hydrogen peroxide. As shown in Figure 3, coliforms were inactivated with the contact time of 30 minutes with UV irradiation, regardless of the addition of hydrogen peroxide. Increases in the concentrations of hydrogen peroxide yielded the short contact time to meet the criteria of total coliform bacteria for reuse. With the hydrogen peroxide concentrations

of 50 mg/L, complete removal was achieved only with a contact time of 6 minutes. In general, the UV irradiation was effective to meet the criteria for total coliform concentration.
Color removal in the UV/H2O2 system

The secondary effluents have relatively high values of color in spite of low concentration of organic matter. Without enhanced treatments, it is difficult to reclaim the wastewater effluents for toilet flushing and other non-potable uses such as cleaning for individual buildings, which are the most popular ways of reuse in Korea. In the system with UV irradiation alone, the high energy of UV irradiation might reduce color. In addition, the use of H2O2 probably improves the reduction of color. The color removal by the UV irradiation alone and UV with H2O2 was compared as shown in Figure 4. The color removal with the UV irradiation alone was rather increased with increasing UV doses. Note that it is consistent with the results of turbidity and dissolved organic carbon concentrations in Figure 2. The slight increases at dose of 15 mWh/cm2 might stem from inference of turbid matter or change of some dissolved organic carbon to the more colored organic matter. However, the latter explanation is unlikely. Therefore, removal of turbid matter before the UV system is the main reason of the improved performance. The addition of H2O2 with the concentrations of 25 and 50 mg/L significantly reduced the color. The color criteria, i.e., lower than 20 Pt-Co unit, was satisfied with the UV dose of higher than 20 mW-h/cm2 at the concentration of 25 mg/L. At the high H2O2 concentration (50 mg/L), only UV dose of 17 mW-h/cm2 was needed to meet the criteria (Table 5). The concentration of H2O2 radicals is critical to remove organic matter in the systems with UV and H2O2 since the radicals actually destruct organic matter with the oxidizing potential of 2.8V (Crittenden et al., 1999). In UV/H2O2 processes, direct photolysis of H2O2 under UV irradiation, ranging approximately from 200 nm to 280 nm, produces the very reactive hydroxyl radicals: H2O2 + h 2 OH
7 6

K.H. Ahn et al.

(1)
6

(a) UV radiation only

(b) UV/H 2O2 (50 mg/L)

5 4 3 2 1 0 0 5 10 15 20 contact time (min) 25 30 35

NTU or mg/L

5 4 3 2 1 0
0 5 10 15 20 25 30 35

Turbidity

DOC

contact time (min)

Figure 2 Reduction of particle and organic matter. (a) UV irradiation alone and (b) UV/H2O2 system
6 50 mg/L 5 25 mg/L 0 mg/L

Lo g C ol ifo rm (/1 00 mL )

0 0 5 10 15 20 Contact Time (min) 25 30 35

Figure 3 Disinfection by the UV systems with or without hydrogen peroxide

NTU or mg/L

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Table 5 Water quality from experiments with or without sand ltration (H2O2 addition: 50~52 mg/L, contact time: 6 minutes)
Run 1 Raw UV/H2O Run 2 Raw Sand-lter UV/H2O2

Turbidity (NTU) Color (Pt-Co unit) DOC (mg/L C) E. Coliform (1/100 mL)

3.9 29 5.0 73,000

3.2 (18%) 15 (48%) 4.2 (16%) N.D. (~99.9%)

4.3 28 3.9 47,000

1.3 (70%) 1.5 (65%) 27 (4%) 7 (75%) 3.8 (3%) 3.6 (8%) 31,000 (34%) N.D. (~99.9%)

