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1 大韓環境工學會誌總說 - Review Paper 453~ 상수원에서의잔류의약물질검출, 거동, 분포현황및독성 Occurrence of Residual Pharmaceuticals and Fate, Residue and Toxic Effect in Drinking Water Resources 손희종 장성호 *, Hee-Jong Son Seong-Ho Jang*, 부산광역시상수도사업본부수질연구소 * 부산대학교지역환경시스템공학과 Water Quality Institute, Busan Water Authority *Department of Environment System Engineering, Pusan National University (2011 년 6 월 3 일접수, 2011 년 6 월 26 일채택 ) Abstract : Residual pharmaceutical compounds have been recognized as emerging environmental pollutants and are widely distributed all over the world. These compounds cause bioaccumulation and biomagnification during present for a long time in the environment: thereby after adversely biota and human bodies. It is difficult to remove residual pharmaceutical compounds using conventional water/wastewater treatment because of resistant property to photodegradation, biodegradation and chemical decomposition. Moreover, domestic literature data on the pollution of residual pharmaceutical compounds in rivers and lakes are limited. In this paper, species, sources, fate and risk of residual pharmaceutical compounds as well as behavior properties in freshwater resources are demonstrated to encourage the domestic concern about residual pharmaceutical compounds. An extensive review of existing data in the form of figures and tables, encompassing many therapeutic classes are presented. Key Words : Residual Pharmaceutical Compounds, Drinking Water Resource, Occurrence, Fate, Toxic Effect 요약 : 오늘날전세계적으로수환경에서의잔류의약물질들의오염에대한연구결과들이많이보고되고있다. 이들잔류의약물질들은다양한종류와그들이가지는물리 화학적인특성들로인해수환경에서의거동, 오염현황, 영향및독성등도매우다양하여수환경및수처리공정에서의거동을예측 평가하기가어렵다. 선진외국의경우환경중에서의오염현황및사용량을정량화하기위한조사를이미시작하였고, 잔류의약물질들의인체에대한잠재적위험성뿐만아니라상수나하수처리공정에서의제거기술에관한다양한연구도활발히진행하고있다. 그러나국내의경우잔류의약물질들에대해전국주요하천과상수원에대한모니터링결과도매우부족한실정이다. 우선국내의경우는상수원으로이용되는전국주요하천과호소에대해주기적이고체계적인오염현황평가가선행되어야하며, 잔류의약물질들이비교적고농도로검출되는상수원에대해서는주오염원에대한조사도병행되어야한다. 또한, 의약물질사용량은지속적으로증가할것으로전망되기때문에하수처리시설에대한부하도지속적으로증가할것이다. 따라서수환경에서의유해도를저감시키기위해효과적인하수처리공법의도입이절실하며, 상수에대한안전성확보를위해서도잔류의약물질들의수환경중에서의물리 화학적거동에대한면밀한연구가요구된다. 주제어 : 잔류의약물질, 상수원, 현황, 거동, 독성 1. 서론 최근에는환경중의잔류의약물질들로인한환경오염과환경독성에대한많은연구가진행되고있다. 의약물질들은인간의질병치료및예방목적으로사용되거나동물들의질병치료, 예방, 성장촉진및면역력증강등의다양한목적으로동물사료와치료제에혼합되어널리사용되어오고있다. 1) 환경중에잔류하는의약물질들은의약물질생산공정및저정과정에서의유출, 가정과병원을비롯한도시하수, 축산폐수등과같은다양한경로를통하여우리들의상수원인강이나호소로유입되어수중에잔류하며, 2~7) 장시간동안생물학적활성을가지면서수중에존재하기때문에수중생태계에지속적으로위해를가하는것으로알려져있다. 8~10) 의약물질들은특정생리적기능들을가지며, 사람과동 물의체내에투여된후약리적인역할을수행하기전까지는생분해되지않도록제조되기때문에체내에서완전히대사 (metabolite) 되지않고체외로배출된의약물질들은수생태계로유입되어생물축적 (bioaccumulation) 및독성을유발한다. 8,9) 또한, 이들잔류의약물질들은기존의살충제, 소독제등과같은오염물질들과는달리수환경중에서수 ng/l~ 수 µg/l 정도의매우낮은농도로존재하기때문에높은저항력을유발하지않으면서지속적으로수생태계에독성효과를나타낸다. 9,11~13) 의약물질들은사용용도에따라다양한군으로분류되며, 분류군별로그들이가지는물리 화학적인특성도많은차이를나타낸다. Fig. 1에는의약물질들의친 / 소수도에따른분류도를계략적으로나타내었으며, 의약물질군별로다양하게분포되어있는것을볼수있다. 이러한특성차이가환경중에서의이들의거동에많은영향을미치는것으로 Corresponding author jangsh@pusan.ac.kr Tel: Fax:

2 454 大韓環境工學會誌總說손희종 장성호 알려져있다. 14) 즉, 환경중으로유입된의약물질들중소수성이강한의약물질들은토양또는강이나호소의저질중에오랜시간동안잔류하며, 친수성이강한의약물질들은빠른시간내에수환경으로유입된다. 최근에는분석기술의발달로인해수환경에서검출되는잔류의약물질들의종류와검출빈도가높아지고있으며, 15,16) 전세계적으로수환경중에서의잔류의약물질들의검출, 거동, 영향및수처리공정에서의제거에대해많은연구자들이관심을가지고연구중에있다. 17~21) 이미선행된많은연구결과들에서잔류의약물질들이지표수, 2~6) 지하수, 22~24) 해수 25) 및음용수 26~29) 에서검출되는것으로보고되었으며, 이들에의한오염이수생태계뿐만아니라인체에도유해한영향을미칠가능성이높은것으로보고되고있다. 비록, 일부연구결과들에서잔류의약물질들이수생태계에미치는영향이매우미미한정도로평가 30) 된경우도있으나여러세대에걸쳐지속적으로잔류의약물질들에노출된다면우려할만한영향을미칠가능성이높다. 31) 현재전세계적으로다양한종류의의약물질들이생산되어처방되고있으며, 이들의종류및생산량은점점더증가하고있는실정이다. 9,32) 국내의경우, 가축들의질병예방목적으로사용되는항생제들의사용량이다른의약물질군들보다높은것으로보고되고있으며, chlortetracycline과 oxytetracycline의경우는연간사용량이 2,762 톤과 1,549 톤으로다른의약물질들에비해월등히높다. 33) 의약물질사용량은매년증가추세에있고, 한연구결과에따르면네덜란드의의약물질소비량의경우, 2020년에는 2007년에비해 17% 정도증가, 2050년에는 37% 정도까지증가할것으로예측하고있다. 34) 이러한추세는네덜란드뿐만아니라우리나라를비롯해세계각국의경우도비슷한추세이다. 따라서현재수준의의약물질관리시스템과환경중에분 Fig. 1. Level of hydrophilicity and hydrophobicity of pharmaceutical compounds. 14) 포하는잔류의약물질에대한관심으로는향후사용량이지속적으로증가되는의약물질이환경에미치는영향은매우부정적이라할수있다. 따라서본연구에서는미량으로생태계및인간에게유해한영향을미치며, 환경독성이높아기초환경시설에서의공학적인제어가요구되는잔류의약물질들에대해현재까지국내 외에서보고된연구내용을중심으로잔류의약물질들의수생태계로의유입경로, 종류, 거동, 오염현황, 영향및독성등을총체적으로기술하여향후연구방향및연구내용을제시하고자한다. 2. 잔류의약물질유래및수환경으로의유입경로 잔류의약물질들의수환경으로의유입은 Fig. 2에나타낸바와같이시간및공간을달리하여다양하고많은의약물질들이복합적으로수생태계로유입되기때문에수생태계유입량에대한정량적인평가는매우힘들다. 잔류의약물질들의수생태계로의주요유입경로 (Fig. 2) 를살펴보면우선각가정에서복용후인체내에서완전히대사 (metabolize) 되지못한의약물질들과그대사산물 (metabolite) 들이분변을통하여오수정화조로유입되거나각가정에서폐기되는의약물질들이변기나싱크대를통하여오수정화조로유입되어주변의토양으로유출 침출되어지하수를오염시키는경우 36~40) 와오염된토양에잔존하면서강우에의해강이나호소로유입되는경우, 가정, 병원, 의약물질생산시설에서하수구를통해유출되는의약물질들이하수처리장에서완전히처리되지못하고강이나호소로유입되거나하수처리장의슬러지에함유되어있던잔류의약물질들이슬러지처리시토양으로유입되어지하수또는강이나호소로유입되는경우가있으며, 강이나호소에있는양식농가에서사료에함유된의약물질들이강이나호소로직접유입되는경우, 축산농가에서발생하는가축들의분변을포함한축산폐기물에함유되어있던잔류의약물질들이토양에버려져침출되어지하수를오염시키거나강우에의해강이나호소로유입되는경우 41~43) 및각가정에서폐기되는의약물질들이쓰레기로매립장으로유입되어매립장침출수에함유된잔류의약물질들이지하수로침출되는경우 37~40) 등이있다. 각가정의오수정화조와하수처리장의처리공정은잔류의약물질들과같이강한극성을띄는물질들의처리에는부적절하며, 이들의처리효율은이들물질고유의특성과처리공정의설계인자에따라제거율이 0~100% 로많은차이를나타낸다. 44,45) 도시의가정하수의경우는하수처리장으로이송 재처리되어강이나호소로방류되지만시골의경우는각가정의오수정화조에서바로강이나호소로방류되기때문에배출농도는시골지역이높은것으로보고되고있으며, 36) 합류식하수관거를사용하는경우는폭우로 Journal of KSEE Vol.33, No.6 June, 2011

