Occurrence and Removal of Pharmaceuticals and Endocrine Disrupter

8/12/2019 Occurrence and Removal of Pharmaceuticals and Endocrine Disrupter

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Occurrence and removal of pharmaceuticals and endocrinedisruptors in South Korean surface, drinking,and waste waters

Sang D. Kim a , Jaeweon Cho a , In S. Kima , Brett J. Vanderford b, Shane A. Snyder b,a Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology, 1 Oryong-dong, Buk-gu,Gwangju 500-712, South Koreab Southern Nevada Water Authority, 1350 Richard Bunker Avenue, Henderson, NV 89015, USA

a r t i c l e i n f o

Article history:Received 28 February 2006Received in revised form25 May 2006Accepted 23 June 2006Available online 23 August 2006

Keywords:WastewaterTreatmentEfuentDrinking waterReuseMembrane bioreactorMembrane ltrationActivated carbonReverse osmosisNanoltrationUltraltration

A B S T R A C T

Liquid chromatography/tandem mass spectrometry (LCMS/MS) with electrospray ioniza-tion (ESI) and atmospheric pressure chemical ionization (APCI) was used to measure theconcentrations of 14 pharmaceuticals, 6 hormones, 2 antibiotics, 3 personal care products(PCPs), and 1 ame retardant in surface waters and wastewater treatment plant efuents inSouth Korea. Tris (2-chloroethyl) phosphate (TCEP), iopromide, naproxen, carbamazepine,and caffeine were quite frequently observed ( 4 80%) in both surface waters and efuents.The analytes of greatest concentration were iopromide, TCEP, sulfamethoxazole, andcarbamazepine. However, the primary estrogen hormones, 17 a-ethynylestradiol and 17 b-estradiol, were rarely detected, while estrone was detected in both surface water andwastewater efuent. The elimination of these chemicals during drinking water andwastewater treatment processes at full- and pilot-scale also was investigated. Conventionaldrinking water treatment methods were relatively inefcient for contaminant removal,while efcient removal ( E 99%) was achieved by granular activated carbon (GAC). Inwastewater treatment processes, membrane bioreactors (MBR) showed limited targetcompound removal, but were effective at eliminating hormones and some pharmaceuticals(e.g., acetaminophen, ibuprofen, and caffeine). Membrane ltration processes using reverseosmosis (RO) and nanoltration (NF) showed excellent removal ( 4 95%) for all targetanalytes.

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1. Introduction

Around the world, researchers are discovering trace levels of pharmaceuticals and human hormones in water associatedwith wastewater treatment plant (WWTP) efuents ( Halling-Sorensen et al., 1998 ; Routledge et al., 1998; Daughton andTernes, 1999 ; Snyder et al., 1999, 2001a, b, 2003, 2005; Terneset al., 1999a,b ; Ternes et al., 2001 ). The earliest report onhuman hormones in water was published in 1965, showing

that steroids were not completely eliminated during waste-water treatment ( Stumm-Zollinger and Fair, 1965 ). Whileother reports demonstrating the presence of human hor-mones were published in the 1970s and 1980s ( Tabak andBunch, 1970; Tabak, et al., 1981 ; Aherne et al., 1985 ; Aherneand Briggs, 1989), little attention was focused on these tracepollutants until their occurrence became linked to toxicolo-gical impacts in sh ( Bevans et al., 1996 ; Desbrow et al., 1998 ; Jobling et al., 1998; Kramer et al., 1998 ; Renner, 1998; Snyder

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Corresponding author. Tel.: +17028563668; fax: +17028563647.E-mail address: [email protected] (S.A. Snyder).

