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1 +,PSFBO4PD&OWJSPO&OH _ Original Paper IUUQTEPJPSH,4&& *44/F*44/ Ú f x n q m Occurrence Characteristics of Parabens in Nakdong River Basin n p p Ò Ð* m* ** Hoon-Sik Yoom Hee-Jong Son Hee-Young Kim Dong-Choon Ryu Jae-Don Shin* Yun-Ho Lee* Chang-Won Kim** * }sœ vw}s ** s vw}s} Water Quality Institute, Busan Water Authority *School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST) **Department of Environmental Engineering, Pusan National University (Received April 5, 2018; Revised April 23, 2018; Accepted May 4, 2018) Abstract : In this study, methyl paraben (MP), ethyl paraben (EP), propyl paraben (PP), and butyl paraben (BP) were analyzed to identify their occurrence characteristics at various sampling sites (the effluent from the wastewater treatment plant, the main stream and tributaries to which the effluent is introduced) in the Nakdong River basin during various sampling periods (January, April, August, and October). Among the four parabens, MP was detected with the highest detection frequency (100%), followed by PP (80~100%), EP (13~43%), and BP (3~20%). In case of detection level, MP showed the highest concentration with 3.2 to 33.9 ng/l as an average, followed by PP (8.2 to 28.4 ng/l), EP (2.2 to 8.0 ng/l), and BP (1.0 to 2.4 ng/l). In August, when the use of personal care products increased sharply, parabens that had not been completely removed from the wastewater flowed into the water system and showed typical patterns of contamination of the water sources. At the upstream sites, the detection level of the parabens was relatively lower than other sites, but the parabens were found to be high in the tributaries and the main stream from the midstream where the wastewater treatment plants were densely located. For discharge loads calculated using effluent concentration, large wastewater treatment plants with a treatment capacity of 100,000 ton/day or more were the major contamination pathway of parabens in the Nakdong River basin. The results of calculations of non-carcinogenic risk for parabens detected in the main stream of Nakdong River, tributaries and wastewater treatment plants were evaluated as no risk, but long-term monitoring and management were required for long-term toxicity in water environment. Key Words : Parabens, Personal Care Products, Nakdong River Basin, Wastewater Treatment