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Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters
Sang D. Kima, Jaeweon Choa, In S. Kima, Brett J. Vanderfordb, Shane A. Snyderb,
a Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology, 1 Oryong-dong, Buk-gu, Gwangju 500-712, South Korea b Southern Nevada Water Authority, 1350 Richard Bunker Avenue, Henderson, NV 89015, USA

art i cle info


Article history: Received 28 February 2006 Received in revised form 25 May 2006 Accepted 23 June 2006 Available online 23 August 2006 Keywords: Wastewater Treatment Efuent Drinking water Reuse Membrane bioreactor Membrane ltration Activated carbon Reverse osmosis Nanoltration Ultraltration

A B S T R A C T

Liquid chromatography/tandem mass spectrometry (LCMS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure the concentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products (PCPs), and 1 ame retardant in surface waters and wastewater treatment plant efuents in South Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine, and caffeine were quite frequently observed (480%) in both surface waters and efuents. The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, and carbamazepine. However, the primary estrogen hormones, 17a-ethynylestradiol and 17bestradiol, were rarely detected, while estrone was detected in both surface water and wastewater efuent. The elimination of these chemicals during drinking water and wastewater treatment processes at full- and pilot-scale also was investigated. Conventional drinking water treatment methods were relatively inefcient for contaminant removal, while efcient removal (E99%) was achieved by granular activated carbon (GAC). In wastewater treatment processes, membrane bioreactors (MBR) showed limited target compound removal, but were effective at eliminating hormones and some pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine). Membrane ltration processes using reverse osmosis (RO) and nanoltration (NF) showed excellent removal (495%) for all target analytes. & 2006 Elsevier Ltd. All rights reserved.

1.

Introduction

Around the world, researchers are discovering trace levels of pharmaceuticals and human hormones in water associated with wastewater treatment plant (WWTP) efuents (HallingSorensen et al., 1998; Routledge et al., 1998; Daughton and Ternes, 1999; Snyder et al., 1999, 2001a, b, 2003, 2005; Ternes et al., 1999a, b; Ternes et al., 2001). The earliest report on human hormones in water was published in 1965, showing
Corresponding author. Tel.: +1 702 856 3668; fax: +1 702 856 3647.

that steroids were not completely eliminated during wastewater treatment (Stumm-Zollinger and Fair, 1965). While other reports demonstrating the presence of human hormones were published in the 1970s and 1980s (Tabak and Bunch, 1970; Tabak, et al., 1981; Aherne et al., 1985; Aherne and Briggs, 1989), little attention was focused on these trace pollutants until their occurrence became linked to toxicological impacts in sh (Bevans et al., 1996; Desbrow et al., 1998; Jobling et al., 1998; Kramer et al., 1998; Renner, 1998; Snyder

E-mail address: shane.snyder@snwa.com (S.A. Snyder). 0043-1354/$ - see front matter & 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2006.06.034

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et al., 2001a, b). The rst reports on pharmaceuticals in wastewater efuents and surface waters were published in the United States in the 1970s (Tabak and Bunch, 1970; Garrison et al., 1975; Hignite and Azarnoff, 1977). Similar to the steroid hormones, pharmaceuticals as environmental contaminants did not receive a great deal of attention until the link was established between a synthetic birth-control pharmaceutical (ethynylestradiol) and impacts on sh (Purdom et al., 1994; Desbrow et al., 1998; Jobling et al., 1998; Snyder et al., 2001a, b). It is now well established that pharmaceuticals and human hormones are ubiquitous contaminants of wastewater efuents. Most often, these compounds occur at sub-mg/L concentrations. While pharmaceuticals and personal care products (PPCPs) are a mostly well-dened group of compounds, endocrine disrupting chemicals (EDCs) are an extremely diverse group of compounds that interfere with the functioning of natural hormones in animals. It is difcult to determine which chemicals should or should not be classied as endocrine disruptors. The US Environmental Protection Agency (USEPA) established the Endocrine Disruptor Screening Program (EDSP) to identify screening methods and toxicity testing strategies that can be used to determine whether chemicals are endocrine disruptors, but this process is incomplete (Snyder et al., 2003). The European Organization for Economic Co-operation and Development (OECD) is also currently developing methods to identify EDCs. However, there currently is no consensus within the scientic community for a strategy to denitively determine whether a chemical is an endocrine disruptor, and denitions of the term vary. Some naturally occurring and man-made chemicals are widely considered to be endocrine disruptors, including certain pharmaceuticals, pesticides, industrial chemicals, combustion byproducts, phytoestrogens, and hormones excreted by animals and humans. There are many other chemicals for which there is limited, incomplete evidence of potential endocrine activity or for which the evidence of endocrine activity is controversial. An even greater number of chemicals have not yet been tested for potential endocrine activity using any of the available methods. Additionally, therefore, any list of chemicals dened as EDCs is speculative. While it is infeasible to remove all microcontaminants to levels below the detection limit of modern analytical instrumentation, some treatment processes are clearly more effective than others for reducing the concentration of a broad range of trace contaminants. Coagulation, occulation, and precipitation processes are largely ineffective for removing dissolved organic contaminants (Ternes et al., 2002; Westerhoff et al., 2005). Oxidative processes such as chlorination and ozonation are effective for reducing the concentrations of several classes of microcontaminants; however, removal efcacy is a function of the contaminant structure and oxidant dose (Zwiener and Frimmel, 2000; Adams et al., 2002; Huber et al., 2003; Snyder et al., 2003; Ternes et al., 2003; Pinkston and Sedlak, 2004; Huber et al., 2005). Biological processes, such as activated sludge, bioltration, and soilaquifer treatment, have been shown to greatly reduce the concentration of compounds which are biodegradable and/or readily bind to particles (Tabak et al., 1981; Alcock et al., 1999;