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et al., 2001a,b). The rst reports on pharmaceuticals in waste-water efuents and surface waters were published in theUnited States in the 1970s ( Tabak and Bunch, 1970 ; Garrisonet al., 1975; Hignite and Azarnoff, 1977 ). Similar to the steroidhormones, pharmaceuticals as environmental contaminantsdid not receive a great deal of attention until the link wasestablished 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 humanhormones are ubiquitous contaminants of wastewater efu-ents. Most often, these compounds occur at sub- mg/Lconcentrations. While pharmaceuticals and personal careproducts (PPCPs) are a mostly well-dened group of com-pounds, endocrine disrupting chemicals (EDCs) are anextremely diverse group of compounds that interfere withthe functioning of natural hormones in animals. It is difcultto determine which chemicals should or should not beclassied as endocrine disruptors. The US EnvironmentalProtection Agency (USEPA) established the Endocrine Disrup-tor Screening Program (EDSP) to identify screening methodsand toxicity testing strategies that can be used to determinewhether chemicals are endocrine disruptors, but this processis incomplete ( Snyder et al., 2003 ). The European Organizationfor Economic Co-operation and Development (OECD) is alsocurrently developing methods to identify EDCs. However,there currently is no consensus within the scientic commu-nity for a strategy to denitively determine whether achemical is an endocrine disruptor, and denitions of theterm vary. Some naturally occurring and man-made chemi-cals are widely considered to be endocrine disruptors,including certain pharmaceuticals, pesticides, industrialchemicals, combustion byproducts, phytoestrogens, andhormones excreted by animals and humans. There are manyother chemicals for which there is limited, incompleteevidence of potential endocrine activity or for which theevidence of endocrine activity is controversial. An evengreater number of chemicals have not yet been tested forpotential endocrine activity using any of the availablemethods. Additionally, therefore, any list of chemicalsdened as EDCs is speculative.

While it is infeasible to remove all microcontaminants tolevels below the detection limit of modern analytical instru-mentation, some treatment processes are clearly moreeffective than others for reducing the concentration of abroad range of trace contaminants. Coagulation, occulation,and precipitation processes are largely ineffective for remov-ing dissolved organic contaminants ( Ternes et al., 2002 ;Westerhoff et al., 2005 ). Oxidative processes such as chlorina-tion and ozonation are effective for reducing the concentra-tions of several classes of microcontaminants; however,removal efcacy is a function of the contaminant structureand 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). Biologicalprocesses, such as activated sludge, bioltration, and soil-aquifer treatment, have been shown to greatly reduce theconcentration of compounds which are biodegradable and/orreadily 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 allorganic contaminants; however, removal capacity is limitedby 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 barriersfor rejection of contaminants, while microltration andultraltration (UF) membranes provide selective removal forcontaminants with specic properties ( Snyder et al., 2006 ).

The study presented here shares occurrence data fromdrinking, waste, and surface water in South Korea. Addition-ally, this study demonstrates the ability of membranes,activated sludge, coagulation, ultraviolet (UV) irradiation,chlorination, and granular activated carbon (GAC) for theremoval of a suite of endocrine disruptors and pharmaceu-ticals in drinking and wastewater treatment facilities. To thebest of the authors knowledge, this is the rst report showing the occurrence and treatment of these compounds in thewaters of South Korea.

2. Materials and methods

2.1. Description of the sites

Efuent samples were collected from seven WWTPs in SouthKorea, one at Jeju Island and six in the South Jeolla province.The six South Jeolla province WWTPs discharge efuents intothe Youngsan River, which has a total length of 115 km andwatershed area of 2.8 103 km 2 (Fig. 1). This river starts atDamyang, runs through Gwangju, and empties into the

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Fig. 1 A map of sampling sites in South Korea. Thenumbers indicate the sampling sites in wastewatertreatment plant efuents.

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Yellow Sea. Efuents consist of about 85% domestic waste-water, 18% industrial wastewater, and 2% livestock waste-water. Of the seven WWTPs, six (Jeju, Gwangju, Naju, Jangsung, Damyang, and Young-am) use activated sludgetreatment consisting of three main steps: preliminary andnal clarication and an aeration tank. The Hwasoon siteuses a rotating biological contactor (RBC). Wastewater sourcecharacteristics are different at each site; for example,Damyang and Young-am treatment plants receive agro-industrial wastewater, Gwangju WWTPs receive both muni-cipal and industrial wastewaters, and Naju, Hwasoon, and Jangsung WWTPs are linked to the treatment of manure.

Samples from three major rivers, the Han River, theNakdong River, and the Youngsan River, were collected todetermine 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 shownin Fig. 1. The major rivers were selected for study because of their importance to public usage. These rivers were assumedto have frequent exposure to large amounts of micropollu-tants due to the inuence of WWTP efuents. Samples weretaken from one site upstream and two sites downstream inthe Han River, one site downstream in the Nakdong River, andone site upstream and three sites downstream in the Young-san River.