3 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 455 Fig. 2. Origin and routes of residual pharmaceuticals. 35) 인해하수처리장의부하가클경우하수처리장으로유입된하수가그대로강이나호소로방류되어하수중에잔존하는잔류의약물질들이수생태계에영향을미치기도한다. 46) 또한, 최근에는병원에서외래환자들에게경구투여가가능한의약물질들의종류및처방이증가하기때문에각가정에서의의약물질배출량이증가하는추세다. 47) 3. 잔류의약물질의수환경에서의거동 사람과동물의체내에투입된의약물질들은 Fig. 3에나타낸바와같이 2단계의체내대사과정을거치면서다양한생화학적인반응에의해대사산물 (metabolite) 들을생성하며, 48,49) 이들대사산물들은단계를거칠수록친수성화및수용성화가진행되어체내에서의배출이용이하도록유도된다. 50) 따라서 Fig. 4에서볼수있듯이사람과동물의체내에서대사과정을거친후분변을통하여체외로배출시에는체내에서완전히대사 (metabolize) 되지못한의약물질 (parent compound, PC) 과대사산물 (metabolite, M) 의형태로배출 19) 되어 Fig. 2와같이다양한경로를통하여수환경으로유입된다. 수환경으로유입된잔류의약물질들은수 ng/l~ 수 µg/l의낮은농도로잔존하면서수중의콜로이드성물질, 부유성입자물질또는저질에흡착되거나용존성유기물질들에흡착또는결합되어존재 51) 하면서태양광에의한광분해 (photodegradation) 나수중미생물에의한생물분해 (biodegradation) 등과같이수환경에서의생물학적또 Fig. 4. Transformation pathways of pharmaceuticals, PC: parent compound, M: metabolite, TP: transformation product, WWTP: waste water treatment plant, DWT: drinking water treatments. 19) 는물리 화학적인요인들에의해구조적인변형 (transformation) 이유발되며, 52,53) 이러한반응들은복합적으로일어난다. 54) 3.1. 광분해 (photodegradation) 수환경으로유입된대부분의잔류의약물질들은직접또는간접적으로태양광에의해광분해된다. 52,53,55) 직접적인광분해형태는수중의잔류의약물질들이태양광을흡수하여변형을유발하는경우이고, 간접적인광분해의경우는수중에존재하는질산염 (nitrate) 및휴믹산 (humic acid) 들과같은감광제 (photosensitize) 들이태양광과반응하여생성되는 OH 라디칼과같은산화제에의해분해되는경우이다. 52,53,55~58) 광분해의경우는태양광의강도, 수역의부영양화정도와유기물질조성, 수심, 수역의위도 (latitude) 및계절등과같은요소에많은영향을받는다. 8,59) 잔류의약물질들의광분해부산물들은매우다양하며, 이들도수생태계에유해한영향을미친다. 항경련제 (antiepileptic) 인 carbamazepine의경우, 광분해부산물로독성, 돌연변이성 (mutagenicity) 및발암성 (carcinogenicity) 을나타내는 acridine을생성하며, 60) Andreozzi 등은 carbamazepine의광분해반감기가대략 100일정도로 sulfamethoxazole의 2.4 일, diclofenac의 5일, ofloxacin의 10.6일및 propranolol의 16.8일에비해매우긴것으로보고하고있다. 61) 항종양제 (antineoplastic) 인 cyclophosphamide와 ifosfamide는직접적인 Fig. 3. Schematic representation of pharmaceutical bio-transformation to increase their polarity. 31) 대한환경공학회지제 33 권제 6 호 2011 년 6 월

4 456 大韓環境工學會誌總說손희종 장성호 광분해보다는간접적인광분해메카니즘에의해부산물들을생성하는것으로알려져있다. 58) 비스테로이드성항염증제 (NSAID) 인 diclofenac과 β-blocker인 propranolol은광분해에의한반감기가 24시간이내로매우짧은것으로알려져있으며, 61~63) 호수로유입된 diclofenac의 90% 이상이직접적인광분해로제거된다. 61,64,65) Diclofenac의광분해부산물로는세포용해 (cell lysis) 를유발하는 chlorocarbazole이생성되며, 이물질은 diclofenac 보다세포용해율이높은것으로알려져있다. 66) 또한, sulfonamide계항생제들의경우는직접적인광분해메카니즘에의해다양한광분해부산물들이생성 67) 되지만 tetracycline계항생제들의경우는대부분강이나호소의저질에흡착되기때문에광분해메카니즘및광분해부산물에대해서는보고된것이없다. 56,68) 또한, 수중에휴믹산과같은감광제가존재할경우에 carbamazepine과 diclofenac의광분해율은저감되며, sulfamethoxazole, clofibric acid, oflaxocin 및 propranolol의광분해율은증가되는것으로알려져있다. 61) 이처럼잔류의약물질들의종류가다양하며, 물질고유의특성또한많은차이를보이기때문에광분해메카니즘과광분해속도는다양하게나타나고있다. 69,70) 3.2. 생물분해 (biodegradation) 수환경으로유입된잔류의약물질들은수중에서식하는미생물들에의해분해되어변형을유발한다. 비스테로이드성항염증제 (NSAID) 계열인 ibuprofen의경우여름철에강하구에서효과적으로생물분해 (~50%) 되며, 71), Kagel 등 72) 은 Sphingomonas sp. 를이용하여 ibuprofen의생물분해능을평가하였다. 또한, Santos 등 73) 은 1년간스페인남부의 63개의하수처리장의생물학적처리공정에서의 ibuprofen의제거율을조사한결과, 평균 87.5% 정도제거되는것으로보고하였다. Alexy 등 74) 과 Gartiser 등 75) 은 17~18종의항생제에대해생분해능을평가한결과, penicillin-g를제외한나머지항생물질들은매우낮은생분해율을나타내었다고보고하였다. Yamamoto 등 76) 은 8종의의약물질 (acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid 및 propranolol) 에대한생물분해능을조사한결과에서이들물질들이생물분해에대해저항성을가지는것으로보고하고있다. X-ray 조영제인 iopromide는장기간의생분해실험결과, 2종류의대사산물이생성되었고, 77,78) 태양광을차단한경우가차단하지않은경우보다 4배정도높은 iopromide의 free amine 생분해율 (90% 정도 ) 을나타내었다고보고하였다. 79) 항생제인 triclosan은토양에서의생물분해에의한반감기가 18일정도이며, 80) 하수처리장의활성슬러지공정에서생물분해에의해 80% 이상제거되는것으로알려져있다. 81) 성호르몬인 estrone의경우는하수처리장의혐기성생물학적처리에의해 17α-estradiol로전환되기때문에하수리장의방류수에서 estrone 보다 17α-estradiol의검출농도가높다. 82) 따라서잔류의약물질들이하수처리장의생물학적처리공정을거친후생물분해되어제거되었더라도 잔류의약물질들의독성들이완전제거되었다고판단하기는어려우며, 생물학적처리과정에서생성되는독성을내포한예측불가능한대사산물들에대한주의가필요하다. 31,59,83) 3.3. 흡착 (sorption) 수환경에서의잔류의약물질들이저질에흡착되거나용존유기물질과결합 (complexation) 하는비율은앞서기술한광분해나생물분해에비해매우높다. 흡착은주로저질의표층에서일어나며, 흡착율은잔류의약물질들의물리 화학적특성들과저질의지질적특성들에의해많이좌우된다. 잔류의약물질들이가지는극성, 용존성및낮은휘발성과같은일반적인특성들로인해수환경중에서의이동성 (mobility) 과저질, 토양및슬러지에서의잔존율이높다. 42) 잔류의약물질들의토양과저질에서의흡착특성을연구한결과들에서잔류의약물질들의물-옥탄올분배계수 (octanolwater partitioning coefficients, log K ow) 와토양 / 저질에서의흡착율은높은상관성을나타내며, 68,84~86) 이것은토양 / 저질에함유된유기물질들과수중의잔류의약물질들과의소수성인력 (hydrophobic interaction) 에의한것으로보고하고있다. 68,87) 또한, 최근의연구결과에서는잔류의약물질을구성하는몇몇관능기들의중성 ph에서의이온화영향이토양 / 저질에서의흡착에많은영향을미치는것으로보고하고있다. 88) 잔류의약물질이함유된물의 ph와잔류의약물질자체의산 / 염기적특성이수중의유기물질과잔류의약물질간의인력 (interaction) 에많은영향을미친다. 89~91) 대부분의비스테로이드성항염증제 (NSAID) 들은산성물질인반면, β- blocker, 호르몬류, 페놀계항생제및 macrolide들은염기성물질 (basic compound) 이며, 92,93) ofloxacin, ciprofloxacin, norfloxacin 등의많은항생제들은산성과염기성특성을동시에가지고있다. 46) Tetracycline계항생제들은수중의다가양이온금속종 (Ca 2+ 등 ) 들과결합하여염을형성하는것으로알려져있다. 43) Rogers는 log K ow 값을이용하여토양이나슬러지에서의흡착율을평가한연구 94) 에서물질들의 log K ow 값의분포범위에따라 log K ow <2.5( 낮은흡착율 ), log K ow 2.5~4.0( 보통 ) 및 log K ow >4.0( 높은흡착율 ) 의 3 부분으로나누어토양이나슬러지에서의흡착율을평가하였다. 또한, 잔류의약물질들중거대분자량을가진경우는쉽게저질 / 토양에흡착되며, 아민 (amine) 기를가진잔류의약물질들도흡착율이높은것으로알려져있다. 76) 몇몇잔류의약물질들의광분해, 생물분해및저질 / 토양에대한흡착능을평가한결과를 Table 1에요약하여나타내었다. Table 1에서볼수있듯이 carbamazepine의경우는인체내에서는매우빠른대사반응을나타내지만수환경중에서는매우안정적으로존재하며, 78) 성호르몬인 17αethinylestradiol은생물분해에대한내성을가지지만저질 / 슬러지에대한흡착율은다른물질들에비해높은것으로평가되었다. Journal of KSEE Vol.33, No.6 June, 2011