Ternes et al., 1999a, b; Drewes et al., 2002; Snyder et al., 2004; Joss et al., 2005). Activated carbon can remove nearly all organic contaminants; however, removal capacity is limited by contact time, competition from natural organic matter, contaminant solubility, and carbon type (Ternes et al., 2002; Yoon et al., 2003; Snyder et al., 2006). Reverse osmosis (RO) and nanoltration (NF) membranes provide effective barriers for rejection of contaminants, while microltration and ultraltration (UF) membranes provide selective removal for contaminants with specic properties (Snyder et al., 2006). The study presented here shares occurrence data from drinking, waste, and surface water in South Korea. Additionally, this study demonstrates the ability of membranes, activated sludge, coagulation, ultraviolet (UV) irradiation, chlorination, and granular activated carbon (GAC) for the removal of a suite of endocrine disruptors and pharmaceuticals in drinking and wastewater treatment facilities. To the best of the authors knowledge, this is the rst report showing the occurrence and treatment of these compounds in the waters of South Korea.

2.
2.1.

Materials and methods


Description of the sites

Efuent samples were collected from seven WWTPs in South Korea, one at Jeju Island and six in the South Jeolla province. The six South Jeolla province WWTPs discharge efuents into the Youngsan River, which has a total length of 115 km and watershed area of 2.8 103 km2 (Fig. 1). This river starts at Damyang, runs through Gwangju, and empties into the

Fig. 1 A map of sampling sites in South Korea. The numbers indicate the sampling sites in wastewater treatment plant efuents.

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Yellow Sea. Efuents consist of about 85% domestic wastewater, 18% industrial wastewater, and 2% livestock wastewater. Of the seven WWTPs, six (Jeju, Gwangju, Naju, Jangsung, Damyang, and Young-am) use activated sludge treatment consisting of three main steps: preliminary and nal clarication and an aeration tank. The Hwasoon site uses a rotating biological contactor (RBC). Wastewater source characteristics are different at each site; for example, Damyang and Young-am treatment plants receive agroindustrial wastewater, Gwangju WWTPs receive both municipal and industrial wastewaters, and Naju, Hwasoon, and Jangsung WWTPs are linked to the treatment of manure. Samples from three major rivers, the Han River, the Nakdong River, and the Youngsan River, were collected to determine the degrees of contamination by micropollutants. These rivers ow in the north (Han), the southeast (Nakdong), and the southwest (Youngsan) parts of South Korea as shown in Fig. 1. The major rivers were selected for study because of their importance to public usage. These rivers were assumed to have frequent exposure to large amounts of micropollutants due to the inuence of WWTP efuents. Samples were taken from one site upstream and two sites downstream in the Han River, one site downstream in the Nakdong River, and one site upstream and three sites downstream in the Youngsan River.

2.3.

Analytical methods

All target compounds were extracted using solid phase extraction and analyzed by liquid chromatography with tandem mass spectrometry (LCMS/MS). A detailed description of the analytical method has been described previously in Vanderford et al. (2003).