2.2. Treatment process of micropollutants

2.2.1. Drinking water treatmentTwo samples were taken from both Paldang and DongbokLakes, near the intake points for the water supply of the twocities of Seoul and Gwangju. All drinking water sources

in these cities are derived from these two lakes. The watersfrom Paldang and Dongbok Lakes are introduced into water-works and treated for drinking water through severalconventional treatment steps: coagulation, sand ltration,and chlorination for Gwangju, and coagulation, UF, and GACfor Seoul. Samples were collected after each step of thepurication process.

2.2.2. Wastewater treatmentContaminant removal efciency was evaluated at a WWTPdesigned for possible agricultural, recreational, and potablewater reuse of wastewater efuents. This treatment plantholds several pilot-scale treatment processes and receiveswastewater from campus dormitories and student apart-ments at Gwangju Institute of Science and Technology (GIST).The pilot process, having a ow capacity of 1m 3 /day, includesa membrane bioreactor (MBR) followed by membrane ltra-tion (MF) processes such as RO and NF, as well as MFprocesses combined with UV irradiation (e.g., RO-UV andNF-UV). The MBR system consists of an activated sludge tankfollowed by commercially available plate and frame typemembrane modules (Pure-Envitech Co., Ltd, Korea) and ahollow-ber membrane module (Kolon Co., Ltd, Korea). ROand nanotration (NF) were evaluated using spiral-woundmembranes (RE4040-FL for RO and NE4040-90-RF for NFproduced by Saehan Industries Inc., Korea). Samples werecollected before and after each unit process.

2.3. Analytical methods

All target compounds were extracted using solid phaseextraction and analyzed by liquid chromatography withtandem mass spectrometry (LCMS/MS). A detailed descrip-tion of the analytical method has been described previouslyin Vanderford et al. (2003) .

2.3.1. Sample preparationSamples were collected during periods of normal operation in2004 and 2005 from the sites described above, using pre-cleaned amber glass containers. Samples were kept on iceduring transit to the laboratory, adjusted to pH o 2 by theaddition of concentrated sulfuric acid, and stored at 4 1 C untilextraction. The use of sulfuric acid has been shown pre-viously to effectively preserve samples without degradationof these target analytes ( Vanderford et al., 2003 ).

2.3.2. Solid phase extraction

In brief, 1000 mL samples were loaded onto Waters HLB(hydrophiliclipophilic balance) solid phase extraction car-tridges at 15 mL/min. The cartridges had been previouslyconditioned using dichloromethane, tert -butyl methyl ether(MTBE), methanol, and reagent water. After loading, thecartridges were rinsed with reagent water and dried with astream 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 mLusing a gentle stream of nitrogen.

2.3.3. Liquid chromatographytandem mass spectrometryAll samples were analyzed using LCMS/MS in one of threemodes: ESI positive, ESI negative, or APCI positive. Briey, abinary pump (Agilent G1312A, Palo Alto, CA) and an auto-sampler (HTC- PAL, CTC Analytics, Zwingen, Switzerland)were used for all analyses. All analytes were separated using a250 4.6 mm Synergi Max-RP C12 column with a 4 mm particlesize (Phenomenex, Torrance, CA). A binary gradient consist-ing 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 asfollows: 5% B held for 3.5 min, increased linearly to 80% by10 min and held for 3 min, stepped to 100% and held for 8min.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 thisextraction/analysis method. These two compounds wereanalyzed using APCI positive. Estriol and estrone both hadprecursor ions of m/z 271. This indicates that estriol loseswater in the source [M H2 O+H]+ to become estrone [M+H] + .Consequently, both estrone and estriol had the same production 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/estrioldifferentiation due to chromatographic separation of the twoanalytes. Other compound-specic parameters for estriol andestrone, respectively, are as follows: declustering potential(46, 31 V); collision energy (19, 23 eV); and collision cell exitpotential (10, 16 V).

