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J. Korean Soc. Environ. Eng., 37(8), 472~479, 2015 Original Paper http://dx.doi.org/10.4491/ksee.2015.37.8.472 ISSN 1225-5025, e-issn 2383-7810 Occurrence of UV Filters in Nakdong River Basin : Mainstreams, Tributaries and STP Effluents 서창동 손희종 최진택 유평종 장성호 * Chang-Dong Seo Hee-Jong Son Jin-Taek Choi Pyung-Jong Yoo Seong-Ho Jang* 부산광역시상수도사업본부수질연구소 * 부산대학교바이오환경에너지학과 Water Quality Institute, Water Authority *Department of Bioenvironmental Energy, Pusan National University (Received July 15, 2015; Revised August 28, 2015; Accepted August 30, 2015) Abstract : This study was investigated occurrence and distribution patterns of UV filters in Nakdong River basin (mainstream, tributaries and sewage treatment plant (STP) effluents). 5 (EHS, BP-3, 4-MBC, BZC and EHMC) out of 7 UV filters were detected in 5 out of 20 sampling sites (mainstream and tributaries), 7 UV filters were not detected in mainstream samples, and the EHS, BP-3, 4-MBC, BZC and EHMC concentration levels in tributary samples were ND~60.8 ng/l, ND~72.1 ng/l, ND~57.2 ng/l, ND~60.1 ng/l and ND~85.2 ng/l, respectively. 5 (EHS, BP-3, 4-MBC, BZC and EHMC) out of 7 UV filters were detected in effluents of 11 STPs around the Nakdong River basin. The EHS, BP-3, 4-MBC, BZC and EHMC concentration levels in 11 STP effluents were ND~89.3 ng/l, ND~90.8 ng/l, ND~88.1 ng/l, ND~118.5 ng/l and ND~104.4 ng/l, respectively. According to the sampling season, distribution patterns and detected concentrations of 5 UV filters were similar in June and September 2014, but change ranges of distribution patterns and detected concentrations of 5 UV filters were highly variable in April and November 2014. Key Words : UV Filters, Personal Care Products, Nakdong River Basin, STP Effluent, GC-MS/MS 요약 : 낙동강수계에서의자외선차단제류검출현황을조사한결과, 본류및지류 20 지점중 5 지점에서 EHS, BP-3, 4-MBC, BZC 및 EHMC 5 종이검출되었으며, 본류에서는검출되지않았다. 지류의경우는금호강상류, 신천, 금호강하류, 진천천및양산천에서 EHS 가 ND~60.8 ng/l, BP-3 가 ND~72.1 ng/l, 4-MBC 가 ND~57.2 ng/l, BZC 가 ND~60.1 ng/l 및 EHMC 가 ND~ 85.2 ng/l 의농도로검출되었다. 낙동강주변에위치한 11 개하수처리장방류수들에서는 EHS, BP-3, 4-MBC, BZC 및 EHMC 5 종이각각 ND~89.3 ng/l, ND~90.8 ng/l, ND~88.1 ng/l, ND~118.5 ng/l 및 ND~104.4 ng/l 의농도로검출되었다. 낙동강수계및낙동강주변에위치한 11 개하수처리장방류수들에서의계절별자외선차단제류의분포비율은, 6 월과 9 월에는대체적으로유사한분포특성을나타내었으나, 4 월과 11 월에는검출농도뿐만아니라구성종비율의변화폭도매우크게나타났다. 주제어 : 자외선차단제, 개인위생용품, 낙동강수계, 하수처리장방류수, GC-MS/MS 1. 서론 최근사용한후폐기되는과정에서유출되거나생활하는가운데유출되는다양한생활기인오염물질들에대한관심이증가하고있다. 이들생활기인오염물질들은대부분이개인위생용품등으로이들은환경중에서의높은잔류성과생물농축성으로인해새로운유해물질로부각되고있다. 전세계적으로수환경중에서의잔류의약품들및개인위생용품들 (pharmaceuticals and personal care products, PPCPs) 의검출및분포에대한조사가활발히진행중이다. 최근에는자외선조사량증가에따른화상, 피부노화및 피부암등으로부터피부를보호하기위한자외선차단제품 의사용량이급증하는추세에있다. 