Plant Effluents, Occurrence. ²Òv jj, a Ø² dd (methyl paraben, MP), dd (ethyl paraben, EP), i jd (propyl paraben, PP) dd (butyl paraben, BP) 4 ¼ k d ² 1, 4, 8 10 j á d j º. j, d á Ðaa d ²MP ì á Ø, º PP (80~100%), EP (13~43%), BP (3~20%) º. á Ð ÐMPaf 13.2~33.9 ng/l a íá Ø, º PP (8.2~ 28.4 ng/l), EP (2.2~8.0 ng/l), BP (1.0~2.4 ng/l) º. } h j²j (8 ) j p ÑØ jd a j Ø ² l e º. í ²d á Ð² j í j ² í í d á í, jd j, 100,000 / ¼lj í Òv d º. Òv á Ùd Ð ¼ kð j ² k ²ä faø m Ð ¼k ² aj jä º.. d, } h, Òv, j, á 1. d ²p-hydroxybenzoic acid alkyl ester h, b h, h } h î aø k aj ² Ð, n e í j² Ø º. 1~3) dp, m h ² d aa m Ø, 4,5), m h 0.4%~0.8% j aùº. 1) d ² dd (methyl paraben, MP), dd (ethyl paraben, EP), i jd (propyl paraben, PP), i jd (isopropyl paraben, ipp), dd (butyl paraben, BP), dd (isobutyl paraben, ibp) d (benzyl paraben, BeP) î 1), d k d a vk º. BP EP k4 Ðvj k³ Corresponding author menuturk@hanmail.net Tel: Fax:

2 194 +,PSFBO4PD&OWJSPO&OH n p p Ò Ð m a º. 1) l h, b h, h } h î a MP PPaa Ø º. 6) í j, h, j, Ò Ðd aá Ø, 7~9) dp, MP, EP, PP BP á Ða, á Ð² MP PPaº d k îp ä j º. 1) j f v Ð m k ²ä Ø º. 1) Peng î 10) v(pearl river) 9} ¼ MP PP á Ð j, MP² ¼1062 ng/l, PP ² ¼3142 ng/l Ð á Ø º j º. j, Ðh Ð j í ¼ d á Ð jyamamoto î 11) ² MPa25~676 ng/l, PPa< 0.8~207 ng/l BPa< 0.6~ 163 ng/l Ð á Ù ä j º. j, Kang î 12) í (urine) d á Ð j, á Ð á ÐaMP² 60.6~451.5 µg/l 98%, EP²16.9~202.8 µg/l 100%, PP ²0.94~65.4 µg/l 98% í í ¼j ä j º. d a e j í í k, í í² n (estrogenic effect) jº. 13,14) j, ² (breast tumor) Ø º. 15) j, d a j, Ð j² j j, Ð Å vj jº º. 16,17) ²Òv k ² 50,000 / j a Ø² a k ² ¼ MP, EP, PP BP Ð á d faj kn j m j m j j º. Table 1. 1IZTJDPDIFNJDBM QSPQFSUJFT PG QBSBCFOT $PN.8 'PSNVMBS Q,B QPVOET HNPM.FUIZM -PH,PX 4PMVCJMJUZ H 4USVDUVSF N- QBSBCFO $ ) 0.1 &UIZM QBSBCFO $ ) 0 &1 1SPQZM QBSBCFO $ ) 0 11 #VUZM QBSBCFO #1 $ ) 0 4PMVCJMJUZJOXBUFSBU mj d Table 1 º. a Log K ows aj, ¼j kð(25 )a p q jº j Òv 10} k ² 6} Òv Ø²j ( 50,000 / ) 11} j, Fig. 1 Òv º. Fig. 1 î Òv 10}, 6}, j 11} h j º. Table 2 ²11} 2. l 2.1. h Ù4 d ²MP, EP, PP BP, AccuStandard (USA) h ( Ð: 99%) j º. j, 4 h CDN Isotopes (Canada) h j, methyl 4-hydroxybenzoate-2,3,5,6-d 4 (d 4-MP), ethyl 4-hydroxybenzoate-2,3,5,6-d 4 (d 4-EP), n-propyl 4-hydroxybenzoate-2,3,5,6-d 4 (d 4-PP) n-butyl 4-hydroxybenzoate-2,3,5,6-d 4 (d 4-BP) º. d î (J.T. Baker (USA))²HPLC î j, ammonim acetate formic acid² Sigma-aldrich (USA) d j º. ¼ d 4 ¼j Fig. 1. %FTDSJQUJPO PG UIF TBNQMJOH TJUFT JO /BLEPOH SJWFS CBTJO Journal of KSEE Vol.40, No.5 May, 2018