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3. Results and discussion

3.1. Recoveries and detection limits

Recoveries for this method have been published previously(Vanderford et al., 2003 ). Analytical recoveries ranged from68% to 112%, except for acetaminophen which had a recoveryof 41%. Estriol and estrone had spike recoveries of 101% and90%, respectively (n 17). All relative standard deviationswere less than 20%. An instrument detection limit (IDL) studywas performed by consecutively injecting 2.5 pg of eachcompound on column 10 times as discussed in Vanderfordet al. (2003). The IDL was then calculated by multiplying thestandard deviation of the replicate measurements by theappropriate Students T value for nine degrees of freedom.Instrument reporting limits (IRL) were chosen to be greaterthan the IDL and were generally at least three times the IDL.Reporting limits were calculated by dividing the IRL by 1000due to the concentration factor from the SPE. Reporting limitsfor all compounds were 1.0ng/L, except for caffeine and TCEPat 10 ng/L and estriol at 5 ng/L. Caffeine and TCEP had higherreporting limits due to occasional blank contamination. Dueto the complex nature of some wastewater samples, less

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

3.2. Occurrence of micropollutants

3.2.1. Surface waterThe occurrence of pharmaceuticals, hormones, antibiotics,and a ame retardant was investigated in Korean surfacewaters, including several lakes and rivers ( Table 1 ). Concen-trations 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 variouschemicals with high concentrations in some sites. Thefrequency of detection was about 44% (17% in upstream and53% in downstream) in all sampling sites. These rivers receivesecondary efuents from WWTPs and are located in indus-trialized areas. Because of human activities, the watersinvestigated are readily exposed to contaminants throughmany routes. For instance, the concentrations of iopromideand caffeine were quite high (20361 and 10194 ng/L,respectively). The compounds of highest occurrence fre-quency ( 4 80%) included TCEP, DEET, iopromide, acetamino-phen, naproxen, ibuprofen, carbamazepine, and caffeine. Theconcentrations observed are similar to those of Ternes et al.

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Table 1 Summary of concentrations for 26 selected micropollutants in efuents and surface waters

Compound Class Efuents Surface waters

NODa Concentration b NOD Conc.

Erythromycin Pharmaceutical 5 130 (8.9294) 5 3.4 (1.84.8)Sulfamethoxazole Pharmaceutical 4 136 (3.8-407) 5 20 (1.736)TCEP Miscellaneous 7 537 (922620) 8 42 (1481)DEET Miscellaneous 5 27 (6.460) 7 22 (2.069)Oxybenzone Miscellaneous 5 11 (1.030) 2 2.0 (1.22.7)Triclosan Miscellaneous 4 12 (1.332) 0 NA c

Estriol Hormone 3 16 (8.925) 0 NA17a-ethynylestradiol Hormone 1 1.3 0 NAEstrone Hormone 5 14 (2.236) 3 3.6 (1.75.0)17b-estradiol Hormone 0 o 1.0 0 NATestosterone Hormone 1 1.1 0 NAAndrostenedione Hormone 3 2.3 (1.03.5) 1 2.6Iopromide Pharmaceutical 6 2630 (11704030) 7 134 (20361)Hydrocodone Pharmaceutical 4 41 (1370) 3 1.6 (1.32.2)

Acetaminophen Pharmaceutical 3 9.5 (1.819) 6 33 (4.173)Trimethoprim Pharmaceutical 5 58 (10188) 4 4.0 (3.25.3)Pentoxifylline Pharmaceutical 2 2.9 (1.64.2) 1 1.6Meprobamate Pharmaceutical 1 6.0 0 NADilantin Pharmaceutical 6 44 (8.8181) 6 4.3 (1.18.9)Naproxen Pharmaceutical 7 128 (20483) 6 11 (1.818)Ibuprofen Pharmaceutical 5 65 (10137) 6 28 (1138)Diclofenac Pharmaceutical 7 40 (8.8127) 3 3.0 (1.16.8)Carbamazepine Pharmaceutical 6 226 (73729) 7 25 (4.561)Caffeine Pharmaceutical 6 228 (23776) 8 105 (2.9194)Fluoxetine Pharmaceutical 1 1.7 0 NAGembrizil Pharmaceutical 3 11.2(3.917) 3 6.6 (1.89.1)

a Number of samples detected among seven total samples for efuents and eight total samples for surface waters.b Indicates mean concentration with the minimum and maximum values in parentheses.c

Not applicable.