5 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 457 Table 1. Fate processes identified to remove pharmaceuticals from surface water Pharmaceuticals Photodegradation (sunlight) ref) Biodegradation ref) Sorption ref) Acetaminophen (NSAID) Atenolol (β-blockers) Carbamazepine (Antiepileptic) Ibuprofen (NSAID) Indomethacin (NSAID) Mefenamic acid (NSAID) Propranolol (β-blockers) 17α-ethinylestradiol (sex hormone) Slow (t p1/2: 35~56 h, k p: 0.013~0.020 h -1 ) Slow (t p1/2: 77~730 h, k p: ~0.009 h -1 ) Poor (t p1/2: 84~2100 h, k p: ~ h -1 ) Poor (t p1/2: 600~9900 h, k p: ~ h -1 ) Slow (t p1/2: 16~21 h, k p: 0.034~0.044 h -1 ) Slow (t p1/2: 78~97 h, k p: ~ h -1 ) Easy (t p1/2: 4.4~8.3 h, k p: 0.084~0.12 h -1 ) 61,76 76, ,76 Slow (t b1/2: 50~1400 h, k b: ~0.014 h -1 ) Slow (t b1/2: 48~2900 h, k b: ~ h -1 ) Poor (t b1/2: 3000~5600 h, k b: ~ h -1 ) Slow (aerobic) (t b1/2: 250~480 h, k b: ~ h -1 ) Poor (anaerobic) (t b1/2: 1198 h, k b: h -1 ) Slow (t b1/2: 410~430 h, k b: ~ h -1 ) Poor (t b1/2: 300~2500 h, k b: ~0.011 h -1 ) Slow (t b1/2: 36~620 h, k b: ~ h -1 ) 76 Log K d: 0.28~1.04 (sediment) 76,87 76,96 Log K d: 0~0.94 (sediment) 76,87, ,98 Log K d: -1.15~0.32 (sediment) Log K d: 1.31~1.83 (sludge) Log Kd: -1.19~0.79 (sediment) Log K d: 1.00~1.78 (sludge) 76,97 76,97 76 Log K d: -1.00~0.88 (sediment) Log K d: 0.70~1.40 (sediment) 76 76,96 Log K d: 0.23~2.28 (sediment) 76,96 Slow (t p1/2: < 36 h) 99 Persistent 100 Log K d: 2.08~2.85 (sludge) 97 k p = photodegradation coefficient, k b = biodegradation coefficient, k d = sorption coefficient, t p1/2=photodegradation half-life, t b1/2=biodegradation half-life. 4. 수중에서검출되는잔류의약물질들종류및특성 1996년에서 2009년사이에의약물질의연구및개발에관한논문 183편을분석한연구결과에서다양한종류의의약물질들이개발되고있으며, 그중에서항생제, 비스테로이드성항염증제 (non-steroidal anti-inflammatory drugs, NSAID) 및고지혈증치료제 (blood lipid lowering agent, BLLA) 가차지하는비율이월등히높은것으로보고하고있다. 21) 개 Fig. 5. Therapeutic classes detected in the environment, expressed in relative percentage. Data collected from 134 articles published between 1997 and ) 발된신종의약물질들은인간과가축을대상으로처방 사용된후에는 Fig. 2에나타낸경로를통해서환경중으로유출될가능성이매우높다. Fig. 5에서볼수있듯이치료용도별로잔류의약물질들이환경에서검출되는비율로평가한경우에도비스테로이드성항염증제 (NSAID) 가 16% 로가장높은비율을차지하였으며, 다음으로항생제가 15% 였고, 고지혈증치료제와호르몬류가 12% 정도차지하는것으로나타나연구개발이활발히진행되는의약물질들이환경에서의검출빈도가높은것으로나타났다. 21) Table 2에는환경중에서검출되는다양한의약물질들을치료용도별로분류하여대사산물들및부산물들과함께나타내었다. 비스테로이드성항염증제 (NSAID) 에는하수처리장방류수및수환경에서의검출빈도가높아서많이알려져있는 diclofenac, 101,102) ibuprofen, 6,103) naproxen, 5,104) 및 acetaminophen 104,105) 등이있으며, 이들은수중의식물성플랑크톤및어류에독성을나타내며, 106,107) 수생태계에미치는독성은 diclofenac이가장큰것으로보고되고있으며, 108) acetaminophen의경우도낮은농도에서독성을유발하는것으로보고되었다. 105) 항생제의경우는 β-lactam계, cycline계, lincosamide계, macrolide계, sulfonamide계, quinolone계, pyrimidine계등매우다양한물질군으로세분화되며, 물질의종류도매우다양하다. 또한, 다른의약물질들에비해서사람이나동물에대해높은농도로처방되기때문에환경으로많은양의항생제들이유입될가능성이매우높다. 21) 따라서항생제의지속적인환경노출로인한항생제저항세균의출현과이로인한항생제치료효과의감소가가장큰문제점으로부각된다. 109,110) 대한환경공학회지제 33 권제 6 호 2011 년 6 월

6 458 大韓環境工學會誌總說손희종 장성호 고지혈증치료제 (blood lipid lowering agent, BLLA) 의경우는지방대사를조절하는의약물질들로혈중콜레스테롤과 tryglyceride의농도를낮추기위해서주로선진국에서많이처방되고있다. 21) 이들은 stain계와 fibrate계로분류되며, 환경중에서는주로 fibrate계가많이검출되는것으로보고되고있다. 21) Fibrate계의 gemfibrozil의경우는내분비 계장애를유발하는것으로보고되었으며, 111) clofibrate의대사산물인 clofibric acid의경우는분해가잘되지않는특징으로인해하수처리장방류수, 112) 지표수, 2,4) 음용수 102) 및북해의바닷물 25) 에서도검출이된다. 성호르몬의경우는경구용피임약의과도한사용으로인해환경중에서의검출농도가증가하고있다. 113,114) Estro- Table 2. Human and veterinary pharmaceuticals, metabolites and degradation products in the environment 19) Therapeutic use Compounds (metabolites ) Antiacid Antiasthmatic Antibiotic β-lactams Cyclines Fluoroquinolones/ Quinolones Lincosamides Macrolides Nitrofurans Phenicols or Propanediols Phenols Pyrimidines Sulfonamides other chemical classes Anticoagulant Antidepressant Anti-diabetic Antiepileptic Antihelminthic Antifungal Antihistamine Antihypertensive Antineoplastic Beta(β)-blocker BLLA Fibrate Stain Bronchodilator Cardiac stimulant Contrast media Diuretic NSAID and analgesic Opioidanalgesic Psycho-stimulant Sex hormone Cimetidine, Ranitidine Albuterol Amoxicillin, Cefuroxime, Ceftriaxone, Penicillin G1/2-benzathine salt, Penicillin V potassium salt Demeclocycline, Doxycycline, Minocycline Oxytetracycline HCl, Chlortetracycline, Tetracycline Ciprofloxacin, Danofloxacin, Difloxacin, Enoxacin, Enrofloxacin, Flumequine, Lomefloxacin, Nalidixic acid, Norfloxacin, Ofloxacin, Oxolonic acid, Pipemidic acid, Sarafloxacin Clindamycin, Lincomycin Azithromycin, Clarithromycin, Erythromycin (Erythromycin-H 2O), Oleandomycin, Roxithromycin, Spiramycin, Tylosin, Tylosin tartrate Furaltadone, Furazolidone, Nitrofurantoin Chloramphenicol Triclosan, Triclocarban, Methyltriclosan Trimethoprim Sulfachlorpyridazine, Sulfadiazine, Sulfadimethoxine, Sulfamerazine, Sulfamethazine, Sulfamethizole, Sulfamethoxazole, Sulfapyridine, Sulfathiazole Carbadox, Cephalexin, Gentamicin sulfate, Imipenem, Metronidazole, Miconazole, Monensin, Nistatin, Ornidazole, Roxarsone, Virginiamycin, Vancomycin hydrochloride Warfarin Amitryptiline, Citalopram, Diazepam (Nordiazepam, Oxazepam), Citalopram, Doxepine, Fluoxetine (Norfluoxetin), Imipramine, Meprobamate, Oxazepam, Paroxetine, Sertraline, Thioridazine, Venlafaxine Metformin, Glibenclamide Carbamazepine (10,11-dihydro dihydroxycarbamazepine, 10,11-dihydro epoxycarbamazepine, 2-,3-hydroxycarbamazepine, 10,11-dihydro-10-hydroxycarbamazepine), Dilantin, Gabapentin, Primidone Ivermectin Clotrimazole Diphenhydramine Diltiazem, Enalapril 5-Fluorouracil, Cyclophosphamide, Epirubicin/Doxorubicin, Ifosfamide, Methotrexate, Tamoxifen Acebutolol, Atenolol, Celiprolol, Metoprolol, Nadolol, Pindolol, Propranolol, Sotalol Bezafibrate, Clofibrate (Clofibric acid), Fenofibrate (Fenofibric acid), Gemfibrozil Atorvastatin (o- and p-hydroxyatorvastatin), Lovastain, Pravastain, Simvastatin (Simvastatin hydroxy acid) Clenbuterol, Salbutamol, Terbutaline Digoxin (Digoxigenin) Diatrizoate, Gadolinium, Iopromide, Iomeprol, Iohexol, Iopamidol Bendroflumethiazide, Furosemide 5-Aminosalicylic acid, Aminopyrine, Aspirin (Salicylic acid), Diclofenac, DMAA(dimethylaminophenazone), Fenoprofen, Flufenamic acid, Flurbiprofen, Ibuprofen, Indomethacin, Ketoprofen, Meclofenamic acid, Mefenamic acid, Naproxen, Nimesulide, Paracetamol(acetaminophen), Phenazone, Propyphenazone, Sulfapyridine, Sulfasalazine, Tolfenamic acid Codeine (Norcodeine), Fentanyl, Morphine (6-Acetylmorphine, Normorphine), Methadone, Tramadol, EDDP Caffeine (1,7-dimethylxanthine), Amphetamine Ethynylestradiol (EE2, Estradiol), Estradiol (E2), Estriol (E3), Estrone (E1), Progesterone, Testosterone Journal of KSEE Vol.33, No.6 June, 2011