1) 자외선차단을위해사용되는자외선차단물질은유기계와무기계로나뉘며, 2) para-amino benzoate계, cinnamate계, benzophenone계, dibenzoylmethane계, camphor derivative계및 benzimidazole계등 의유기계와 titanium dioxide (TiO 2) 와 zinc oxide (ZnO) 의 무기계가있으며, 무기계에비해유기계의사용량이월등히 많은것으로알려져있다. 3~5) 유기계자외선차단제는자외선방지크림뿐만아니라일반적으로미용목적으로사용되는스킨, 크림및로션과같 은각종화장품류, 헤어스프레이및샴푸와같은다양한 생활용품등에함유되어있으며, 그사용량은해마다증가 하고있는추세이다. 각종생활용품등에첨가되는자외선차단제의함유량은 0.1%~10% 정도인것으로보고되고있다. 6) 최근에는자외선조사량의증가에따라자외선차단지수 (sun protect factors, SPFs) 가높은제품의제조및판매량 이급증하고있으며, 또한, 섬유, 플라스틱, 페인트및자동차광택제등에도제품의보호를위해첨가된다. 7) 자외선 차단제들의수환경중으로유입경로는계곡및강에서물 놀이나수영을통해직접유입되거나샤워및세탁후가정 하수로배출된자외선차단제들이하수처리장에서완전히 제거되지않고강이나호수등으로유출되는간접적인유 입경로가있다. 8~10) 하수처리공정에서의자외선차단제류 의제거특성을평가한연구결과에서 2-phenylbenzimidazole- 5-sulfonic acid (PBSA) 는 21% 정도의제거율을나타내었 Corresponding author E-mail: menuturk@hanmail.net Tel: 051-669-4788 Fax: 051-669-4669

J. Korean Soc. Environ. Eng. 473 으며, 2-hydroxy-4-methoxybenzophenone (benzophenone-3, BP-3) 와 5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid (benzophenone-4, BP-4) 의경우는 60% 정도의제거율을나 타낸것으로보고되었다. 11) 지표수에서의최대검출농도는 하절기에 2,700 ng/l 에육박하였으며 8,12) 일부유기계자외 선차단제류는친유성 (lipophilic) 으로인해높은생물농축 성을나타내며, 어류를비롯한다양한수생생물들에서고 농도로검출된다. 12~15) 또한, 이들의생체내에서발정및항 발정호르몬작용 (estrogenic and antiestrogenic activity) 을 유발하는것으로알려져있다. 16,17) 유기계자외선차단제인 BP-3 와 BP-4 는어류의성호르몬을교란하여생식에악영향 을끼치며, 간과콩팥에장기독성 (chronic toxicity) 을일으키기도한다. 15,18~20) 본연구에서는최근수중에함유된미량오염물질들의전 처리에간편하면서도효율적인교반막대추출법 (stir bar sorptive extraction, SBSE) 을이용 21,22) 하여낙동강수계의본류, 주요지천및하수처리장의방류수에함유된유기계자외선차단제 7종에대한수환경에서의잔류량평가및물질별검 출특성을분석함으로써향후생활기인오염물질의관리방 안마련을위한기초자료를제공하고자하였다. 2. 실험재료및방법 2.1. 표준물질 유기계자외선차단제 7종은 isoamyl benzoate (IBZ), ethylhexyl salicylate (EHS), homosalate (HS), benzophenone-3 (BP-3), 4-methylbenzylidene-camphor (4-MBC), benzylcinnamate (BZC), ethylhexyl-methoxycinnamate (EHMC) 이며, Sigmaaldrich사 (USA), TCI사 (Japan) 및 Accustandard사 (USA) 의제품을사용하였고, 내부표준물질로사용된 BP-d 10 은 Sigmaaldrich사 (USA) 의제품을사용하였다. 본실험에사용된자외선차단제 7종의물리 화학적특성을 Table 1에나타내었다. 2.2. 낙동강및하수처리장방류수채수시료는 2014년 4월, 6월, 9월및 11월에걸쳐 4회채수하였으며, 1 L 갈색유리병에채수한후시료의변질을막기위해 0.5% 메탄올 (v/v) 을첨가하여분석전까지 4 로냉장보관하였다. 시료채수지점은낙동강본류 11지점, 지류 9지점및낙동강 ( 본류및지류 ) 으로방류되는하수처리장 ( 처리용량 50,000 톤 / 일이상 ) 방류수 11지점을선택하여채수하였다. 낙동강 S1: Banbyeon-cheon (Yongjeonggyo) S2: Andong (Younghodaegyo) S3: Naseong-cheon (Gyeongjingyo) S4: Sangju (Sangpunggyo) S5: Nakdong (Nakdangyo) S6: Gam-cheon (Seonjugyo) S7: Gumi (Gumigyo) S8: Woegwan (Woegwangyo) S9: Geumho-up (Mutaegyo) S10: Shin-cheon (Chimsangyo) S11: Guemho-down (Gangchanggyo) S12: Jincheon-cheon (Gura2gyo) S13: Goryeong (Goryunggyo) S14: Daeam (Ugokgyo) S15: Jeokpo (Jeokpogyo) S16: Namgang (Songdogyo) S17: Namji (Namjigyo) S18: Samrangjin (Samrangjingyo) S19: Mulgeum (Withdrawl point) S20: Yangsan-cheon (Hopodaegyo) Fig. 1. Description of the sampling sites in Nakdong river basin. Table 1. Physico-chemical properties of 7 UV filters Compounds