3 +,PSFBO4PD&OWJSPO&OH Òv d á d 195 Table 2. %FTDSJQUJPO PG UIF TVSWFZFE TFXBHF USFBUNFOU QMBOUT XXXLPOFUJDPSLS T 1SPDFTT $BQBDJUZ UPOEBZ 4PVSDFT %JTDIBSHF BSFB (VN "OEPOH "% "4B EPNFTUJDTFXBHFGFDFTBOEVSJOFMJWFTUPDLXBTUFXBUFS NBJOTUSFBN (JNDIFPO ($ "4B EPNFTUJDTFXBHFJOEVTUSJBMXBTUFXBUFS USJCVUBSZ 8POQZFPOH 81 "4 B %/3 C USJCVUBSZ J (. " 0 EPNFTUJDTFXBHFSBJOXBUFSJOEVTUSJBMXBTUFXBUFS NBJOTUSFBN (VNJ (. %/3 EPNFTUJDTFXBHFJOEVTUSJBMXBTUFXBUFSSBJOXBUFSTBOJUJ[FEGFDFTBOEVSJOF NBJOTUSFBN 4JODIFPO 4$ " 0 EPNFTUJDTFXBHFSBJOXBUFSGPPEXBTUFEJTQPTBMGBDJMJUZFGGMVFOU USJCVUBSZ %BMTFPDIFPO %4$ " 0 EPNFTUJDTFXBHFJOEVTUSJBMXBTUFXBUFSTBOJUJ[FEGFDFTBOEVSJOFMBOEGJMMMFBDIBUF USJCVUBSZ #VLCV ## " 0 EPNFTUJDTFXBHFSBJOXBUFS USJCVUBSZ 4FPCV 4# " 0 EPNFTUJDTFXBHFSBJOXBUFSTBOJUJ[FEGFDFTBOEVSJOF USJCVUBSZ +JOKV ++ $/3 D USJCVUBSZ.JMZBOH.: #454** E EPNFTUJDTFXBHFGFDFTBOEVSJOFMJWFTUPDLXBTUFXBUFS USJCVUBSZ B "4BDUJWBUFETMVEHFQSPDFTT D $/3$JMJVNOVUSJFOUSFNPWBMQSPDFTT NPEJGJFE" 0QSPDFTT C %/3%BFXPPOVUSJFOUSFNPWBMQSPDFTT NPEJGJFE" 0QSPDFTT E #454**#JPNFDDBTFXBHFXBTUFXBUFSUSFBUNFOUTZTUFN j, î º. ²b d ² , 4, 8, 10 Ù 4m j º. j ² j ² j k j k d 50 ml ¼0.2 ml 5% Na 2EDTA aj, 0.45 µm (Millipore, USA) j n j º d á bb h k 1~1000 ng/l Ð (10 point) j, ì ¼jd j (limit of quantification, LOQ)²4 Þ1 ng/l º. ²on-line SPEa ÙLC-MS/MS j º. SPE d ²Agilent PLRP-S ( mm, 15~20 µm) j º. autosampler 900 µl j SPE d nlc Ò SPE d p ( )Ù d LC º. LC Agilent poroshell EC-C18 ( mm, 2.7 µm) j º. p Ùd yspe d ²IPA/ACN/MeOH mj n, MeOH m m(reconditioning) º. LC tubing í Ø² d ¼ d j j j² Ð º í Ø²ä j ktrapping ( mm, 5 µm, Agilent) SPE d º j º. Table 3. %FUBJMFE-$NFUIPEBOEPQUJNJ[FE.4QBSBNFUFS 4PMWFOU" 4PMWFOU# 'MPXSBUF (SBEJFOU *OKFDUJPOWPMVNF %SBXBOEFKFDUTQFFE (BTUFNQ (BTGMPX /FCVMJ[FS 4IFBUIHBTUFNQ 4IFBUIHBTGMPX -$ "HJMFOUJOGJOJUZ 8BUFSN."NNPOJVNGPSNBUF 'PSNJDBDJE "$/'PSNJDBDJE N-.4.4 "HJMFOU(" $PNQPTJUJPO 5JNF " # - - 7BMVF - QTJ - j Ò 5 mm ammonium acetate % $BQJMMBSZ 7 formic acid (Solvent A) ACN + 0.1% formic acid (Solvent B), ¼ n k e ô Þ a º j, Ò, Õ Õ Table 3 º. 4 d MS/MS Õ a qða Ø² Õ j, MS/MS /P[[MF 7 Õ Table 4 º. 4 d h í h í mùonline SPE-LC-MS/MS Õ jmrm (multiple reaction monitoring) chromatogram Fig. 2 º. ¼jm jm 40 5m