2.3.1.

Sample preparation

Samples were collected during periods of normal operation in 2004 and 2005 from the sites described above, using precleaned amber glass containers. Samples were kept on ice during transit to the laboratory, adjusted to pHo2 by the addition of concentrated sulfuric acid, and stored at 4 1C until extraction. The use of sulfuric acid has been shown previously to effectively preserve samples without degradation of these target analytes (Vanderford et al., 2003).

2.3.2.

Solid phase extraction

2.2. 2.2.1.

Treatment process of micropollutants Drinking water treatment

In brief, 1000 mL samples were loaded onto Waters HLB (hydrophiliclipophilic balance) solid phase extraction cartridges at 15 mL/min. The cartridges had been previously conditioned using dichloromethane, tert-butyl methyl ether (MTBE), methanol, and reagent water. After loading, the cartridges were rinsed with reagent water and dried with a stream of nitrogen for 1 h. Compounds were eluted using methanol followed by a 10/90 percent mixture of methanol/ MTBE. Extracts were concentrated to a nal volume of 1 mL using a gentle stream of nitrogen.

Two samples were taken from both Paldang and Dongbok Lakes, near the intake points for the water supply of the two cities of Seoul and Gwangju. All drinking water sources in these cities are derived from these two lakes. The waters from Paldang and Dongbok Lakes are introduced into waterworks and treated for drinking water through several conventional treatment steps: coagulation, sand ltration, and chlorination for Gwangju, and coagulation, UF, and GAC for Seoul. Samples were collected after each step of the purication process.

2.3.3.

Liquid chromatographytandem mass spectrometry

2.2.2.

Wastewater treatment

Contaminant removal efciency was evaluated at a WWTP designed for possible agricultural, recreational, and potable water reuse of wastewater efuents. This treatment plant holds several pilot-scale treatment processes and receives wastewater from campus dormitories and student apartments at Gwangju Institute of Science and Technology (GIST). The pilot process, having a ow capacity of 1 m3/day, includes a membrane bioreactor (MBR) followed by membrane ltration (MF) processes such as RO and NF, as well as MF processes combined with UV irradiation (e.g., RO-UV and NF-UV). The MBR system consists of an activated sludge tank followed by commercially available plate and frame type membrane modules (Pure-Envitech Co., Ltd, Korea) and a hollow-ber membrane module (Kolon Co., Ltd, Korea). RO and nanotration (NF) were evaluated using spiral-wound membranes (RE4040-FL for RO and NE4040-90-RF for NF produced by Saehan Industries Inc., Korea). Samples were collected before and after each unit process.

All samples were analyzed using LCMS/MS in one of three modes: ESI positive, ESI negative, or APCI positive. Briey, a binary pump (Agilent G1312A, Palo Alto, CA) and an autosampler (HTC- PAL, CTC Analytics, Zwingen, Switzerland) were used for all analyses. All analytes were separated using a 250 4.6 mm Synergi Max-RP C12 column with a 4 mm particle size (Phenomenex, Torrance, CA). A binary gradient consisting of 0.1% formic acid (v/v) in water (A) and 100% methanol (B) at a ow rate of 700 mL/min was used. The gradient was as follows: 5% B held for 3.5 min, increased linearly to 80% by 10 min and held for 3 min, stepped to 100% and held for 8 min. A 9 min equilibration step at 5% B was used at the beginning of each run to bring the total run time per sample to 30 min. An injection volume of 10 mL was used for all analyses. In addition to the compounds listed in Vanderford et al. (2003), estrone and estriol were added to and analyzed by this extraction/analysis method. These two compounds were analyzed using APCI positive. Estriol and estrone both had precursor ions of m/z 271. This indicates that estriol loses water in the source [MH2O+H]+ to become estrone [M+H]+. Consequently, both estrone and estriol had the same product ion of m/z 253. This product ion is most likely due to a loss of water (m/z 18). This, however, did not affect estrone/estriol differentiation due to chromatographic separation of the two analytes. Other compound-specic parameters for estriol and estrone, respectively, are as follows: declustering potential (46, 31 V); collision energy (19, 23 eV); and collision cell exit potential (10, 16 V).

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3.
3.1.

Results and discussion


Recoveries and detection limits

initial sample volume was used. This raised the reporting limit proportionally on those samples.

3.2. 3.2.1.