7 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 459 gen은환경중에서가장흔히검출되는여성호르몬이며, 경구용피임약에쓰이는대표적인합성 estrogen으로서는 ethinylestradiol (EE2) 이있다. EE2의경우는수중어류들에대해강력한내분비계장애를유발하는것으로알려져있다. 115~118) 환경중에서검출되는 estrogen 농도로는인체에직접적으로영향을미치지는않지만환경중의 estrogen이수생생물에축적 (bioaccumulation) 되어먹이사슬의최상위층에있는사람에게도달할경우에는환경중에서노출되는농도보다훨씬높은농도로노출될수있다. 21) 또한, 수환경중에서대부분 ng/l의농도로검출 119,120) 되지만, 수생태계에는매우유해한농도가될수있다. 21) 항경련제 (antiepileptic) 의경우는주로간질치료제로많이이용되며, 중추신경계에작용하여신경전달물질을억제함으로써신경의활성을전체적으로줄이는기능을한다. 21) 항경련제로흔히이용되는 carbamazepine은 rat를이용한실험에서발암성을나타내었으며, 어류와물벼룩을이용한독성실험에서는수십 µg/l의농도에서어류와물벼룩이폐사하였으나 121) 포유류의경우는돌연변이적특성을나타내지않는것으로보고되었다. 121) 수환경에서의검출빈도가높은 carbamazepine은하수처리장에서의제거율이 7% 미만 122) 으로매우낮아강이나지하수등에서수백 µg/l의농도수준으로검출되었다는보고도있다. 123,124) 이러한결과들은 carbamazepine이수중생태계에심각한위해를가할가능성이있음을의미한다. β-blocker들은고혈압및갑상선기능항진증등의질환에처방되며, 생체내의 β-수용체들을억제하는기능을가지고있다. 가장흔히사용되는 β-blocker는 propranolol이며, 생체내의 β1-수용체와 β2-수용체를모두억제하며, metoprolol 과 atenolol은 β1-수용체를특이적으로억제한다. 21) 어류를비롯한척추동물들은심장, 간및생식기에 β-수용체를가지고있다. 125,126) 따라서지속적으로 β-blocker에노출되면위해를입을가능성이있다. β-blocker들중 propranolol은하수처리장방류수및지표수에서수십 ~ 수백 ng/l로검출되며, 5,112,127) atenolol과 metoprolol 같은다른 β-blocker들의경우도하수처리장방류수, 지표수및지하수에서수백 ng/l까지도검출되는것으로보고되었다. 4,5,22,128) 항우울제 (antidepressant) 는뇌의신경전달물질인 serotonin 의분비를촉진시켜우울, 불안등의감정을줄이는역할을한다. serotonin은호르몬과신경계에작용하여여러가지조절작용과내분비물질로작용하기때문에생체내에서 serotonin의변화는식욕, 면역력, 생식기및기타행동장애로나타날수있다. 8,31) 또한, 하등척추동물과무척추동물은 serotonin에대해아주다른반응을나타내기때문에환경에예상치못한영향을미칠수있다. 21) 수환경중에서의이들의검출농도는 ng/l 수준으로다른잔류의약물질들에비해비교적낮은편으로보고되었다. 3,24,29) 항암제 (antineoplastic) 는인체내의암세포를죽이고성장을억제하는목적으로개발 합성된의약물질로진핵생물 (eukaryotic organism) 들에게는유사한기능을하는것으로 알려져있으며, 47) 많은항암제들이유전독성, 발암성, 기형유발등의부작용을가지고있다. 21) 또한, 인체에투여된항암제의 14~53% 정도가인체내에서대사되지않고뇨와변으로다시배출되어환경에유해한영향을미친다. 114) 항암제들중 cyclophosphamide의경우수환경에서 ng/l~µg/l의범위로검출되며, 6,58,128,129) 다른항암제들은 ng/l의농도비교적낮게검출된다. 21) 조영제 (contrast media) 의경우는 X-선조영제가대표적으로 X-선을이용하여부드러운조직을진단시에진단부위의이미지를선명하게나타내주는역할을한다. 요오드계조영제의경우는매우친수성이강하기때문에수환경중에널리분포하며, 21) 조영제들은인체내에서대사되지않고체내에서배출되며, 이러한이유로하수처리장의생물학적처리공정에서제거율이매우낮다. 21) 따라서하수처리장방류수, 지표수, 지하수및음용수에서도 µg/l 수준으로검출된경우도있다. 22,130~135) 비록여러독성실험결과에서생체독성이낮은것으로알려져있지만수환경에서의지속적노출과먹이사슬에의한생물농축등으로인한생체독성이유발될가능성이있다. 21) 4. 상수원에서의검출및오염현황 세계각국의지표수와지하수와같은상수원수에서의잔류의약물질검출현황을 Fig. 6과 Table 3에나타내었다. Fig. 6에는 Table 3에나타낸세계각국에서검출되는잔류의약물질들중비교적검출농도와검출빈도가높은 59종에대해우리나라를포함하여세계각국의최대검출농도를비교해서함께나타내었다. Fig. 6에나타낸잔류의약물질들을계열별로보면항생제가 25종으로가장높은비율을차지하였으며, NSAID가 8종, 다음으로 β-blocker와조영제가각각 5종으로나타났다. 가장높게검출된잔류의약물질들은 NSAID 계열로나타났으며, acetaminophen의경우는세르비아에서최대 78,170 ng/l의농도로검출되었으며, 다음으로 salicycic acid가캐나다에서최대 17,000 ng/l의농도로검출되었고, diclofenac은독일에서최대 15,033 ng/l의농도로검출되었다. Ibuprofen과 naproxen의경우는캐나다에서각각 6,400 ng/l와 4,500 ng/l의최대검출농도를나타내었다. 국내의경우는 ibuprofen이 414 ng/l로검출되어 NSAID 계열중에서가장높은검출농도를나타내었다. 신경흥분제계열의 caffeine은루마니아에서 11,121 ng/l 의최대검출농도를나타내었으며, 국내의최대검출농도는 480 ng/l로나타났다. 또한, 진통 마취제계열의 tramadol은영국에서 7,731 ng/l의최대검출농도를나타내었다. 항생제계열은 triclosan이인도에서 5,160 ng/l의최대검출농도를나타내었으며, sulfamethoxazole, ciprofloxacin 및 norfloxacin의경우는호주에서각각 2,000, 1,300 및 1,150 ng/l의최대검출농도를나타내었고, 국내에서가장높은 대한환경공학회지제 33 권제 6 호 2011 년 6 월

8 460 大韓環境工學會誌總說손희종 장성호 Fig. 6. Maximum detection concentrations of pharmaceuticals in surface waters and groundwaters in the world. Journal of KSEE Vol.33, No.6 June, 2011

9 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 461 Table 3. Summary of pharmaceuticals occurrence in surface waters and groundwaters in the world Therapeutic use Compounds Nation [water source, detected concentration (ng/l), detection frequency (%)] Ref. Antiacid Cimetidine UK (RW, <0.5~220, 0~100), USA (SW, 12, -) 137~139 Antibiotic β-lactam Quinolone Lincosamide Macrolide Phenicol Phenol Pyrimidine Sulfonamide Ranitidine Italy (RW, Max: 38.5, -), Spain (RW, 1.8~4.9, -), UK (RW, <3~73, 0~86), USA (SW, ND~13, -) 137~142 Amoxicillin Australia (SW, Max: 200, 30), China (SW, ND, 0), Italy (RW, ND~9.9, -), UK (RW, <10~522, 0~100), USA (SW, 200, -) 137,138,141,143,144 Penicillin G Australia (SW, Max: 250, 28), USA (SW, 100, -) 137,143 Penicillin V Australia (SW, Max: 100, 10), USA (SW, 100, -) 137,143 Ciprofloxacin Australia (SW, 23~1300, 30), Finland (RW, <24~35, 100), Italy (RW, ND~37.5, -), USA (SW, ND~360, 10) 3,4,137,142,143, 145~150 Enrofloxacin Australia (SW, Max: 300, 44), USA (SW, ND~10, -) 143,146 Lomefloxacin USA (SW, 50, -) 137 Norfloxacin Australia (SW, 30~1150, 78), China (RW, Max: 13~251, 17~100), Finland (RW, <24, 100), USA (SW, 5~50, -) 137,143~145,148 Ofloxacin Finland (RW, <2.6~5, 100), Hong Kong (RW, Max: 16~108, 17~100), Italy (RW, 0.65~306.1, -), USA (SW, 10~50, -) 137,141,144,145,150 Sarafloxacin USA (SW, 5~50, -) 137 Clindamycin Australia (SW, Max: 10, 57) 143 Lincomycin Australia (SW, Max: 50, 67), Italy (RW, 3.1~248.9, -), Korea (SW, 12~165, -), Spain (RW, 13.4~17.9, -), USA (SW & GW, ND~320, 8~17) 3,4,24,137,140,141, 143,146,150,151 Azithromycin Spain (RW, 8.0~17.6, -) 140 Clarithromycin Italy (RW, 0.49~44.76, -), Korea (RW, ND~443, -) 4,123,141,150 Erythromycin Erythromycin-H 2O Italy (RW, 0.8~15.9, -), Korea (SW, ND~137, 63), Spain (RW, 21.4~33.0, -), UK (RW, <10~1022, 17~38), USA (SW, ND~40, ~17) China (RW, 30~636, ~100), Italy (RW, 1.7~30.5, -), Korea (SW, 23~121, -), UK (RW, <0.5~351, 20~100), USA (SW, ND~220, -) 4,7,72,137,140, 141,149,150 3,138,144,146,150~1 54 Oleandomycin Italy (RW, <0.31~74.2, -) 4,150 Roxithromycin Australia (SW, Max: 350, 63), China (RW, 16~169, 92~100), USA (SW, 50~100, -) 3,137,143,144, 152,155 Spiramycin Italy (RW, ND~74.2, -) 4,141,150 Tylosin Chloramphenicol Triclosan Australia (SW, Max: 60, 81), Italy (RW, ND~2.77, -), Spain (RW, 0.5~1.6, -), USA (SW & GW, ND~100, -) China (RW, 41~266, ~100), Singapore (RW, <1~27, -), Switzerland (SW, 10~30, -), UK (RW, <2~40, 0~15) Australia (SW, <3~75, ~100), Canada (RW, <4~8, -), China (SW, 1.2~1023, 100), Germany (SW, <3~90, -), India (RW, 4~5160, 100), Italy (SW, <2.0~4.0, -), Japan (RW, 130~190, 100), Romania (RW, <30~64.3, -), Spain (RW, ND~285, 67~100), Sweden (RW, ND~70, 50), Switzerland (SW, <0.4~20, -), UK (RW, <5~95, 43~80), USA (SW & GW, ND~730, 0~100) 3,4,137,140, 143,146, ,139,144, 152,156,157 5,6,16,27,138, 139,158~179 Triclocarban China (SW, 1.2~338, 100) 165 Triclosan-methyl Spain (SW, ND~12, 0~100) 173,179 Trimethoprim Australia (SW, Max: 150, 64), Canada (SW, Mean: ND~134, -), Korea (SW, ND~5.3, 0~50), Serbia (SW & GW, 24~174, -), Spain (RW, 9.5~22.8, -), Sweden (RW, <1~20, 100), UK (RW, ND~569, 0~100), USA (SW & GW, ND~150, 32~74) 3,5,7,16,137~140,14 2,143,146,147,149,1 54,163,180~182 Sulfadiazine China (RW, 38~336, ~100), Italy (RW, 236, -), USA (SW, 50, -) 137,144,152,183 Sulfadimethoxine Italy (RW, 28~74, -), Korea (SW, ND~240, 0~25), Luxembourg (RW, <0.3~3, -), Spain (RW, ~8.3, -), USA (SW & GW, ND~68, 0~8) 3,23,137,140,146,15 4,183~186 Sulfamerazine Korea (SW, ND~115, 0~13) 154,186 Sulfamethazine Sulfamethoxazole Korea (SW, ND~250, 0~63), Luxembourg (RW, <0.3, -), Spain (RW, ~113, -), Switzerland (SW, 54, -), USA (SW & GW, ND~360, 0~17) Australia (SW, Max: 2000, 73), China (RW, 37~193, ~100), Germany (LW, 250, -), Italy (RW, ND~402, -), Korea (SW, ND~150, 0~13), Luxembourg (RW, 0.3~22, -), Spain (RW, 58~149, -), Sweden (RW, <1~10, 50), UK (RW, <50, 0~100), USA (SW & GW, ND~1100, 0~91) 23,24,137,140,154,1 57,184,186,187 3,5,7,16,24,137~140, 142~144,146,147,149, 150,152~154, 163,183~190 대한환경공학회지제 33 권제 6 호 2011 년 6 월