Abbreviation CAS No. M.W. Molecular formula Log K ow Isoamyl benzoate IBZ 94-46-2 192.2 C 12H 16O 2 4.14 Ethylhexyl salicylate EHS 118-60-5 250.3 C 15H 22O 3 5.97 a) Homosalate HS 118-56-9 262.3 C 16H 22O 3 - Benzophenone-3 BP-3 131-57-7 228.2 C 14H 12O 3 3.79 a) 4-methylbenzylidene-camphor 4-MBC 36861-47-9 254.4 C 18H 22O 4.95 a) Benzylcinamate BZC 103-41-3 238.3 C 16H 14O 2 - Ethylhexyl-methoxycinnamate EHMC 5466-77-3 290.4 C 18H 26O 3 5.80 a) a) Experimental values from database of physico-chemical properties. Syracuse Research Corporation: http://www.syrres.com/esc/physdemo.htm. 대한환경공학회지제 37 권제 8 호 2015 년 8 월

474 J. Korean Soc. Environ. Eng. 서창동 손희종 최진택 유평종 장성호 Table 2. Description of the 11 surveyed sewage treatment plants (www.konetic.or.kr) STPs Process Capacity (ton/day) Sources Effluent 1 AS a) 108,000 domestic sewage, feces and urine, livestock wastewater main stream 2 AS a) 80,000 domestic sewage, industrial wastewater tributary 3 AS a) +DNR b) 60,000 - tributary 4 A 2O 50,000 domestic sewage, rainwater, industrial wastewater tributary 5 DNR 330,000 domestic sewage, industrial wastewater, rainwater, sanitized feces and urine main stream 6 A 2O 680,000 domestic sewage, rainwater, food waste disposal facility effluent tributary 7 A 2O 400,000 domestic sewage, industrial wastewater, sanitized feces and urine, landfill leachate tributary 8 A 2O 170,000 domestic sewage, rainwater tributary 9 A 2O 520,000 domestic sewage, rainwater, sanitized feces and urine tributary 10 CNR c) 150,000 - tributary 11 ASA d) 98,000 domestic sewage, rainwater, feces and urine tributary a) AS : activated sludge process, b) DNR : Daewoo nutrient removal process (modified A 2O process), c) CNR : Cilium nutrient removal process (modified A 2O process), d) ASA : Advanced step aeration process 본류 ( ), 지류 ( ) 및하수처리장방류수 ( ) 에대한채수지 점을 Fig. 1 에나타내었으며, Table 2 에는 11 개하수처리장 의처리공정, 용량및유입원등을나타내었다. 2.3. 시료전처리및기기분석 22) 시료수의전처리는교반막대추출법 (SBSE) 을이용하였 으며, 교반막대추출시 40 ml VOC 바이알에시료수 40 Table 3. Analytical conditions of the TD and GC - Pre-purge : 2 min - Desorption temperature : 270 - Desorption time : 10 min - Trap setting pre-trap fire purge 1 min, trap low 10 heating rate : 100 /sec trap high 300, trap hold 5 min - Split flow (ratio) : 9 ml/min (10 : 1) - Flow path temp. : 180 GC - Column: 60 m (L) 250 μm (ID) 0.25 μm (film thickness) - Oven temp. Initial Temp. 60, Hold 2 min 1st rate 10 to 200, Hold 10 min 2nd rate 10 to 280, Hold 12 min Table 4. Analytical parameters of MS/MS for UV filters Compounds RT (min) Precursor (m/z) TD Quantification (collision energy) Product (m/z) Confirmation (collision energy) IBZ 19.320 105 77 (10 V) 51 (40 V) BP-d10 (IS) 23.768 110 82 (20 V) 54 (40 V) EHS 28.698 120 92 (10 V) 63 (40 V) HS 30.971 109 67 (10 V) 81 (20 V) BP-3 34.065 151 52 (40 V) 95 (20 V) 4-MBC 34.641 254 105 (30 V) 106 (20 V) BZC 35.265 131 103 (10 V) 77 (30 V) EHMC 38.952 178 161 (20 V) 133 (20 V) ml를취한후시료수의 ph를 7로조절하였으며, PDMS (poyldimethyl siloxane) 가내외부에코팅되어있는교반막대 (32 mm SPE-tD, Markes, UK) 를넣어 1,000 rpm 으로 120 분 간흡착한후정제수로세척, 수분을제거하여분석에사용 하였다. 