4 196 +,PSFBO4PD&OWJSPO&OH n p p Ò Ð m Table QBSBNFUFST GPS UIF BOBMZTJT PG 1BSBCFOT CZ.3. JO OFHBUJWF NPEF $PNQPVOET 1SFDVSTPSJPO $77 1SPEVDU*PO $& 7 2VBOUJGJDBUJPO $POGJSNBUJPO 1PMBSJUZ.1 OFHBUJWF &1 OFHBUJWF 11 OFHBUJWF #1 OFHBUJWF E.1 OFHBUJWF E &1 OFHBUJWF E 11 OFHBUJWF E #1 OFHBUJWF 2.4. k fa Òv, j Ù d (d 4 j) Ð ¼s, s k (average daily intake, ADI) 21) j d á Ð ¼j k faj º. d ² j j º., f ¼ m j kì (2007) j²947.7 ml/day, 62.8 kg 73.2 j º. l d ² Ø kð(hazardous quotient, HQ) j º( (1) (2)). (1) (exposere, E) jº, (2) k (ADI) (E) j kð(hq) j º Exposure (E) = EC DI EF ED (1) BW AT CF, EC : m Ð (environmental concentration), µg/l DI : (drinking water intake), ml/day EF : Ð(exposure frequency), days/year ED : e(exposure duration), year BW: (body weight), kg AT : ¼ (average time), year CF : º m Hazardous quotient (HQ) = ADI E (2) ADI 21) : k (average daily intake), mg/kg d E : (exposure), mg/kg d Òv á d , 4, 8 10 Òv d Fig DISPNBUPHSBNT PG QBSBCFOT BOE EQBSBCFOT JOUFSOBM 45%T 4 á Ð jä Fig. 3 º. Fig. 3 î Òv js2 ( Ò), S4( ), S5 (Ò) d 4 f Ð²bb9.5 ng/l, 9.9 ng/l 9.4 ng/l já Ð º. b º í j (S7: ) á Ða aj² k º. S7 ( ) jj í (WWTP3 WWTP4) WWTP2 (80,000 / ) k ² q (S6) Ùº. (S7) d 4 á Ð ²23.4~96.7 ng/l º. j, S11 ( ) ²12.5~111.6 ng/l Ð(f : 43.4 ng/l) 4 d aá Ø í a á Ð º. S11 Journal of KSEE Vol.40, No.5 May, 2018

5 +,PSFBO4PD&OWJSPO&OH Òv d á d 197 Fig. 3. 7BSJBUJPO PG UPUBM QBSBCFOT DPODFOUSBUJPO JO NBJO TUSFBN PG /BLEPOH SJWFS CBTJO Fig. 4. %FUFDUFE DPODFOUSBUJPOT OVNFSJDBM OH- BOE QSPQPSUJPO SBUFT PG QBSBCFOT JO NBJO TUSFBNT PG /BLEPOH SJWFS ( ) j mv(s9) (S10) k á Ða ajä faø, mv(s9) (S10) j (WWTP6), º j (WWTP7), j (WWTP8) j (WWTP9) a Ø² í º. Òv j á Ð² (S14), (S15) (S16) bb30.4 ng/l, 25.2 ng/l 16.9 ng/l j í kj i á Ð² q j² k º. (S11) j ²mv, v(s13) vî í gj í í j jp n dºùº , 4, 8 10 Òv í á Ùd Fig. 4 º. Fig. 4(a)~(d) î á Ùd MP, 8 (Fig. 4(c)) a (40%~69%), 10 (Fig. 4(d)) a (80%~100%) º. j, 8 º (1, 4 10 ) ki jd í º. f á Ð ²¼ 8 a á Ð, 1 4 j Ð, 10 a á Ð º Òv j á d 11} j í í k e ² 6} í d 4 á d faj ä bb Fig. 5 Fig. 6 º. j í ¼ j Fig. 5 î 8 ²f 135 ng/l (56.8~ 240 ng/l) Ð á Ø a á Ð º. º 1 f 53.7 ng/l (12.2~217 ng/l) Ð á Ø, 4 10 ²f 38.4 ng/l (14.4~ 109 ng/l) 38.5 ng/l (15.8~78.9 ng/l) Ð á Ø º. ô j í d á Ð²8 a Ð, º 1, 4 10 Ñ Ò jí º. Zgola-Grześkowiak î 22) g ì v m ¼ (5, 7 12 ) á d j, j (7 )a º k îp Ð º j, j ²j º ¼jm jm 40 5m

5(b) î 8 j ²4 d a ÈMPa61%~69% a jíá Ø ² k, 8 ²º ²º PPa 58% a jíá Ø, º MP 39.2%, EP 2.0%, BP 0.8% º. 6} ¼ d 4 á d j Fig. 6 º. d 4m j, f á Ða8 113 ng/l (20.7~195 ng/l) a í, º 4 39.3 ng/l (3.10~85.