10 462 大韓環境工學會誌總說손희종 장성호 Sulfonamide Tetracycline Others Sulfapyridine Italy (RW, <12~121, -), UK (RW, <2~142, 0~100) 138,139,183 Sulfathiazole Australia (SW, Max: 40, 21), Luxembourg (RW, 0.3~2, -), Korea (SW, ND~610, 0~88), USA (SW & GW, ND~80, 0~8) 137,143,154, 184,186,187 Chlortetracycline Australia (SW, Max: 600, 57), Korea (SW, ND~100, 0~63), USA (SW, ND~420, -) 3,137,143,146, 153,154,186,187 Demeclocycline USA (SW, 125~325, -) 153 Doxycycline Australia (SW, Max: 400, 34), Korea (SW, ND~20, 0~75), USA (SW, 100, -) 137,143,154,186 Minocycline Korea (SW, 0~200, 63), USA (SW, 18, -) 137,186 Oxytetracycline Tetracycline Australia (SW, Max: 100, 13), Italy (RW, ND~19.2, -), Korea (SW, ND~110, 88), Luxembourg (RW, 0.3~7, -), USA (SW, ND~340, -) Australia (SW, Max: 80, 33), Korea (SW, ND~75, 0~100), Luxembourg (RW, 0.3~8, -), USA (SW, ND~300, -) 3,4,137,143,150, 153,184,186,187 3,137,143,146,153, 154,184,186,187 Metronidazole UK (RW, <1.5~24, 0~91) 138,139 Vancomycin Italy (RW, 0.44~11.69,-) 150 Anticoagulant Warfarin Spain (RW, Mean: 1, Max: 3, -), USA (SW, 12, -) 137,191 Antidepressant Antiepileptic Antihypertensive Antineoplastic Beta-blocker Amitryptiline Canada (RW, 0.87~3.7, -), UK (RW, <0.5~71.6, 0~100) 138,192,193 Citalopram Canada (RW, 3.4~11.5, -) 192 Diazepam Fluoxetine Germany (RW, 33, -), Italy (RW, ND~2.13, 0~100), Romania (RW, 22.8~40.7, -), Spain (RW, Mean: 3, Max: 12, -), UK (RW, ~10, 50), USA (SW, 0.43~62, 11) Canada (SW, ND~50, -), UK (RW, Mean: 9.0, Max: 13.5, 50), USA (SW & GW, ND~56, 0~16) 1,4,6,141,163,191, 193~195 3,24,137,142,161, 163,182,192,193 Meprobamate USA (SW, ~73, 84~91) 16,163 Nordiazepam* France (SW, 2.4, -), UK (RW, Mean: 3.2, Max: 5.5, 83) 193,196 Norfluoxetine* Canada (SW, ND~1.3, -), UK (RW, <5, 88), USA (SW, <0.5~2.88, 0~1) 142,163,182,192,193 Oxazepam Spain (RW, Mean: 20, Max: 46, -), UK (RW, Mean: 11.4, Max: 17.4, 83) 191,193 Paroxetine Canada (RW, 1.3~3.0, -) 192 Sertraline Canada (RW, 0.84~2.4, -), Spain (RW, Mean: 11, Max: 12, -), USA (SW, 2.4~12.4, 3) 142,191,192 Venlafaxine Carbamazepine Canada (RW, 12.9~45.9, -), Spain (RW, Mean: 12, Max: 59, -), UK (RW, Mean: 35.1, Max: 71.6, 100) Austria (RW, 23.0~133.1, -), Canada (SW, 0.3~650, 7~100), Finland (RW, <1.4~80, -), Germany (SW & GW, 45~1100, -), India (RW, ~128, 100), Italy (RW, Max: 175.3, -), Korea (SW, ND~595, 90), Romania (RW, <30~81.2, -), Serbia (SW & GW, 8~130, -), Spain (SW, <2~110, -), Sweden (RW, <1~500, 100), Taiwan (RW, <0.5~120, -), UK (RW, <0.5~794, 0~100), USA (SW & GW, ND~113.7, 79~92) 191~193 5~7,22,59,92,122~124, 137~139,141,142,145, 151,154,160,163,164, 180,182,185,190, 191,197~203 Dilantin Korea (SW, 1.1~8.9, 75), USA (SW, Mean: 13, Max: 40, 91) 7,16 Gabapentin UK (RW, <0.6~1887, 0~100) 138,139 Primidone Spain (RW, Mean: 39, Max: 200, -) 191 Diltiazem Spain (RW, Mean: 4, Max: 9, -), UK (RW, <1~65, 0~100), USA (SW, 1.3~16, 10) 137,138,142,191 Enalapril Italy (RW, Max: 0.5, -) 141 Cyclophosphamide Canada (SW, Mean: ND~6, -), Italy (RW, ND, 0), Romania (RW, <30~64.8, -) 6,141,182 Tamoxifen Spain (RW, Mean: 0.15, Max: 0.1, -), UK (SW, <10~212, -) 112,127,149,191 Acebutolol Finland (RW, <0.8~14, 100), Spain (RW, Mean: 44, Max: 170, -) 145,191,197 Atenolol Metoprolol Propranolol Finland (RW, <11.8~55, 100), Italy (RW, 3.44~241, -), Korea (RW, ND~690, -), Spain (RW, Mean: 470, Max: 900, -), Sweden (RW, 10~60, 100), UK (RW, <1~560, 0~100), USA (SW, Mean: 10, Max: 36~48, 63~74) Finland (RW, <3.8~116, 100), Spain (RW, Mean: 90, Max: 380, -), Sweden (RW, 30~70, 100), UK (RW, <0.5~12, 50~100) Korea (RW, ND~40.1, -), Spain (RW, Mean: 54, Max: 270, -), Sweden (RW, <1~10, 100), UK (SW, <0.5~215, 14~100) 4,5,16,123,138,139, 141,145,163,191,197 5,138,139,145, 191,197 5,112,123,127,138, 139,149,190,191 Sotalol Finland (RW, <3.9~86, 100), Germany (GW, 560, -), Spain (RW, Mean: 100, Max: 160, -) 22,145,191,197 Bronchodilator Salbutamol Italy (RW, Max: 2.5, -), Spain (RW, Mean: 27, Max: 86, -), UK (RW, <0.5~8, 0~43) 138,141,191 BLLA Fibrate Bezafibrate Austria (RW, 1.6~12.5, -), Brazil (RW, <25, -), Canada (SW, ND~470, 0~77), Finland (SW, ND~20, 43~100), Germany (RW, <50~88, 100), Italy (RW, 0.8~57.2, -), Spain (RW, 26.7~78.4, -), UK (RW, <10~90, 0~83) 2,4,138~141,145, 182,203~206 Journal of KSEE Vol.33, No.6 June, 2011