Occurrence of micropollutants Surface water

Recoveries for this method have been published previously (Vanderford et al., 2003). Analytical recoveries ranged from 68% to 112%, except for acetaminophen which had a recovery of 41%. Estriol and estrone had spike recoveries of 101% and 90%, respectively (n 17). All relative standard deviations were less than 20%. An instrument detection limit (IDL) study was performed by consecutively injecting 2.5 pg of each compound on column 10 times as discussed in Vanderford et al. (2003). The IDL was then calculated by multiplying the standard deviation of the replicate measurements by the appropriate Students T value for nine degrees of freedom. Instrument reporting limits (IRL) were chosen to be greater than the IDL and were generally at least three times the IDL. Reporting limits were calculated by dividing the IRL by 1000 due to the concentration factor from the SPE. Reporting limits for all compounds were 1.0 ng/L, except for caffeine and TCEP at 10 ng/L and estriol at 5 ng/L. Caffeine and TCEP had higher reporting limits due to occasional blank contamination. Due to the complex nature of some wastewater samples, less

The occurrence of pharmaceuticals, hormones, antibiotics, and a ame retardant was investigated in Korean surface waters, including several lakes and rivers (Table 1). Concentrations ranged from below detection to several hundred ng/L. The samples collected from the Han River, the Nakdong River, and the Youngsan River showed frequent detection of various chemicals with high concentrations in some sites. The frequency of detection was about 44% (17% in upstream and 53% in downstream) in all sampling sites. These rivers receive secondary efuents from WWTPs and are located in industrialized areas. Because of human activities, the waters investigated are readily exposed to contaminants through many routes. For instance, the concentrations of iopromide and caffeine were quite high (20361 and 10194 ng/L, respectively). The compounds of highest occurrence frequency (480%) included TCEP, DEET, iopromide, acetaminophen, naproxen, ibuprofen, carbamazepine, and caffeine. The concentrations observed are similar to those of Ternes et al.

Table 1 Summary of concentrations for 26 selected micropollutants in efuents and surface waters Compound Class NODa
Erythromycin Sulfamethoxazole TCEP DEET Oxybenzone Triclosan Estriol 17a-ethynylestradiol Estrone 17b-estradiol Testosterone Androstenedione Iopromide Hydrocodone Acetaminophen Trimethoprim Pentoxifylline Meprobamate Dilantin Naproxen Ibuprofen Diclofenac Carbamazepine Caffeine Fluoxetine Gembrizil
a b c

Efuents Concentrationb
130 (8.9294) 136 (3.8-407) 537 (922620) 27 (6.460) 11 (1.030) 12 (1.332) 16 (8.925) 1.3 14 (2.236) o1.0 1.1 2.3 (1.03.5) 2630 (11704030) 41 (1370) 9.5 (1.819) 58 (10188) 2.9 (1.64.2) 6.0 44 (8.8181) 128 (20483) 65 (10137) 40 (8.8127) 226 (73729) 228 (23776) 1.7 11.2(3.917)

Surface waters NOD


5 5 8 7 2 0 0 0 3 0 0 1 7 3 6 4 1 0 6 6 6 3 7 8 0 3

Conc.
3.4 (1.84.8) 20 (1.736) 42 (1481) 22 (2.069) 2.0 (1.22.7) NAc NA NA 3.6 (1.75.0) NA NA 2.6 134 (20361) 1.6 (1.32.2) 33 (4.173) 4.0 (3.25.3) 1.6 NA 4.3 (1.18.9) 11 (1.818) 28 (1138) 3.0 (1.16.8) 25 (4.561) 105 (2.9194) NA 6.6 (1.89.1)

Pharmaceutical Pharmaceutical Miscellaneous Miscellaneous Miscellaneous Miscellaneous Hormone Hormone Hormone Hormone Hormone Hormone Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical Pharmaceutical

5 4 7 5 5 4 3 1 5 0 1 3 6 4 3 5 2 1 6 7 5 7 6 6 1 3

Number of samples detected among seven total samples for efuents and eight total samples for surface waters. Indicates mean concentration with the minimum and maximum values in parentheses. Not applicable.