6 198 +,PSFBO4PD&OWJSPO&OH n p p Ò Ð m Fig. 5. 5PUBM DPODFOUSBUJPOT PG QBSBCFOT B BOE QSPQPSUJPO C BDDPSEJOH UP NPOUI JO T Fig. 6. 5PUBM DPODFOUSBUJPOT PG QBSBCFOT B BOE QSPQPSUJPO C BDDPSEJOH UP NPOUI JO USJCVUBSJFT (deodorant) î z m h } h aj²ä ä faj º. j, Fig. 5(b) î 8 j ²4 d a ÈMPa61%~69% a jíá Ø ² k, 8 ²º ²º PPa 58% a jíá Ø, º MP 39.2%, EP 2.0%, BP 0.8% º. 6} ¼ d 4 á d j Fig. 6 º. d 4m j, f á Ða8 113 ng/l (20.7~195 ng/l) a í, º ng/l (3.10~85.4 ng/l), ng/l (14.3~48.0 ng/l), ng/l (14.1~ 50.3 ng/l) º. j í í kj í k Ò j í á Ð º 2 ~3 Ð Ð º. j, 8 j ²MPa65~87% a jíá Ø² k, 8 PP 58%, MP 39%, EP 2%, BP 1% á Ú j j k º. b j í á Ù d Ð j j j j Table 5 º. j j b á Ù 4 d j j 21) j º. f j j (WWTP6) kg/d a í, º j (WWTP5) kg/d, j (WWTP9) Table 5. %JTDIBSHF MPBET PG QBSBCFOT JO UIF T JO /BL EPOHSJWFSCBTJO T %JTDIBSHF N E 1BSBCFOTEJTDIBSHFMPBE LHE +BO "QS "VH 0DU "WFS kg/d, j (WWTP10) kg/d º. a j f j (WWTP3), á Ð²62.5 ng/l 5 j (WWTP6) º 13 Ð ( kg/d) º. j á Ùd Ð ¼s (WWTP11) s(wwtp8) a 4 Ù j ² Ð º² e k e 100,000 / j m d m Ø º j í k Journal of KSEE Vol.40, No.5 May, 2018

7 +,PSFBO4PD&OWJSPO&OH Òv d á d 199 Fig. 7. 7p ph pi h yhpy ƒf t y q VVSI pqqw py ƒtg fƒtp fyi xfty ƒpfx q Gfvi yr Qt pƒ gf ty ty Cfy fƒ fyi 4 r $ ² í í d á d º ífaj Ð Òv Ð d á Ð h j ä Fig. 7 º. Fig. 7(a) (b) î j í, í í d á Ð a º. dp, 1 k8, j n Ø² d Ða aj S7( ) Ða j, ¼lj í(wwtp6~9) j mv(s9) (S10) Ð1 k8 á Ða îp í º. Table 5 î mv j j í(wwtp6~9) d j (kg/d) Ð1 k8 4.5 ~10.5 Ð ajä º. j, í í k e ² í( (S11), ¼ (S12), (S14) î) á ÐÐj j º. ô } h j² j j p ÑØ j d a j Ø ² l e º. Table 6 ² 4m jòv í, í j í á Ù4 d f á Ð(Aver.), (Min.) ¼á Ð(Max.) á Ð(detection frequency, D.F.) î j º. MP,, j Þ 100% á Ð, PPaj ²100% á, ²80% á Ð MP º á Ða º. EP BP ²j á Ðabb 43% 20% MP PP k îp á Ð á Ð, j á Ð á Ð k á Ð á Ð jbb12.5~41.7%, 2.2~4.1 ng/l 2.5~16.7%, 1.0~2.1 ng/l MP PP k îp í º. Table 6. 6 yhpy ƒf t y wp pw q! fƒfgpy yre ty xfty ƒpfx ƒtg fƒtp fyi qtyfw pqqw py q RSI.1 &1 11 #1.BJO 5SJCV &GGM.BJO 5SJCV &GGM.BJO 5SJCV &GGM.BJO 5SJCV &GGM "WFS B 4% C.BY.JO %' D B "WFS BWFSBHFDPODFOUSBUJPO C 4% TUBOEBSEEFWJBUJPO D %' EFUFDUJPOGSFRVFODZ ¼jm jm 40 5m

8 200 +,PSFBO4PD&OWJSPO&OH n p p Ò Ð m 3.3. á lm v j á Ùd í á Ð jä Table 7 º. Table 7 î v j d á Ð², MP PP á Ð aepbp k º. j, Òv á Ù Ð² á j j º. a á Ð k Table 7. $PNQBSJTPO PG EFUFDUFE DPODFOUSBUJPOT PG QBSBCFOT 6 x yi FI 8I JOWBSJPVTSJWFSXBUFSBSPVOEUIFXPSME Vf pƒ ƒhp yre Qt pƒˆf pƒ 6 y ƒ Qpq %"!$# I wfyi # % R fty " G7 % Byitf! & B R fty $ " #$# Cf fy "! Cf fy & $ TR4 % % & 6styf % % D ƒpf Sst i G7 I wfyi! R fty " "! Byitf! # B R fty $ #! Cf fy G7 Cf fy & G7 TR4 % G7 &! 6styf G7 %" D ƒpf Sst i G7 " I wfyi % R fty " G7 "$ Byitf!!" B R fty $ II % $ Cf fy G7 TR4 %!& " Cf fy & G7 "#" 6styf G7 & D ƒpf Sst i G7 I wfyi! B R fty $ G7 Byitf! # # Cf fy 5I G7 Cf fy & G7 TR4 % G7!" 6styf G7! D ƒpf Sst i G7'y ip ph pi B f pƒfrp, Ð 24) z } Ð v j á Ða 11) f 23,25) z Ð jv j ² Ð d á Ø º. j 8) ²Òv á Ð ºn á º Òv k fa d ² m Ø á Ùd 4 ² k faaj jº. ô Òv í, í j í á Ù4 d / ¼á Ð j kð(hq) fajä Table 8 º. 26) kð²1 j s a ² a ³j kð faj º. Table 8 a Ð Ø²j Ð kð²1 ºn s k ²ä faø º. j Ð Ù a³, Ð Ø² j Ð Å vj mù aj jº. 15) Table 8. 