11 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 463 Fibrate Statin Contrast media Diuretic NSAID Opioidanalgesic Clofibrate USA (SW, ND~890, -) 162 Clofibric acid* Gemfibrozil Brazil (RW, <10~30, -), Canada (SW, ND~175, 0~54), China (RW, NQ~248, 88), Germany (SW & GW, <1~70, 15~100), Italy (RW, 0.41~5.77, -), Korea (SW, 3~14, -), Spain (SW, 10~20, -), Taiwan (RW, <3, -), UK (SW, <0.3~164, 11~100), USA (SW, ND~630, -) Canada (SW, ND~580, 0~46), China (RW, ND~22.4, -), Germany (SW, <2~27, 4~100), Korea (SW, 1.0~9.1, 38), Spain (SW, <56~1,550, 67~100), Sweden (RW, 1~170, 100), USA (SW, ~38, 58~78) 2,4,102,124,127, 138~140,151,154, 158,160~162,182, 200,201,205~208 5,7,16,104,137,140, 154,158,163,182, 205,206,208~210 Atorvastatin Canada (SW, 1~16, -), USA (SW, 3.0~101.3, 5) 142,182,211 Lovastatin USA (SW, 10.6~102.9, 2) 142 Pravastatin Spain (RW, ~40.4, -), UK (RW, <60, 0) 138~140 Simvastatin Spain (RW, ~7.5, -), UK (RW, <50, 0~9) 138~140 Diatrizoate Germany (SW & GW, 30~2,000, -), Spain (RW, ~58.8, -) 131,134,135,140,212 Iohexol Germany (RW, 40~360, -), Spain (RW, ~71.4, -) 134,140 Iomeprol Germany (SW, 10~890, -) 131,134 Iopamidol Germany (SW & GW, 160~2,800, -) 22,131,134,212 Iopromide Australia (GW, 168, -), Germany (SW & GW, <10~1,600, -), Korea (SW, 20~361, 88), Spain (RW, 74.4~505, -), USA (SW & GW, ND~22.4, -) 7,131,132,134,135, 140,151,212 Bendroflumethiazide UK (RW, <0.5~15, 0~9) 138 Furosemide Italy (RW, Max: 254.7, -), Spain (RW, Mean: 22, Max: 110, -), UK (RW, <6~630, 0~100) 138,139,141,191 Acetaminophen 5-Aminosalicylic acid Diclofenac Germany (RW, <5~66, 100), Korea (SW, ND~76, 0~75), Serbia (RW, 310~78170, -), Spain (RW, 163~260, -), UK (SW, <1.5~2382, 0~100), USA (SW & GW, ND~380, 13~75) 7,24,127,137~140, 142,151,154,180, 205,213 UK (RW, <15~190, 0~89) 138,139 Austria (RW, 15.8~35.5, -), Brazil (RW, 20~60, -), Canada (SW, ND~194, 0~23), China (RW, ND~147, -), Finland (SW, ND~55, 57~100), Germany (SW & GW, ND~ 15033, 37~100), Italy (SW, 1~69, -), Korea (SW, 1.1~6.8, 38), Luxembourg (RW, 0.3~55, -), Slovenia (RW, 9~282, 69), Spain (SW, <2~610, 67~100), Sweden (RW, 10~120, 50), Switzerland (SW, 20~150, -), Taiwan (RW, 24~62, -), UK (SW, <0.5~568, 0~100), USA (SW, Max: 1.2, 21) 2,5,7,22,59,102,104, 127,138~140,145,149, 163,181,182,184,190, 199~207,209,217 Fenoprofen Canada (SW, ND~64, 0~14), Germany (SW, <2~54, 7~100) 182,205,206,208 Ibuprofen Brazil (RW, <10, -), Canada (SW, ND~6400, 0~50), China (RW, ND~1417, 82), Finland (SW, ND~69, 71~100), Germany (SW, <2~152, 22~100), Iran (RW, 19, 100), Italy (RW, ND~78.5, -), Korea (SW, ND~414, 0~75), Luxembourg (RW, 9~2383, -), Romania (RW, <30~115.2, -), Singapore (RW, <2~76, -), Spain (SW, <8~2700, 67~100), Sweden (RW, 10~220, 100), Taiwan (RW, <12~30, -), Switzerland (SW, 10~400, -), UK (SW, <0.3~5044, 20~100), USA (SW & GW, ND~5850, 0~67) 2,4~7,24,61,102,104, 112,123,127,137~141, 145,149,151,154,156, 158~162,182,184, 199~201,204~208, 210,218,219 Indomethacin Canada (SW, ND~150, 0~13), Germany (SW, <5~60, 4~100), Korea (RW, <1~33.5, -) 123,182,205,206,208 Ketoprofen Canada (SW, ND~79, 0~23), Finland (SW, ND~28, 29~100), Spain (SW, ND~300, 0~33), Sweden (RW, 10~70, 75), Switzerland (SW, ND~5, -), Taiwan (RW, 110~620, -), UK (RW, <0.5~14, 22~69) 5,104,138,139,145, 182,200,201,204, 206,210,215,219 Meclofenamic acid Canada (SW, 80~115, 100) 104 Mefenamic acid Naproxen Austria (RW, <0.4~13.6, -), China (RW, ND~22.4, -), Korea (SW, 5~326, -), UK (SW, <0.3~366, 0~100) Brazil (RW, <10~50, -), Canada (SW, ND~4500, 0~75), China (RW, ND~328, 23), Finland (SW, ND~45, 43~100), Germany (RW, ND~70, 0~100), Iran (RW, 9, 100), Korea (SW, 1.8~18, 75), Singapore (RW, 8~108, -), Slovenia (RW, 17~313, 69), Spain (SW, ND~2000, 33~100), Sweden (RW, 90~250, 75), Switzerland (SW, 10~400, -), UK (RW, <0.3~146, 20~100), USA (SW, ND~145, 0~100) 123,127,138,139, 149,151,154,203,209 2,5,7,16,102,104,138~ 140,145,151,154,156, 158,159,161~163,182, 204~206,209,210, 214,215,218~220 Phenazone Germany (RW, <10~85, 100) 205 Salicylic acid* Canada (SW, 130.4~17000, 13~100), China (RW, 9~2098, 100), Germany (SW, <50, -), Romania (RW, <30~41.8, -), Spain (SW, 18~8800, ~100), UK (RW, <0.3~302, 60~100) 6,104,138~140,158, 206,210,221 Sulfasalazine UK (RW, <1.5~168, 0~100) 138 Codeine Romania (RW, <30~63.2, -), Spain (RW, 29.9~149, ~100), Switzerland (SW, <1~18, 31~57), Taiwan (RW, Mean: 16, Max: 57, 82), UK (RW, <1.5~815, 0~100), USA (SW & GW, ND~10, 8) 6,137~140,151, 193,222~224 대한환경공학회지제 33 권제 6 호 2011 년 6 월

12 464 大韓環境工學會誌總說손희종 장성호 Opioidanalgesic Psycho-stimulant Sex hormone EDDP Switzerland (SW, 0.6~12.2, 100), UK (RW, Mean: 19.1, Max: 38.2, 100) 193,223 Methadone Spain (RW, ND, 0), Switzerland (SW, <0.2~4.6, 97~100), UK (RW, Mean: 10.0, Max: 18.4, 100) 193,223,224 Morphine Spain (RW, 89, 100), Switzerland (SW, ND~14, 0~41), UK (RW, ND~35.8, 17) 193,223,224 Norcodeine UK (RW, Mean: 8.9, Max: 19.9, 83) 193 Tramadol UK (RW, <30~7731, 0~100) 138,139,193 Caffeine Canada (SW, ND~1590, 33~47), Korea (SW, ND~480, 0~100), Romania (RW, 363~11121, 100), Spain (RW, 291~526, -), Sweden (RW, <5~110, 100), UK (RW, Mean: 265, Max: 437, 100), USA (SW & GW, ND~224.8, 92~100) 5~7,104,137,140, 142,151,154,182, 193,225,226 Amphetamine Spain (SW, ND~12.1, 0~7), UK (RW, <1~14, 0~100) 138,193,224,227 17α-Estradiol 17β-Estradiol Estriol Estrone 17α-Ethinylestradiol Austria (SW & GW, ND~0.31, 4~7), China (RW, ND~2, 22), France (GW, 0.8~3.5, -), USA (SW, 30, -) Austria (SW & GW, ND~1.2, 52~60), China (RW, ND~120, 11), France (SW & GW, 0.3~4.4, -), Germany (SW, <0.2, -), Italy (RW, 0.11~6, -), Japan (SW, <0.3~32, ~100), Luxembourg (RW, 1~35, -), Spain (RW, 6.3, -), USA (SW, ND~17, 5) Austria (SW & GW, ND~1.9, 2~8), China (RW, ND~1, 5), France (SW, 1.0~2.9, -), Italy (RW, 0.33~5, -), Japan (RW, <0.2~5.5, ~100), Spain (RW, 8~72, -), Singapore (RW, <3~451, -), USA (SW, 19, -) 3,158,228~230 3,119,120,156,158, 159,161,163,184, 209,228~239 3,158,191,229, 232~237,239 Austria (SW & GW, ND~4.6, 18~76), China (RW, ND~200, 65), France (SW & GW, 3,7,16,119,120,156, 0.3~57.8, -), Germany (SW, 0.11~0.21, -), Italy (RW, 1.5~12, -), Japan (RW, 0.2~47.6, 158,159,161,163,184, ~100), Korea (SW, 1.7~5.0, 38), Luxembourg (RW, 0.3~27, -), Singapore (RW, 191,209,228~236, <1~304, -), Spain (RW, 4.3, -), UK (RW, ND~10, 62), USA (SW, ND~27, 0~79) 239~241 Austria (SW & GW, ND~0.94, 1~2), China (RW, ND~1, 5), France (SW & GW, 0.5~3.0, -), Germany (SW, <0.2, -), Italy (RW, ND~1, -), Japan (RW, <0.2, 100), Luxembourg (RW, <2.0, -), USA (SW, <0.05~73, 5) 3,120,141,158,163, 184,228,229, 232~235,238 Progesterone USA (SW, Max: 3.2, 21) 163 Testosterone USA (SW, Max: 1.2, 11) 163 * : Metabolite, SW : surface water, RW : river water, GW : groundwater, ND : not detected, NQ : detected but too low to be quantified 검출농도를나타낸항생제는 sulfathiazole로 610 ng/l의최대검출농도를나타내었다. 조영제의경우는독일에서 iopamidol과 diatrizoate가각각 2,800 및 2,000 ng/l로검출되어최대검출농도를나타내었으며, 국내의경우는 iopromide 가 361 ng/l의최대농도로검출되었다. 국 내외적으로비교적높은검출농도를나타낸잔류의약물질들은대부분이강이나호소의상류에위치한하수처리장방류수의유입때문이며, 실제로하수처리장방류수중의잔류의약물질농도는지표수의수 ~ 수십배이상높게검출된다. 122) 따라서수환경에서의잔류의약물질들에의한오염을저감시키기위해서는하수처리공정에고도산화, 활성탄흡착, 막여과등과같은고도화된수처리공정의도입이필수적이다. 136) 우리나라와외국의잔류의약물질별최대검출농도를비교해보면외국에비해검출농도가비교적낮게나타나고있다. 그러나국내의경우는수계에서의잔류의약물질들에대한오염현황을체계적으로조사한연구결과가매우부족한실정이기때문에 Fig. 6과 Table 3에나타낸우리나라의검출농도수준이정확하다고평가할수는없다. 외국의경우도보고된연구결과들의대부분이북미지역과유럽에위치한국가들이대부분이며, 최근에는중국의잔류의약물질분포현황에대한연구결과가많이보고되고있고, 후진국과개발도상국들이많이위치한아시아, 남미및아프리카지역의경우는수중의잔류의약물질현황및분 포에대한연구결과들이거의전무하다. 5. 잔류의약물질들의생태독성 수중에존재하는잔류의약물질들은수생태계에유해한영향을가지는것으로알려져있으며, 다양한배출원과유입, 이동경로를통해수환경중으로이동 확산되어잔류하다생물체내로침투하여생태계및인간의건강에심각한영향을끼친다. 대표적인영향으로는개체수감소, 생식능력저하, 생장저해, 암유발및면역기능저해등을야기할수있는것으로추정된다. 20) 이에따라생태독성을정량적으로평가하는방법들이개발되고있으며, 기본적인접근방식은물벼룩, 물고기, 조류 (algae) 등의수생동 / 식물을활용한다양한독성실험들이있다. 실험대상생물들중물벼룩이잔류의약물질들에가장민감하게반응하며, 조류 (algae) Table 4. Toxicity classification of residual pharmaceuticals in water environment 242) Eco-toxicity Low Moderate High Very high LC/EC/IC 50 (fish, crustacean, algae) >100 mg/l >10~100 mg/l 1~10 mg/l <1 mg/l Journal of KSEE Vol.33, No.6 June, 2011