% r em o val

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The rate constant of OH radicals to organic matter is reported in the range of 109 and 1010 M1s1, thus the organic matter removal is substantial with infinitesimal concentrations of OH radicals (Wang et al., 2001). However, the molar extinction coefficient of H2O2 at 254 nm is quite low, i.e., 19.6 M1 cm1, compared with ozone, i.e., 3,300 M1 cm1. Therefore, relatively high concentrations of H2O2 are needed to produce enough OH radicals for color and organic removal. Figure 5 shows the relationship of H2O2 concentrations with removal efficiencies of color and DOC. Hydrogen peroxide was added based on raw water CODCr since H2O2 was consumed in proportion to organic matter. The abscissa of the graph was the molar ratio of H2O2 to CODCr of influents, which is used to normalize differences in organic matter concentration of samples. The results showed that the color removal efficiency is greater than the DOC removal efficiency. The organic concentrations in the inflow of the system already met the criteria for reuse, therefore the small removal of DOC would produce a good quality of treated water in terms of organic content. The greater removal efficiencies of color are preferable results to reuse the secondary effluents in case that the color content should stratify the criteria. The maximum removal rate, i.e., 60% for DOC and 82% for color, was occurred with the molar ratio of approximately 1.4 and the addition of H2O2 to the greater molar ratio did not improve the color removal. Therefore, the UV system with the H2O2 could be a promising option for the reuse of the secondary effluents for the specific purposes, for example, toilet flushing and cleaning water for individual buildings.
Conclusions

The UV/ H2O2 system with the low-pressure UV lamp was evaluated for reuse of the secondary effluents from the municipal wastewater treatment plant. Several parameters such as H2O2 doses, contact times, and the presence of sand-filtration were investigated to meet the criteria for reuse in Korea. Some conclusions are:
100 80 60 40 20 0 -20 R aw 0.00 0.71 1.42 1.45 molar ratio H2O2/COD

color DOC

Figure 4 Color removal in the UV system with or without hydrogen peroxide

Figure 5 Removal efciency of organic and color with different H2O2 concentration

1. The turbid matter significantly interfered the performance of the UV/H2O2 system, therefore a pretreatment to reduce particulate matter needs to be considered. 2. The UV irradiation has excellent disinfection efficiency, but shows very limited removal of color and dissolved organic. The addition of H2O2 is necessary to obtain the sufficient removal of color causing compounds. 3. The color removal by the UV/H2O2 system was substantial with more than 25 mg/L of H2O2, which is approximately 0.7 molar ratio of H2O2 to the COD. 4. There was an optimum H2O2, i.e., effective dose, because more than 1.4 molar ratio of H2O2 and COD showed little improvement on the removal of DOC and color.
Acknowledgements

K.H. Ahn et al.

This research was supported by a grant (4-1-1) from Sustainable Water Resources Research Center (SWRRC) of 21st century frontier R&D program through the Water Reuse Technology Center (WTRC) at Kwangju Institute of Science & Technology (KJIST). The authors also would like to thank Dr. Jung-Sung Kim and Dr. Min-Woo Jung for helpful discussions, and Mr. Jun-Suk Hong for coliform analysis.
References
Ahn, K.H., Lee, S.H., Ahn, S., Kim, K.P., Jung, M.W. and Maeng, S.K. (2002). Effect of suspended matter on the degradation of dissolved organic carbon in secondary effluent by catalyzed UV oxidation with hydrogen peroxide. J. Korean Soc. Water and Wastewater, 16, 333340 (in Korean). APHA, AWWA, and WEF (American Public Health Association, American Water Works Association, and Water Environment Federation) (1998). Standard Methods for the Examination of Water and Wastewater. 20th ed. APHA , Washington, DC. Coma, J., Jabbouri, A., Grasmick, A. and Elmaleh, S. (1991). Intensive primary-treatment of urban wastewater. Wat. Sci. Tech., 24(7), 217222. Crittenden, J.C., Hu, S., Hand, D.W. and Green, S.A. (1999). A kinetic model for H2O2/UV process in a completely mixed batch reactor. Wat. Res., 33, 23152328. Ince, N.H. (1999). Critical effect of hydrogen peroxide in photochemical dye degradation. Wat. Res., 33, 10801084. Kim, N.C. (1989). Environmental Engineering Experiments for Water and Wastewater. Dongwha publication. Seoul, Korea. (in Korean). The Ministry of Construction and Transportation (2001). Water Vision 2020, Seoul, Korea (in Korean). The Ministry of Environment (MOE) (2000). A Comprehensive Plan for Efficient Water Use, Seoul, Korea (in Korean). Wang, G.S. Hsieh, S.T. and Hong, C.S. (2000). Destruction of humic acid in water by UV light catalyzed oxidation with hydrogen peroxide. Wat. Res., 34, 38823887. Wang, G.S., Chen, H.W., and Kang, S.F. (2000). Catalyzed UV oxidation of organic pollutants in biological treated wastewater effluents. Sci. Total Environ., 277, 9794.

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