3JTL BTTFTTNFOU SFTVMU PG QBSBCFOT GSPN DBMDVMBUJPO UISPVHI FR 6 x yi Ffty ƒpfx Sƒtg fƒtp 8qqw py 4. 6 yh re 8 ƒp xrvr i 47B xrvr i AP xty! %8 %8% xf # %!8 %!8$ xty &"!$8!$8# xf 8 8% xty &%8 &%8% xf! %8 %8# ² Òv Òv j j d 4 á d j, º z º. 1) j, d á Ða a d ² dd ì á Ø, º i jd (80~100%), dd (13~43%), d d (3~20%) º. 2) j, á Ð Ð dd f 13.2~33.9 ng/l a íá Ø, º i j d (8.2~28.4 ng/l), d d (2.2~8.0 ng/l), dd (1.0~2.4 ng/l) º. 3) } h j² j (8 ) Journal of KSEE Vol.40, No.5 May, 2018

9 +,PSFBO4PD&OWJSPO&OH Òv d á d 201 j p ÑØ j d a j Ø ² l e º. 4) í ² d á Ð² j í j ² í í d a í á Ø, j d j, 100,000 / ¼l j í Òv d º. 5) Òv, j á Ù d Ð ¼ kð j ² k ² ä faø m Ð ¼k ² aj jä º. References 1. Bledzka, D., Gromadzinska, J. and Wasowicz, W., Parabens from environmental studies to human health, Environ. Int., 67, 27~42(2014). 2. Guo, Y. and Kannan, K., A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure, Environ. Sci. Technol., 47, 14442~14449(2013). 3. Dodge, L. E., Kelly, K. E., Williams, P. L., Williams, M. A., Hernández-Díaz, S., Missmer, S. A. and Hauser, R., Medications as a source of paraben exposure, Reprod. Toxicol., 52, 93~100(2015). 4. Cashman, A. L. and Warshaw, E. M., Parabens: a review of epidemiology, structure, allergenicity, and hormonal properties, Dermatitis, 16, 57~66(2005). 5. Janjua, N. R., Mortensen, G. K., Andersson, A. M., Kongshoj, B., Shakkebaek, N. E. and Wulf, H. C., Systemic uptake of diethyl phthalate, dibutyl phthalate, and butyl paraben following whole-body topical application and reproductive and thyroid hormone levels in humans, Environ. Sci. Technol., 41, 5564~5570(2007). 6. Núnez, L., Tadeo, J. L., García-Valcárcel, A. I. and Turiel, E., Determination of parabens in environmental solid samples by ultrasonic-assisted extraction and liquid chromatography with triple quadrupole mass spectrometry, J. Chromatogr. A., 1214, 178~182(2008). 7. Carmona, E., Andreu, V. and Picó, Y., Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: from waste to drinking water, Sci. Total Environ., 484, 53~63(2014). 8. Renz, L., Volz, C., Michanowicz, D., Ferrar, K., Christian, C., Lenzner, D. and El-Hefnawy, T., A study of parabens and bisphenol A in surface water and fish brain tissue from the Greater Pittsburgh Area, Ecotoxicology, 22, 632~ 641(2013). 9. Terasaki, M., Takemura, Y. and Makino, M., Parabenchlorinated derivatives in river waters, Environ. Chem. Lett., 10, 401~406(2012). 10. Peng, X., Yu, Y., Tang, C., Tan, J., Huang, Q. and Wang, Z., Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China, Sci. Total Environ., 397, 158~166(2008). 11. Yamamoto, H., Tamura, I., Hirata, Y., Kato, J., Kagota, K., Katsuki, S., Yamamoto, A., Kagami, Y. and Tatarazako, N., Aquatic toxicity and ecological risk assessment of seven parabens: Individual and additive approach, Sci. Total Environ., , 102~111(2011). 12. Kang, S., Kim, S., Park, J., Kim, H. J., Lee, J., Choi, G., Choi, S., Kim, S., Kim, S. Y., Moon, H. B., Kim, S., Kho, Y. L. and Choi, K., Urinary paraben concentrations among pregnant women and their matching newborn infants of Korea, and the association with oxidative stress biomarkers, Sci. Total Environ., , 214~221(2013). 