13 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 465 Table 5. Toxicity data of pharmaceuticals for non-target organism Therapeutic use Antibiotic Compounds Test organism Acute toxicity Taxon Species Test Data β-lactam Amoxicillin Algae M. aeruginosa EC 50 (72 h) mg/l, growth inhibition 243 Algae S. capricornutum NOEC (72 h) 250 mg/l, growth inhibition 243 Algae S. leopoliensis EC µg/l, growth inhibition 244 Algae S. leopoliensis NOEC 0.78 µg/l, growth inhibition 244 Bacteria V. fischeri EC 50 (15 min) 3597 mg/l, luminescence 245 Penicillin G Algae M. aeruginosa EC mg/l, growth rate 246 Algae S. capricornutum NEOC 100 mg/l, growth rate 246 Quinolone Enrofloxacin Crustacean D. magna EC 50 (48 h) 56.7 mg/l, immobilization 245 Crustacean D. magna NOEC (21 d) 5 mg/l, reproduction 245 Norfloxacin Algae S. capricornutum EC mg/l, growth inhibition 247 Algae S. capricornutum NEOC 4.01 mg/l, growth inhibition 247 Algae C. vulgaris EC mg/l, growth inhibition 247 Algae C. vulgaris NOEC 4.02 mg/l, growth inhibition 247 Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 248 Ofloxacin Algae M. aeruginosa EC 50 (72 h) mg/l, growth inhibition 243 Algae P. subcapitata EC 50 (72 h) 1.44 mg/l, growth inhibition 248 Rotifer B. calyciflorus EC 50 (48 h) 0.53 mg/l, population growth inhibition 248 Crustacean D. magna EC 50 (24 h) mg/l, immobilization 248 Lincosamide Lincomycin Algae P. subcapitata EC 50 (72 h) 0.07 mg/l, growth inhibition 248 Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 248 Rotifer B. calyciflorus EC 50 (48 h) 0.68 mg/l, population growth inhibition 248 Crustacean D. magna EC 50 (24 h) mg/l, immobilization 248 Crustacean T. platyurus LC 50 (24 h) mg/l, mortality 248 Macrolide Clarithromycin Algae P. subcapitata EC 50 (72 & 96 h) 72 h: mg/l, 96 h: 11 µg/l, growth inhibition 248,249 Algae P. subcapitata NOEC (96 h) 3.1 µg/l, growth inhibition 249 Crustacean D. magna EC 50 (24 h) mg/l, immobilization 248 Fish O. latipes LC 50 (96 h) >100 mg/l, mortality 250 Erythromycin Algae P. subcapitata EC 50 (72 h) 0.02 mg/l, growth inhibition 248 Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 248 Rotifer B. calyciflorus EC 50 (48 h) 0.94 mg/l, population growth inhibition 248 Crustacean T. platyurus LC 50 (24 h) mg/l, mortality 248 Crustacean D. magna EC 50 (24 h) mg/l, immobilization 248 Fish O. latipes LC 50 (96 h) >100 mg/l, mortality 250 Duckweed Lemna minor EC 50 (7 d) 5.62 mg/l, growth inhibition 251 Spiramycin Algae M. aeruginosa EC mg/l, growth rate 246 Algae S. capricornutum EC mg/l, growth rate 246 Tylosin Algae M. aeruginosa EC mg/l, growth rate 246 Algae S. capricornutum EC mg/l, growth rate 246 Crustacean D. magna EC 50 (48 h) 680 mg/l, immobilization 252 Crustacean D. magna NOEC (21 d) 45 mg/l, reproduction 252 Phenol Triclosan Algae S. subspicatus NOEC (72 h) 500 ng/l, growth 253 Pyrimidine Trimethoprim Algae M. aeruginosa EC 50 (72 h) 112 mg/l, growth inhibition 243 Algae S. capricornutum EC 50 (72 h) 130 mg/l, growth inhibition 243 Bacteria V. fischeri EC 50 (15 min) mg/l 10 Crustacean D. magna EC 50 (48 h) 92 mg/l, immobilization 254 Crustacean M. macrocopa EC 50 (48 h) 54.8 mg/l, immobilization 254 Cnidarian Hydra attenuata LC 50 (96 h) >100 mg/l, morphology 255 Fish O. latipes LC 50 (48 & 96 h) >100 mg/l 10 Ref. 대한환경공학회지제 33 권제 6 호 2011 년 6 월

14 466 大韓環境工學會誌總說손희종 장성호 Sulfonamide Sulfadiazine Algae M. aeruginosa EC 50 (72 h) mg/l, growth inhibition 243 Algae S. capricornutum EC 50 (72 h) 7.8 mg/l, growth inhibition 243 Crustacean D. magna EC 50 (48 h) 212 and 221 mg/l, immobilization 249,254 Sulfadimethoxine Algae S. capricornutum EC 50 (72 h) 2.3 mg/l, growth inhibition 247 Algae C. vulgaris EC mg/l, growth inhibition 247 Bacteria V. fischeri EC 50 (15 min) >500 mg/l 10 Crustacean D. magna EC 50 (48 & 96 h) 48 h: 248 mg/l, 96 h: mg/l, immobilization 10 Fish O. latipes LC 50 (48 & 96 h) >100 mg/l 10 Sulfamethazine Bacteria V. fischeri EC 50 (15 min) mg/l 10 Crustacean D. magna EC 50 (48 & 96 h) 48 h: mg/l, 96 h: mg/l, immobilization 10 Fish O. latipes LC 50 (48 h) >100 mg/l 10 Sulfamethoxazole Algae P. subcapitata EC 50 (72 h) 0.52 mg/l, growth inhibition 248 Algae S. capricornutum EC mg/l, growth inhibition 247 Bacteria V. fischeri EC 50 (15 & 30 min) 15 min: 78.1 mg/l, 30 min: 23.3 mg/l, luminescence 10,248 Crustacean D. magna EC 50 (24 h) 25.2 mg/l, immobilization 248 Cnidarian Hydra attenuata LC 50 (96 h) >100 mg/l, morphology 255 Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 248 Rotifer B. calyciflorus EC 50 (48 h) 9.63 mg/l, population growth inhibition 248 Fish O. latipes LC 50 (48 h) >750 mg/l 10 Sulfapyridine Cnidarian H. attenuata LC 50 & EC 50 (96 h) LC 50: >100 mg/l, EC 50: mg/l, morphology 255 Sulfathiazole Bacteria V. fischeri EC 50 (15 & 30 min) >1000 mg/l 10 Crustacean D. magna EC 50 (48 & 96 h) 48 h: mg/l, 96 h: 85.4 mg/l, immobilization 10 Fish O. latipes LC 50 (48 & 96 h) >500 mg/l 10 Tetracycline Chlortetracycline Algae M. aeruginosa EC mg/l, growth inhibition 246 Bacteria V. fischeri EC 50 (15 min) 13.0 mg/l, luminescence 245 Crustacean D. magna EC 50 (24 & 48 h) 24 h: mg/l, 48 h: 225 mg/l, immobilization 245 Fish O. latipes LC 50 (24 & 48 h) 24 h: 88.4 mg/l, 48 h: 78.9 mg/l, mortality 245 Oxytetracycline Algae M. aeruginosa EC 50 (72 h) mg/l, growth inhibition 243 Bacteria V. fischeri EC 50 (15 & 30 min) 15 min: 87 mg/l, 30 min: 64.5 mg/l, luminescence 245,248 Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 248 Cnidarian H. attenuata LC 50 & EC 50 (96 h) LC 50: >100 mg/l, EC 50: mg/l, morphology 255 Crustacean C. dubia EC 50 (24 h & 7 d) 24 h: mg/l, immobilization, 7 d: 0.18 mg/l, population growth inhibition 248 Fish O. latipes LC 50 (24 & 48 h) 24 h: mg/l, 48 h: mg/l, mortality 245 Tetracycline Algae M. aeruginosa EC mg/l, growth rate 246 Algae S. capricornutum EC mg/l, growth rate 246 Crustacean D. magna EC 50 (21 d) 44.8 mg/l, reproduction 252 Duckweed L. minor EC 50 (7 d) 1.06 mg/l, growth inhibition 251 Others Metronidazole Crustacean D. magna NOEC (21 d) 250 mg/l, reproduction 252 Antidepressant Citalopram Crustacean C. dubia LC 50 (48 h) 3.9 mg/l, 256 Diazepam Algae T. chuii IC mg/l 257 Crustacean A. parthenogenetica LC mg/l 257 Crustacean D. magna LC mg/l 258 Cnidarian H. vulgaris capacity of regenerate polyps <1 mg/l, chronic toxicity: 10 µg/l 259 Fluoxetine Algae D. tertiolecta EC 50 (96 h) µg/l, growth inhibition 107 Algae P. subcapitata EC 50 (120 h) 24 µg/l, growth 260 Crustacean C. dubia LC 50 (48 h) 234 µg/l 260 Crustacean D. magna LC 50 (48 h) 820 µg/l 260 Fish P. pimelas LC 50 (48 h) 705 µg/l 260 Paroxetine Crustacean C. dubia LC 50 (48 h) 0.58 mg/l, 256 Journal of KSEE Vol.33, No.6 June, 2011