수중의자외선차단제류들을교반막대 (Markes, UK) 에흡착시킨후 Markes 사의 thermal desorber (TD-100, Markes, UK) 를이용하여 300 에서탈착시켜 GC-MS/MS (7890N, Agilent, USA / 7000 triple Quad, Agilent, USA) 로주입하였 다. TD의흡착관 (cold trap) 은 general purpose hydrophobic trap (U-T2GPH-2S, Markes, UK) 을사용하였고, GC 컬럼은 DB-5MS (J&W Scientific, USA) 를사용하였다. TD와 GC 및 MS/MS의분석조건을 Table 3과 4에각각나타내었다. 모든시료수에서자외선차단제류들의 LOQ (limit of quantification) 는 6.8~27.5 ng/l 범위였다. 3. 결과및고찰 3.1. 낙동강수계에서의자외선차단제류검출현황및특성 2014 년 4 월, 6 월, 9 월및 11 월에채수하여분석한낙동강 본류 11지점과지류 9지점에서검출된자외선차단제류 5 종의검출현황을 Table 5에나타내었다. 낙동강본류및지류의 20개채수지점중본류에위치한 채수지점들에서는검출되지않았으며, 지류들중에서도금 호강상류 (S9), 신천 (S10), 금호강하류 (S11), 진천천 (S12) 및 양산천 (S20) 에서만 EHS, BP-3, 4-MBC, BZC 및 EHMC 5 종이검출되었다. 이들지류 5지점들은직접적으로하수처 리장방류수의영향을받고있는지류들로금호강과신천 (S9~S11) 및진천천 (S12) 은 STP6~STP9 가위치하고있으 며, 양산천 (S20) 은 STP11 이위치하고있어이들하수처리 장들의방류수에함유된자외선차단제류들이영향을미친 것으로보이며, 서등 23) 과손등 24) 의연구결과에서도하수 처리장방류수에서기인하는인공사향물질이나과불화화 Journal of KSEE Vol.37, No.8 August, 2015

J. Korean Soc. Environ. Eng. 475 Table 5. Detected concentrations (ng/l) of 5 UV filters in Nakdong river basin (20 sites) from Jun. to Nov. 2014 Sampling site EHS BP-3 4-MBC BZC EHMC Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov S1 : Banbyeon-cheon a) ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S2 : Andong ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S3 : Naseong-cheon a) ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S4 : Sangju ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S5 : Nakdong ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S6 : Gam-cheon a) ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S7 : Gumi ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S8 : Woegwan ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S9 : Geumho-up a) <LOD <LOQ 18.1 <LOD <LOQ 11.4 11.2 <LOD ND <LOQ <LOQ <LOD <LOD <LOQ <LOD <LOD <LOD <LOQ <LOQ <LOD S10 : Shin-cheon a) <LOQ 15.1 14.2 <LOD 11.2 23.8 19.2 <LOQ <LOQ 23.1 20.9 <LOD <LOD <LOQ 20.2 <LOD <LOD 27.6 <LOQ <LOD S11 : Guemho-down a) <LOQ 14.0 12.7 <LOQ <LOQ 26.7 22.3 <LOQ <LOQ 22.6 21.2 <LOQ ND 23.7 20.1 <LOD <LOQ 28.3 <LOQ <LOD S12 : Jincheon-cheon a) 14.2 60.8 50.3 <LOQ 30.6 72.1 54.0 12.7 <LOQ 57.2 47.4 22.4 ND 60.1 47.0 <LOQ 42.1 85.2 74.4 <LOQ S13 : Goryeong ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S14 : Daeam ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S15 : Jeokpo ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S16 : Namgang a) ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S17 : Namji ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S18 : Samrangjin ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S19 : Mulgeum ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S20 : Yangsan-cheon a) ND 23.4 <LOQ ND ND 32.2 20.5 ND <LOQ 23.2 <LOQ ND ND 22.5 <LOQ ND <LOD 30.8 <LOQ ND Avg. 14.2 28.3 23.8-20.9 33.2 25.4 12.7-31.5 29.8 22.4-35.4 29.1-42.1 43.0 74.4 - SD - 22.1 17.8-13.7 23.0 16.5 - - 17.1 15.2 - - 21.4 15,5 - - 28.2 - - Min. ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND Max. 14.2 60.8 50.3 <LOQ 30.6 72.1 54.0 12.7 <LOQ 57.2 47.4 22.4 <LOD 60.1 47.0 <LOQ 42.1 85.2 74.4 <LOQ DF 1/20 4/20 4/20 0/20 2/20 5/20 5/20 1/20 0/20 4/20 3/20 1/20 0/20 3/20 3/20 0/20 1/20 4/20 1/20 0/20 a) tributary, Avg : average, SD : standard deviation, DF : detection frequency 합물과같은미량오염물질들이비교적고농도로검출되는것으로보고하고있다. Fig. 2에서와같이채수시기에따른이들지류들 (S9~S12 및 S20) 에서의검출농도를살펴보면 4월에는 11.2~86.9 ng/l 의농도로검출되었으나 6월과 9월에는각각 11.4~335.4 ng/l 및 20.5~273.1 ng/l의농도범위로검출되었으며, 11월에는진천천 (S12) 에서만 35.1 ng/l의농도로검출되었다. 비교적 저농도로검출된 4월과 11월에는검출된지류들의수도각각 2지점 (S10과 S12) 과 1지점 (S12) 으로 Fig. 2(b) 와 (c) 에나타낸 6월과 9월의결과에비해검출농도와검출빈도가낮았다. 이는자외선량이증가하는 6월과 9월의경우, 자외선차단제류함량이높은각종개인위생용품들의사용량증가에기인한것으로이러한현상은해변과하수처리장방류수가영향을미치는지역에서의자외선차단제류의검 Fig. 2. Detected concentrations (numerical, ng/l) and proportion rates of UV filters in 5 tributaries of Nakdong river. 대한환경공학회지제 37 권제 8 호 2015 년 8 월

476 J. Korean Soc. Environ. Eng. 서창동 손희종 최진택 유평종 장성호 출특성을조사한 Li 등 25) 과 Rodríguez 등 26) 의연구결과에 서도보고되었다. 4월 ~11월까지 5개 ( 금호강상류 (S9), 신천 (S10), 금호강하 류 (S11), 진천천 (S12) 및양산천 (S20)) 의지류들에서검출된 자외선차단제류들의구성비율을 Fig. 2 에나타내었다. 자외 선차단제류들의구성비율을나타낸 Fig. 2 에서자외선차 단제류가 1~2 개의지류에서만검출된 4 월과 11 월의결과 를제외한 6 월과 8 월의결과를보면 6 월의 S9( 금호강상 류 ) 와 8월의 S20( 양산천 ) 을제외하면검출된지천에서 EHS, BP-3, 4-MBC, BZC 및 EHMC의구성비율이유사하게나 타났다. 이것은다양한종류의자외선차단제류들이다양한 제품들에함유되고있으며, 직 간접적인경로를통하여수 계로유출되는것을의미한다. 3.2. 하수처리장방류수에서의자외선차단제류검출현황및특성낙동강본류와지류로방류되는하수처리장 (STP) 중에서 50,000 m 3 /day 이상의처리용량을가진 11 곳의하수처리장 최종방류수를분석한결과를 Fig. 3에나타내었다. 4월, 6월, 8월및 11월에채수한시료수들에대한결과를살펴보면 7 종의자외선차단제류들중에서 EHS, BP-3, 4-MBC, BZC 및 EHMC 5종이검출되었다. 특히, STP8과 STP9의방류수 에서의자외선차단제류들의검출농도가각각 61.1~413.8 ng/l 및 58.0~437.8 ng/l의범위로나타나가장높은검출 농도를나타내었다. 또한, STP7 의경우는 ND~100.6 ng/l 로 11 개하수처리장중에서가장낮은검출농도를나타내었으 며, 9 월의경우는 EHMC 단 1 종만이검출되었다. 이러한 이유로는유입수중의공업폐수비율이타하수처리장들에 비해높아개인위생용품에서기인하는자외선차단제류들 의유입농도가낮기때문인것으로판단된다. 또한, 낙동강 5 개지천들에서의자외선차단제류들의검출농도와구성 비율을나타낸 Fig. 2에서와같이 Fig. 3의 4월 (a) 과 11월 (d) 에서의경우에도전체적으로하수처리장방류수에서의검출 농도가낮게나타나고있으며, 구성종의수도적은것을알수있다. 이는하수처리장의처리효율과는무관하게하수처리장유입수중의자외선차단제류들의유입농도가 6월과 9월에비해낮기때문인것으로판단된다. 25,26) 하수처리장방류수의경우도앞에서서술한낙동강지류들의검출특성결과와마찬가지로채수시기에따라검출농도뿐만아니라구성종비율의변화폭도매우큰것으로조사되었다. 