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(1998), who investigated these compounds in German rivers and streams. However, most hormone compounds were observed consistently below detection limits in all sites, similar to ndings by Boyd et al. (2003), with the exception of estrone which measured between 1.5 and 5.0 ng/L. However, other investigators reported much higher concentrations of hormones in surface waters. For example, Kolpin et al. (2002) reported 17b-estradiol, 17a-ethynylestradiol, and testosterone to be present at averages of 9, 73 and 116 ng/L, respectively, in surface water. Ethynylestradiol and 17b-estradiol were also previously reported at concentrations ranging from 0.2 to 2.6 ng/L (Snyder et al., 1999). In general, the types and concentrations of PPCPs detected here are similar to those published previously (Halling-Sorensen et al., 1998; Daughton and Ternes, 1999; Snyder et al., 2001a, b, 2004; Heberer, 2002; Metcalfe and Miao, 2003). Of the sampling sites, Paldang and Dongbok Lakes located upstream of wastewater inuenced rivers were relatively low in target compounds, with only 17% of compounds detected and at low concentrations (Table 2). However, Paldang Lake did have a high concentration of iopromide (143 ng/L). In contrast, Dongbok Lake in the Gwangju area showed little contamination, with only small amounts of TCEP and oxybenzone present.

concentrations (up to 4030 ng/L). This is in agreement with Ternes et al. (1998), who reported that many PhACs were detected in the efuents and measured at high concentrations due to incomplete elimination in German sewage treatment plants. In addition, TCEP was quite high (average 537 ng/L) in all efuent samples. However, hormones such as 17a-ethynylestradiol and 17b-estradiol were not detected frequently in efuents. This result is comparable to results from other studies (Ternes et al., 1999a, b; Baronti et al., 2000; Huang and Sedlak, 2001; Kolpin et al., 2002), which showed very rare detection and low concentration for 17a-ethynylestradiol and 17b-estradiol in WWTP efuents. A previous study has shown that the activated sludge treatment step reduces hormones efciently up to about 80%, especially for 17bestradiol (Ternes et al., 1999a, b). Of these natural hormones, estrone was dominant in efuents and surface water samples. Fig. 3 shows the average and standard deviation of the sum of total microcontaminants within the three major classes described in Table 1. The change of concentration of chemicals in each water may be due to several factors: removal rates in WWTPs, dilution by water ows in rivers and rain events, and the introduction of chemicals through nonpoint sources.

3.3. 3.2.2. Wastewater efuents 3.3.1.


Results from chemical analyses at seven WWTPs are summarized in Table 1. Most chemicals were detected (58%) in the WWTP efuents studied. An example LCMS/MS chromatogram from the Jangsung WWTP is shown in Fig. 2. It is likely that occurrence frequency would have been greater if the surface water detection limit had been used. Since a lesser volume of wastewater was extracted, the corresponding reporting limit was greater. The concentrations of chemicals detected in efuent samples were much higher by one order of magnitude than those in surface water samples from rivers. The most frequently detected compounds included TCEP, iopromide, dilantin, naproxen, diclofenac, carbamazepine, and caffeine. Iopromide was found at relatively high

Removal of micropollutants Drinking water treatment

Treatment efciency of micropollutants in drinking water treatment processes was investigated using different purication methods currently operated in both Gwangju and Seoul (Table 2). Overall, the inuent waters were not highly contaminated. Only six target compounds were detected at these drinking water facilities, and at low concentrations with the exception of iopromide. At Gwangju, only the ame retardant TCEP and the sunscreen oxybenzone were detected. Moreover, the concentrations of these two compounds were very near the analytical reporting limits, thus no meaningful treatment predictions can be drawn from Gwangju drinking water treatment data. In Seoul, six target compounds were

Table 2 Removal of micropollutants by purication process during drinking water treatment Compound Dongbok Lake
TCEP DEET Oxybenzone Androstenedione Iopromide Dilantin Ibuprofen Carbamazepine Caffeine 14 o1.0 1.2 o1.0 o1.0 o1.0 o1.0 o1.0 o10

Gwangju Coagulation
o10 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

Seoul Chlorination
o10 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

Sand ltration
o10 o1.0 1.5 o1.0 o1.0 o1.0 o1.0 o1.0 o10

Paldang Lake
25 2.0 o1.0 o1.0 143 o1.0 15 4.8 45

Coagulation

UFltration
38 2.7 ND 1.2 177 1.2 23 7.5 48

GAC
o10 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

28 2.2 o1.0 o1.0 166 o1.0 18 5.3 43

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Fig. 2 Reconstructed chromatogram of Jangsung WWTP efuent.