15 大韓環境工學會誌總說상수원에서의잔류의약물질검출, 거동, 분포현황및독성 467 Sertraline Algae P. subcapitata EC 50 & NOEC (72 h) 0.14 & 0.05 mg/l, inhibition 261 Algae P. subcapitata IC 50 (96 h) µg/l, growth inhibition 262 Crustacean D. magna EC 50 & NOEC (48 h) 1.3 & 0.1 mg/l, immobilization 261 Crustacean D. magna EC 50 & NOEC (21 d) & mg/l, reproduction 261 Shrimp T. platyurus LC 50 & NOEC (24 h) 0.6 & 0.4 mg/l, lethality 261 Fish O. mykiss LC 50 & NOEC (96 h) 0.38 & 0.1 mg/l, lethality 261 Antiepileptic Carbamazepine Algae D. subspicatus EC mg/l, growth inhibition 108 Algae P. subcapitata NOEC (96 h) 100,000 µg/l, growth inhibition 263 Bacteria V. fischeri EC 50 (15 & 30 min) 15 min: 52.2 mg/l, 30 min: >81,000 µg/l 10,263 Crustacean D. magna EC 50 (48 h) >100 mg/l & >13,800 µg/l, immobilization 10,263 Cnidarian Hydra attenuata LC 50 & EC 50 (96 h) LC 50: 29.4 mg/l, EC 50: mg/l, morphology 255 Fish O. latipes LC 50 (48 & 96 h) 48 h: 35.4 mg/l, 96 h: 35.4 & mg/l, mortality 10,250 Duckweed L. minor EC 50 (7 d) 25.5 mg/l, growth inhibition 108 Antineoplastic Cyclophosphamide Algae P. subcapitata EC 50 & NOEC (72 h) >100 mg/l, growth inhibition 264 Crustacean D. magna EC 50 (21 d) >100 mg/l, reproduction 264 Tamoxifen Rotifer B. calyciflorus LC 50 (24 h) 0.97 mg/l, mortality 265 Crustacean D. magna EC 50 (24 h) 1.53 mg/l, immobilization 265 Crustacean T. platyurus LC 50 (24 h) 0.40 mg/l, mortality 265 Beta-blocker Atenolol Algae D. subspicatus EC mg/l, growth inhibition 266 Crustacean D. magna EC 50 (48 h) 313 mg/l, immobilization 266 Fish O. latipes LC 50 (96 h) >100 mg/l, mortality 250 Metoprolol Algae D. subspicatus EC mg/l, growth inhibition 108 Crustacean D. magna EC 50 (48 h) >100 & 438 mg/l, immobilization 108,266 Fish O. latipes LC 50 (48 h) >100 mg/l, mortality 267 Propranolol Algae D. subspicatus EC 50 & EC 50 (48 h) 5.8 & 0.7 mg/l, growth inhibition 108,266 Crustacean D. magna EC 50 (48 h) 7.5 & 7.7 mg/l, immobilization 108,266 Fish O. latipes LC 50 (48 & 96 h) 48 h: 24.3 mg/l, 96 h: 11.4 mg/l, mortality 250,267 Duckweed L. minor EC 50 & EC 50 (7 d) 113 & 114 mg/l, growth rate and growth inhibition 108,266 BLLA Fibrate Bezafibrate Rotifer B. calyciflorus LC 50 (24 h) mg/l, mortality 268 Crustacean D. magna EC 50 (24 h) mg/l, immobilization 268 Cnidarian H. attenuata LC 50 & EC 50 (96 h) LC 50: mg/l, EC 50: mg/l, morphology 255 Clofibrate Fish D. rerio LC 50 (96 h) 0.89 mg/l, mortality 269 Clofibric acid* Algae D. subspicatus EC mg/l, growth inhibition 108 Bacteria V. fischeri EC 50 (30 min) 100 mg/l 270 Ciliates T. pyriformis EC 50 (48 h) 175 mg/l, growth inhibition 270 Crustacean D. magna EC 50 (48 h) 72 mg/l & >200 mg/l, immobilization 108,263 Duckweed L. minor EC 50 (7 d) 12.5 mg/l, growth inhibition 108 Gemfibrozil Algae C. vulgaris EC 50 (24 h) 195 mg/l, growth 271 Algae P. subcapitata EC 50 (72 h) mg/l, growth inhibition 268 Bacteria V. fischeri EC 50 (0.5, 24 & 48 h) 85.74, 64.6 & 45.1 mg/l, bioluminescence 268,271 Crustacean D. magna EC 50 (24, 48 & 72 h) 57.1, 42.6 & 30.0 mg/l, immobilization 271 Statin Atorvastatin Duckweed L. gibba LOEC (7 d) 300 µg/l, growth parameters 272 Simvastatin Algae D. tertiolecta EC 50 (96 h) 22.8 mg/l, growth inhibition 107 Copepod N. spinipes LC 50 (96 h) & LOEC LC 50: 810 µg/l & LOEC: 0.16 µg/l, growth rate 273 Grass shrimp P. pugio LC 50 (96 h) & NOEC 1.18 & mg/l, larvae survival 274 Contrast media Iopromide Algae S. subspicatus EC 50 (72 h) >10.0 g/l, growth inhibition 275 Bacteria V. fischeri EC 50 (30 min) >10.0 g/l, luminescence 275 Crustacean D. magna EC 50 (24 & 48 h) >10.0 & >1 g/l, immobilization 275,276 Fish L. idus LC 50 (48 h) >10.0 g/l, mortality 275 대한환경공학회지제 33 권제 6 호 2011 년 6 월

16 468 大韓環境工學會誌總說손희종 장성호 NSAID Diclofenac Algae D. subspicatus EC & 72 mg/l, growth inhibition 108,277 Algae P. subcapitata NOEC & LOEC (96 h) 10,000 & 20,000 µg/l, growth inhibition 263 Bacteria V. fischeri EC 50 (30 min) 11,454 v 263 Crustacean D. magna EC 50 (48 h) & 68 mg/l, immobilization 263,277 Fish O. mykiss LOEC (28 d) 1 & 5 µg/l, histopathological & cytological alterations 278,279 Fish D. rerio NOEC & LOEC (10 d) 4000 & 8000 µg/l, survival 263 Duckweed L. minor EC 50 (7 d) 7.5 mg/l, growth inhibition 108 Ibuprofen Algae D. subspicatus EC & mg/l, growth inhibition 108,277 Crustacean D. magna EC 50 (48 h) 1~100, & 108 mg/l, immobilization 108,277, 280 Crustacean T. platyurus LC 50 (24 h) mg/l, mortality 250 Cnidarian H. attenuata LC 50 & EC 50 (96 h) LC 50: mg/l & EC 50: 1.65 mg/l, morphology 255 Mollusc P. carinatus LC 50 (72 h) 17.1 mg/l, survival 281 Mollusc P. carinatus NOEC (21 d) 5.36 mg/l: survival, 1.02 mg/l: growth 281 Fish O. latipes LC 50 (96 h) >100 mg/l, mortality 281 Indomethacin Crustacean T. platyurus LC 50 (24 h) mg/l, mortality 250 Fish O. latipes LC 50 (96 h) mg/l, mortality 250 Mefenamic acid Crustacean T. platyurus LC 50 (24 h) 3.95 mg/l, mortality 250 Fish O. latipes LC 50 (96 h) 8.04 mg/l, mortality 250 Naproxen Algae D. subspicatus EC 50 >320 & mg/l, growth inhibition 108,277 Algae P. subcapitata EC 50 (72 h) mg/l, growth inhibition 282 Rotifer B. calyciflorus EC 50 (48 h) 0.56 mg/l, growth inhibition 282 Rotifer T. platyurus LC 50 (24 h) mg/l 282 Crustacean D. magna EC 50 (48 h) & 174 mg/l, immobilization 108,277 Crustacean C. dubia EC 50 (24 h) mg/l, immobilization 282 Cnidarian H. attenuata LC 50 & EC 50 (96 h) LC 50: mg/l & EC 50: 2.62 mg/l, morphology 255 Duckweed L. minor EC 50 (7 d) 24.2 mg/l, growth inhibition 108 Salicylic acid Algae S. subspicatus EC 50 (72 h) >100 mg/l 270 Bacteria V. fischeri EC 50 (30 min) 90 mg/l 270 Ciliates T. pyriformis EC 50 (48 h) >100 mg/l, growth inhibition 270 Crustacean D. magna EC 50 (24 h) 118 mg/l, immobilization 270 Sex hormone 17β-Estradiol Fish O. latipes NOEC & LOEC (21 d) <29.3 & 26.3 ng/l, testis-ova induction α-Ethinylestradiol Fish P. promelas LOEC (21 d) 1 ng/l, plasma VTG induction & ultrastructure testes 116 EC 50: half effective concentration, LC 50: half lethal concentration, IC 50: half inhibitory concentration, NOEC: no observed effect concentration, LOEC: lowest observed effect concentration 와물고기등이높은빈도로사용되며, 20) 반수영향농도 (half effective concentration, EC 50), 반수치사농도 (half lethal concentration, LC 50), 최대무영향농도 (no observed effect concentration, NOEC) 및최소영향농도 (lowest observed effect concentration, LOEC) 등으로평가하고있다. 21) Table 4에는수환경중에잔류하는의약물질들의생태계독성분류표를나타내었으며, 수중에잔류하는의약물질들에대한다양한생체독성결과를 Table 5에나타내었다. 대부분의연구결과들이단기적인급성 (acute) 독성평가들이며, 장기간노출에따른만기 (chronic) 독성에대한연구결과는매우드물다. 21) 단기독성의경우는잔류의약물질들이수환경에일시적인사고로인해일시적으로유출되었을경우, 잔류의약물질들이단기적으로수생태계에미치는영향을파악하기위한것으로대부분의단기독성실험결과들은일반적으로수환경에서의잔류의약물질들의검 출농도보다훨씬낮다. 21) 따라서수환경중에서검출되는농도수준에서장기간노출되었을경우의잔류의약물질들이수생생물들의성장및생식 (reproduction) 에미치는영향과같은만성독성을파악하는것이수환경에서의잔류의약물질들의위해성을올바로평가하는것이라할수있으며, 또한, 각각의개별의약물질들이미치는독성영향들보다는다양한의약물질들이수중에공존할경우의수생생물에미치는독성에대해서도다양한연구가진행되어야할것이다. 6. 결론 오늘날전세계적으로수환경에서의잔류의약물질들의오염에대한연구결과들이보고되고있다. 이들잔류의약물 Journal of KSEE Vol.33, No.6 June, 2011