중국홍콩의 5개하수처리장방류수에대해 12종의자외선차단제류검출특성을조사한 Tsui 등의연구결과 27) 에서는방류수중의자외선차단제류의검출농도는 19.3~2,671.4 ng/l로나타났고, 주요검출종은 BP-3, EHMC, BMDM (butyl methoxydibenzoylmethane) 및 BP-4 순으로보고하고있으며, 각각의하수처리장방류수에함유된자외선차단제류의구성종들은유사하게나타났으나, 이들의검출농도는하수처리장에따라많은차이를보였다. 또한, 호주의한하수처리장을대상으로계절변화에따라처리공정별로 6종의자외선차단제류에대한제거특성을조사한 Liu 등 28) 의연구결과에서는 BP-3와 4-MBC가주요검출종이었으며, 검출농도는각각 32 ng/l~273 ng/l 및 ND~90 ng/l로보고하고있다. 스위스의 11개하수처리장공정별자외선차단제류의제거특성을연구한 Balmer 등의연구결과 8) 에서는하수처리공정을거치면서 4-MBC, BP-3 및 EHMC의제거율이각각 18%~97%, 68%~99% 및 97%~99% 의범위로보고하고있어하수처리공정에서비교적높은제거율을보이는것으로나타났다. Kupper 등의연구결과 29) 에서는자외선차단제류들은활성슬러지에대한흡착제거율뿐만아니라생물분해율또한높기때문에하수처리공정에서의제거율이다른개인위생용품기인오염물질 ( 합성향물질등 ) 들에비해높은것으로보고하고있다. Table 6에는 4, 6, 9월및 11월에채수한하수처리장방류수에서검출된 EHS, BP-3, 4-MBC, BZC 및 EHMC의평균검출농도, 최소및최대검출농도및검출빈도 (detection fre- Fig. 3. Detected concentrations (numerical, ng/l) and proportion rates of UV filters in final effluents of 11 STPs. Journal of KSEE Vol.37, No.8 August, 2015

J. Korean Soc. Environ. Eng. 477 Table 6. Concentration levels of UV filters in the final effluents of 11 STPs EHS BP-3 4-MBC BZC EHMC Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov Apr Jun Sep Nov Avg. 14.1 50.5 31.2 12.6 32.8 55.6 44.8 15.2 22.0 47.3 38.8 24.5 31.5 68.0 42.2-45.7 69.2 52.4 27.9 SD 3.2 25.6 24.1 1.7 19.8 25.7 22.1 3.9 1.1 23.4 18.1 3.2 4.7 35.0 19.2-7.4 24.5 27.4 0.1 Min. ND ND ND ND ND 17.8 ND ND ND 22.6 ND ND ND 22.4 ND - ND ND ND ND Max. 20.4 89.3 70.5 14.9 67.3 90.8 82.1 21.1 23.8 88.1 72.1 29.2 36.3 118.5 72.8-50.9 104.4 93.5 28.0 DF 6/11 10/11 9/11 5/11 9/11 11/11 10/11 6/11 6/11 11/11 10/11 5/11 4/11 11/11 8/11 0/11 2/11 11/11 8/11 2/11 Avg. : average, SD : standard deviation, DF : detection frequency Table 7. Comparison of detected concentrations (ng/l) of UV filters in various water sources around the world Water source Location Total conc. [Analyte No.] Sample No. IBZ EHS HS BP-3 4-MBC BZC EHMC Ref. STP effluent Australia ND~363 [6] 2 NA NA NA 32~273 ND~90 NA NA 28) China 19.3~2,671.4 [12] 17 NA < LOD~128.9 < LOD~154.2 18.4~541.1 < LOD~207.2 NA < LOD~505.2 27) (Hong Kong) Germany 1,010~1,925 [5] 2 NA NA NA < LOQ~96 NA NA NA 30) Germany 131~132 [9] 2 NA < LOD 8~9 42~54 38 NA 11~23 3) Germany 1,326 [4] 1 NA NA NA 431 102 NA 332 31) Spain ND~1,494.5 [9] 5 NA NA NA 7.7~34 ND~23.8 NA NA 32) Switzerland < LOQ~160 [4] 7 NA NA NA NA 50~110 NA 20~40 29) Taiwan 36.1~48.3 [5] 2 NA ND~6.1 ND 12.5~21.4 NA NA NA 33) UK 1~4,485 [4] 1 NA NA NA 143 NA NA NA 34) UK NG [4] 40 NA NA NA < LOQ~2,196 NA NA NA 35) This study ND~437.8 [7] 44 ND ND~89.3 ND ND~90.8 ND~88.1 ND~118.5 ND~104.4 - River water Brazil < LOD [4] 2 NA < LOD NA < LOD NA NA < LOD 36) China 106 [4] 1 NA 8 NA 59 10 NA NA 37) Germany 100~5,303 [5] 3 NA NA NA < LOQ~47 NA NA NA 30) Germany 29~66 [9] 2 NA < LOD < LOD~5 < LOD~30 5~15 NA < LOD~21 3) Japan 1~1,401 [9] 6 NA NA ND ND~4 ND NA 125~1,040 38) Singapore