13. Inui, M., Adachi, T., Takenaka, S., Inui, H., Nakazawa, M., Ueda, M., Watanabe, H., Mori, C., Iguchi, T. and Miyatake, K., Effect of UV screens and preservatives on vitellogenin and choriogenin production in male medaka (Oryzias latipes), Toxicology, 194, 43~50(2003). 14. Terasaki, M., Abe, R., Makino, M. and Tatarazako, N., Chronic toxicity of parabens and their chlorinated byproducts in Ceriodaphnia dubia, Environ. Toxicol., 30, 664~673(2015). 15. Darbre, P. D., Aljarrah, A., Miller, W. R., Coldham, N. G., Sauer, M. J. and Pope, G. S., Concentrations of parabens in human breast tumors, J. Appl. Toxicol., 24, 5~ 13(2004). 16. Canosa, P., Rodríguez, I., Rubí, E., Negreira, N. and Cela, R., Formation of halogenated by-products of parabens in chlorinated water, Anal. Chim. Acta, 575, 106~113 (2006). 17. Terasaki, M., Makino, M. and Tatarazako, N., Acute toxicity of parabens and their chlorinated by-products with Daphnia magna and Vibrio fischeri bioassays, J. Appl. Toxicol., 29, 242~247(2009). 18. Soni, M. G., Carabin, I. G. and Burdock, G. A., Safety assessment of esters of p-hydroxybenzoic acid (parabens), Food Chem. Toxicol., 43, 985~1015(2005). 19. Golden, R., Gandy, J. and Vollmer, G., A review of the endocrine activity of parabens and implications for potential risks to human health, Crit. Rev. Toxicol., 35, 435~458(2005). 20. Jewell, C., Prusakiewicz, J. J., Ackermann, C., Payne, N. A. and Fate, G., Voorman, R. and Williams, F. M., Hydrolysis of a series of parabens by skin microsomes and ¼jm jm 40 5m

10 202 +,PSFBO4PD&OWJSPO&OH n p p Ò Ð m cytosol from human and minipigs and in whole skin in short-term culture, Toxicol. Appl. Pharmacol., 225, 221~ 228(2007). 21. Ministry of Environment, 2015, Sewer statistics, Korea 22. Zgola-Grześkowiak, A., Jeszka-Skowron, M., Czarczyńska- Goślińska, B. and Grześkowiak, T., Determination of parabens in Polish river and lake Water as a function of season, Anal. Lett., 49, 1734~1747(2016). 23. Li, W., Gao, L., Shi, Y., Wang, Y., Liu, J. and Cai, Y., Spatial distribution, temporal variation and risks of parabens and their chlorinated derivatives in urban surface water in Beijing, China. Sci. Total Environ., 539, 262~ 270(2016). 24. Ramaswamy, B. R., Shanmugam, G., Velu, G., Rengarajan, B. and Larsson, D. G. J., GC MS analysis and ecotoxicological risk assessment of triclosan, carbamazepine and parabens in Indian rivers, J. Hazard. Mater., 186, 1586~1593(2011). 25. Gracia-Lor, E., Martínez, M., Sancho, J. V., Peñuela, G. and Hernández, F., Multi-class determination of personal care products and pharmaceuticals in environmental and wastewater samples by ultra-high performance liquidchromatography-tandem mass spectrometry, Talanta, 99, 1011~1023(2012). 26. Kim, H. Y., Jung, H. J., Yoo, J. J., Lim, T. H., Lim, Y. K. and Oh, J. E., Occurrence of pesticides in the Nakdong River basin and risk assessment, J. Korean Soc. Environ. Anal., 19, 1~11(2016). Journal of KSEE Vol.40, No.5 May, 2018

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