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(1998), who investigated these compounds in German riversand streams. However, most hormone compounds wereobserved consistently below detection limits in all sites,similar to ndings by Boyd et al. (2003), with the exceptionof estrone which measured between 1.5 and 5.0 ng/L. How-ever, other investigators reported much higher concentra-tions of hormones in surface waters. For example, Kolpinet al. (2002) reported 17 b-estradiol, 17 a-ethynylestradiol,and testosterone to be present at averages of 9, 73 and116 ng/L, respectively, in surface water. Ethynylestradiol and17b-estradiol were also previously reported at concentrationsranging from 0.2 to 2.6 ng/L ( Snyder et al., 1999 ). In general,the types and concentrations of PPCPs detected here aresimilar 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 locatedupstream of wastewater inuenced rivers were relatively lowin target compounds, with only 17% of compounds detectedand at low concentrations ( Table 2 ). However, Paldang Lakedid have a high concentration of iopromide (143 ng/L). Incontrast, Dongbok Lake in the Gwangju area showed littlecontamination, with only small amounts of TCEP andoxybenzone present.

3.2.2. Wastewater efuentsResults from chemical analyses at seven WWTPs are sum-marized in Table 1. Most chemicals were detected (58%) in theWWTP efuents studied. An example LCMS/MS chromato-gram from the Jangsung WWTP is shown in Fig. 2. It is likelythat occurrence frequency would have been greater if thesurface water detection limit had been used. Since a lesservolume of wastewater was extracted, the corresponding reporting limit was greater. The concentrations of chemicalsdetected in efuent samples were much higher by one orderof magnitude than those in surface water samples fromrivers. The most frequently detected compounds includedTCEP, iopromide, dilantin, naproxen, diclofenac, carbamaze-pine, and caffeine. Iopromide was found at relatively high

concentrations (up to 4030ng/L). This is in agreement withTernes et al. (1998), who reported that many PhACs weredetected in the efuents and measured at high concentra-tions due to incomplete elimination in German sewagetreatment plants. In addition, TCEP was quite high (average537 ng/L) in all efuent samples. However, hormones such as17a-ethynylestradiol and 17 b-estradiol were not detectedfrequently in efuents. This result is comparable to resultsfrom other studies ( Ternes et al., 1999a,b ; Baronti et al., 2000;Huang and Sedlak, 2001 ; Kolpin et al., 2002), which showedvery rare detection and low concentration for 17 a-ethynyles-tradiol and 17 b-estradiol in WWTP efuents. A previous studyhas shown that the activated sludge treatment step reduceshormones efciently up to about 80%, especially for 17 b-estradiol ( Ternes et al., 1999a,b ). Of these natural hormones,estrone was dominant in efuents and surface watersamples. Fig. 3 shows the average and standard deviation of the sum of total microcontaminants within the three majorclasses 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 andrain events, and the introduction of chemicals through non-point sources.

3.3. Removal of micropollutants

3.3.1. Drinking water treatmentTreatment efciency of micropollutants in drinking watertreatment processes was investigated using different puri-cation methods currently operated in both Gwangju andSeoul (Table 2 ). Overall, the inuent waters were not highlycontaminated. Only six target compounds were detected atthese drinking water facilities, and at low concentrations withthe exception of iopromide. At Gwangju, only the ameretardant TCEP and the sunscreen oxybenzone were detected.Moreover, the concentrations of these two compounds werevery near the analytical reporting limits, thus no meaningfultreatment predictions can be drawn from Gwangju drinking water treatment data. In Seoul, six target compounds were

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Table 2 Removal of micropollutants by purication process during drinking water treatment

Compound Gwangju Seoul

DongbokLake

Coagulation Sandltration

Chlorination Paldang Lake

Coagulation UF-ltration

GAC

TCEP 14 o 10 o 10 o 10 25 28 38 o 10DEET o 1.0 o 1.0 o 1.0 o 1.0 2.0 2.2 2.7 o 1.0Oxybenzone 1.2 o 1.0 1.5 o 1.0 o 1.0 o 1.0 ND o 1.0Androstenedione o 1.0 o 1.0 o 1.0 o 1.0 o 1.0 o 1.0 1.2 o 1.0Iopromide o 1.0 o 1.0 o 1.0 o 1.0 143 166 177 o 1.0Dilantin o 1.0 o 1.0 o 1.0 o 1.0 o 1.0 o 1.0 1.2 o 1.0Ibuprofen o 1.0 o 1.0 o 1.0 o 1.0 15 18 23 o 1.0Carbamazepine o 1.0 o 1.0 o 1.0 o 1.0 4.8 5.3 7.5 o 1.0Caffeine o 10 o 10 o 10 o 10 45 43 48 o 10

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

served removal appears to be entirely related to GAC at theSeoul drinking water treatment facility. GAC has been shownpreviously 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 thetargeted compounds with activated carbon based on theirhydrophobicity. In addition, the low concentration of natural

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c o n c e n

t r a

t i o n

, n g

/ L

1

10

100

1000

10000

effluentssurface water

drinking water source

pharmaceuticals hormones miscellaneouscompounds

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

Fig. 2 Reconstructed chromatogram of Jangsung WWTP efuent.