ND [4] 1 NA NA NA ND ND NA NA 39) Spain ND~907.3 [9] 5 NA NA NA ND~37.8 ND~12.6 NA NA 32) Spain 1,476 [8] 1 NA 146 342 428 264 NA NA 7) Switzerland NG [4] 12 NA NA NA 56~68 12~17 NA 6 14) Taiwan 12.3~32.1 [5] 2 NA ND~10.6 ND 12.3~15.4 NA NA NA 33) Thailand NG [12] 2 NA 28~56 29~59 86~116 < LOD NA 88~95 40) UK NG [4] 40 NA NA NA < LOQ~44 NA NA NA 34) This study ND~335.4 [7] 80 ND ND~60.8 ND ND~72.1 ND~57.2 ND~60,1 ND~85.2 - Lake water Germany 12~473 [9] 4 NA < LOD~51 < LOD~5 < LOD~55 < LOD~148 NA < LOD~33 3) Germany 5,636 [4] 1 NA NA NA 83 2,351 NA 150 31) Germany 11,895 [9] 1 NA 748 < LOD 40 1,140 NA 3,009 41) Switzerland <LOD~56 [4] 11 NA NA NA <LOD~35 <LOD~28 NA <LOD~7 8) NG : not given, NA : not analyzed, ND : not detected quency, DF) 등을간략히요약하여나타내었다. BP-3가 4 월, 6월, 9월및 11월에각각 9개, 11개, 10개및 6개하수처리장의방류수에서검출되어검출빈도가가장높았으며다음으로 4-MBC > EHS > BZC 및 EHMC 순이었다. 세계각국의하수처리장방류수, 하천수및호소수에서검출된자외선차단제류들의농도를비교한것을 Table 7에나 타내었다. Table 7에서볼수있듯이본연구에사용된자외선차단제류 7종중에서 BP-3, 4-MBC 및 EHMC가최대검출농도를나타낸횟수가비교적많았으며, 이는 Table 6 에나타낸낙동강주변에위치한하수처리장방류수에서의검출특성을조사한본연구결과와유사한결과이다. 또한, Table 7에나타낸본연구의결과와외국의경우를비교할 대한환경공학회지제 37 권제 8 호 2015 년 8 월

478 J. Korean Soc. Environ. Eng. 서창동 손희종 최진택 유평종 장성호 경우, 낙동강주변에위치한하수처리장의방류수들과낙동 강의지류들에서의검출농도가비교적낮은편으로나타났다. 4. 결론 낙동강수계와낙동강주변에위치한하수처리장들의최종방류수들에서의자외선차단제류검출특성을조사한결과다음과같은결론을얻을수있었다. 1) 낙동강수계에서자외선차단제류가검출된지점은지 류 5 지점에서 EHS, BP-3, 4-MBC, BZC 및 EHMC 5 종이 검출되었으며, 본류에서는검출되지않았다. 2) 낙동강수계에서의검출농도범위는하수처리장방류 수의영향을받는지류들인금호강상류, 신천, 금호강하류, 진천천및양산천에서 EHS가 ND~60.8 ng/l, BP-3가 ND~ 72.1 ng/l, 4-MBC가 ND~57.2 ng/l, BZC가 ND~60.1 ng/l 및 EHMC가 ND~85.2 ng/l의농도로검출되었다. 3) 낙동강주변에위치한 11개하수처리장방류수들에서 는 EHS, BP-3, 4-MBC, BZC 및 EHMC 5종이각각 ND~89.3 ng/l, ND~90.8 ng/l, ND~88.1 ng/l, ND~118.5 ng/l 및 ND~104.4 ng/l의농도로검출되었으며, 낙동강하류에위 치한 STP11의방류수에서총자외선차단제류농도가 58.0~ 437.8 ng/l로가장높게나타났다. 4) 낙동강수계및낙동강주변에위치한 11개하수처리 장방류수들에서의계절별자외선차단제류분포비율은 6 월과 9월에는유사한분포특성을나타내었으나, 4월과 11 월의경우에는검출농도뿐만아니라구성종비율의변화폭도매우크게나타났다. 5) 외국의지표수및하수처리장방류수에서의검출현황 을조사한연구결과들에서도 BP-3, 4-MBC 및 EHMC 3 종 이주요검출종으로나타났으며, 낙동강의지류들및낙동 강주변에위치한하수처리장방류수들에서의검출농도가 외국에비해서비교적낮은편이었다. References 1. Gasparro, F. P., Sunscreens, skin photobiology, and skin cancer: The need for UVA protection and evaluation of efficacy, Environ. Health Perspect., 108, 71~78(2000). 2. Gasparro, F. P., Mitchnick, M. and Nash, J. F., A review of sunscreen safety and efficacy, Photochem. Photobiol., 68, 243~256(1998). 3. Rodil, R. and Moeder, M., Development of a method for the determination of UV filters in water samples using stir bar sorptive extraction and thermal desorption-gas chromatographymass spectrometry, J. Chromatogr. A, 1179, 81~88(2008). 4. Giokas, D. L., Salvador, A. and Chisvert, A., UV filters: from sunscreens to human body and the environment, Trends Anal. Chem., 26, 360~374(2007). 