10000 effluents surface water drinking water source

1000 concentration, ng/L

100

10

pharmaceuticals

hormones

miscellaneous compounds

Fig. 3 Average and standard deviation of compound class concentrations in efuent, surface water, and raw drinking water.

detected in raw water, and all were reduced to below the analytical reporting limits in the nished drinking water (Table 2). These data show concentrations that apparently increase during the treatment processes up to the GAC contactors; however, this rise in concentration is not signicant within the experimental variability (i.e., analytical variability and plug-ow timing of sample collection). Ob-

served removal appears to be entirely related to GAC at the Seoul drinking water treatment facility. GAC has been shown previously as an efcient means to remove many emerging contaminants (Rodriguez-Mozaz et al., 2004; Snyder et al., 2006). This may be due to the high sorption efciencies of the targeted compounds with activated carbon based on their hydrophobicity. In addition, the low concentration of natural

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Table 3 Removal of micropollutants in wastewater by various treatment technologies Compound


Erythromycin Sulfamethoxazole TCEP DEET Oxybenzone Triclosan Estriol Testosterone Androstenedione Hydrocodone Acetaminophen Trimethoprim Naproxen Ibuprofen Diclofenac Carbamazepine Caffeine
a b

Inuent
44 194 284 18 34 74 318 60 140 o10 11500 21 262 5320 10 42 9680

MBR(P)a
40 70 303 19 17 25 o10 o10 o10 14 o10 31 168 52 25 46 o100

MBR(K)b
42 58 283 18 20 20 o10 o10 o10 15 21 28 154 90 22 44 104

RO
o1.0 o1.0 14 o1.0 o1.0 o1.0 o5.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

NF
o1.0 o1.0 13 o1.0 o1.0 o1.0 o5.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

RO-UV
o1.0 o1.0 25 o1.0 o1.0 o1.0 o5.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

NF-UV
o1.0 o1.0 13 o1.0 o1.0 o1.0 o5.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o1.0 o10

Indicates the plate and frame type of module. Indicates the hollow-ber type of module.

organic matter in river waters results in less competition for the binding of these micropollutants to activated carbon (Westerhoff et al., 2005).

3.3.2.

Wastewater treatment

Table 3 summarizes the removal of micropollutants during wastewater treatment using various treatment technologies. In the rst treatment process, an MBR system was found to be efcient for hormones (e.g., estriol, testosterone, androstenedione) and certain pharmaceuticals (e.g., acetaminophen, ibuprofen, and caffeine) with approximately 99% removal. However, the results showed that MBR treatment did not decrease the concentration of erythromycin, TCEP, trimethoprim, naproxen, diclofenac, and carbamazepine. This is comparable to the results of previous studies (Heberer, 2002; Ternes et al., 1999a, b), which indicated very low elimination rates of diclofenac and carbamazepine in WWTP processes in Germany. In the comparison between the two MBR modules used in this study (plate and frame versus hollow-ber), no difference in target compound removal was found. RO and NF membrane processes showed excellent removal rates (495%) for all detectable analytes. However, the combination of membranes with UV irradiation did not provide enhanced removal. Additionally, it was found that RO did not display higher removal percentages when compared with NF. This is important in terms of cost for operating WWTPs. Consequently, wastewater treated by MF using RO or NF is adequate for the effective removal of a variety of micropollutants, such as pharmaceuticals and hormones.

frequently detected in Korean surface waters. Overall, the total concentrations of chemicals measured in all types of waters followed in this order: pharmaceuticals4miscellaneous compounds (e.g., ame retardant)4hormones. Conventional drinking water treatment processes (e.g., coagulation and sand ltration) tested in this study were inefcient for the removal of micropollutants found in the source water. Conventional WWTPs (e.g., activated sludge) showed incomplete removal of 25 micropollutants tested. In order to efciently remove microcontaminants, processes including GAC and MF with RO or NF are suggested because of their high removal rates. Ultimately, a multi-barrier approach using MBR followed by RO or NF could prove the most effective in contaminant removal.

Acknowledgments
This research was supported by a grant (code#4-1-2) from the Sustainable Water Resources Research Center of the 21st Century Frontier Research Program (South Korea) and funding from the American Water Works Association Research Foundation (Project #2758).
R E F E R E N C E S

4.

Conclusions

In conclusion, results indicate that many pharmaceuticals, hormones, antibiotics, PCPs, and a ame retardant were

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