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

3.3.2. Wastewater treatmentTable 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, androstene-dione) and certain pharmaceuticals (e.g., acetaminophen,ibuprofen, and caffeine) with approximately 99% removal.However, the results showed that MBR treatment did notdecrease the concentration of erythromycin, TCEP, trimetho-prim, naproxen, diclofenac, and carbamazepine. This iscomparable to the results of previous studies ( Heberer, 2002 ;Ternes et al., 1999a,b ), which indicated very low eliminationrates of diclofenac and carbamazepine in WWTP processes inGermany. In the comparison between the two MBR modulesused in this study (plate and frame versus hollow-ber), nodifference in target compound removal was found.

RO and NF membrane processes showed excellent removal

rates ( 4 95%) for all detectable analytes. However, thecombination of membranes with UV irradiation did notprovide enhanced removal. Additionally, it was found thatRO did not display higher removal percentages whencompared with NF. This is important in terms of cost foroperating WWTPs. Consequently, wastewater treated by MFusing RO or NF is adequate for the effective removal of avariety of micropollutants, such as pharmaceuticals andhormones.

4. Conclusions

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

frequently detected in Korean surface waters. Overall, thetotal concentrations of chemicals measured in all types of waters followed in this order: pharmaceuticals 4 miscella-neous compounds (e.g., ame retardant) 4 hormones. Con-ventional drinking water treatment processes (e.g.,coagulation and sand ltration) tested in this study wereinefcient for the removal of micropollutants found in thesource water. Conventional WWTPs (e.g., activated sludge)showed incomplete removal of 25 micropollutants tested. Inorder to efciently remove microcontaminants, processesincluding GAC and MF with RO or NFare suggested because of their high removal rates. Ultimately, a multi-barrier approachusing MBR followed by RO or NF could prove the mosteffective in contaminant removal.

Acknowledgments

This research was supported by a grant (code#4-1-2) from theSustainable Water Resources Research Center of the 21stCentury Frontier Research Program (South Korea) and funding from the American Water Works Association ResearchFoundation (Project #2758).

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Table 3 Removal of micropollutants in wastewater by various treatment technologies

Compound Inuent MBR(P) a MBR(K)b RO NF RO-UV NF-UV

Erythromycin 44 40 42 o 1.0 o 1.0 o 1.0 o 1.0Sulfamethoxazole 194 70 58 o 1.0 o 1.0 o 1.0 o 1.0TCEP 284 303 283 14 13 25 13

DEET 18 19 18 o 1.0 o 1.0 o 1.0 o 1.0Oxybenzone 34 17 20 o 1.0 o 1.0 o 1.0 o 1.0Triclosan 74 25 20 o 1.0 o 1.0 o 1.0 o 1.0Estriol 318 o 10 o 10 o 5.0 o 5.0 o 5.0 o 5.0Testosterone 60 o 10 o 10 o 1.0 o 1.0 o 1.0 o 1.0Androstenedione 140 o 10 o 10 o 1.0 o 1.0 o 1.0 o 1.0Hydrocodone o 10 14 15 o 1.0 o 1.0 o 1.0 o 1.0Acetaminophen 11500 o 10 21 o 1.0 o 1.0 o 1.0 o 1.0Trimethoprim 21 31 28 o 1.0 o 1.0 o 1.0 o 1.0Naproxen 262 168 154 o 1.0 o 1.0 o 1.0 o 1.0Ibuprofen 5320 52 90 o 1.0 o 1.0 o 1.0 o 1.0Diclofenac 10 25 22 o 1.0 o 1.0 o 1.0 o 1.0Carbamazepine 42 46 44 o 1.0 o 1.0 o 1.0 o 1.0Caffeine 9680 o 100 104 o 10 o 10 o 10 o 10

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

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Occurrence and Removal of Pharmaceuticals and Endocrine Disrupter