5. Shaath, N. A., Ultraviolet filters, Photochem. Photobiol. Sci., 9(4), 464~469(2010). 6. Schlumpf, M., Cotton, B., Conscience, M., Haller, V., Steinmann, B. and Lichtensteiger, W., In vitro and in vivo estrogenicity of UV screens, Environ. Health Perspect., 109, 239~244(2001). 7. Román, I. P., Chisvert, A. and Canals, A., Dispersive solidphase extraction based on oleic acid-coated magnetic nanoparticles followed by gas chromatography-mass spectrometry for UV-filter determination in water samples, J. Chromatogr. A, 1218, 2467~2475(2011). 8. Balmer, M. E., Buser, H. R., Müller, M. D. and Poiger, T., Occurrence of some organic UV filters in wastewater, in surface waters, and in fish from Swiss Lakes, Environ. Sci. Technol., 39, 953~962(2005). 9. Peck, A. M., Analytical methods for the determination of persistant ingredients of personal care products in environmental matrices, Anal Bionanal. Chem. 386, 907~939(2006). 10. Plagellat, C., Kupper, T., Furrer, R., Alencastro, L. F., Grandjean, D. and Tarradellas, J., Concentrations and specific loads of UV filters in sewage sludge originating from a monitoring network in Switzerland, Chemosphere., 62, 915~925(2006). 11. Rodil, R., Quintana, J. B., Concha-Grana, E., Lopez-Mahia, P., Muniategui-Lorenzo, S. and Prada-Rodriguez, D., Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain), Chemosphere, 86, 1040~1049(2012). 12. Poiger, T., Buser, H. R., Balmer, M. E., Bergqvist, P. A. and Muller, M. D., Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes, Chemosphere, 55, 951~963(2004). 13. Buser, H. R., Balmer, M. E., Schmid, P. and Kohler, M., Occurrence of UV filters 4-methylbenzylidene camphor and octocrylene in fish from various swiss rivers with inputs from wastewater treatment plants, Environ. Sci. Technol., 40, 1427~1431(2006). 14. Fent, K., Zenker, A. and Rapp. M., Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland, Environ. Pollut., 158, 1817~1824(2010). 15. Gago-Ferreo, P. and Diaz-Cruz, M. S., An overview of UVabsorbing compounds (organic UV filters) in aquatic biota, Anal. Bioanal. Chem., 404, 2597~2610(2012). 16. Fent, K., Kunz, P. Y. and Gomez, E., UV filters in the aquatic environment induce hormonal effects and affect fertility and reproduction in fish, Chimia, 62, 368~375(2008). 17. Santos, A. J. M., Miranda, M. S. and Esteves da Silva, J. C. G., The degradation products of UV filters in aqueous and chlorinated aqueous solutions, Water Res., 46, 3167~ 3176(2012). 18. Blüthgen, N., Zucchi, S. and Fent, K., Effects of the UV filter benzophenone-3 (oxybenzone) at low concentrations in zebrafish (Danio rerio), Toxicol. Appl. Pharmacol., 263, 184~194(2012). Journal of KSEE Vol.37, No.8 August, 2015

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