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Korean Journal of Environmental Agriculture Korean J Environ Agric (2012) Online ISSN: 2233-4173 Vol. 31, No. 3, pp. 255-263 http://dx.doi.org/10.5338/kjea.2012.31.3.255 Print ISSN: 1225-3537 Research Article Open Access 대기환경중키랄유기염소계농약의분포특성 최종우, 1 김금희, 1 황승률, 2 이규승 3 1 국립환경과학원환경측정분석센터, 2 국립환경과학원화학물질연구과, 3 충남대학교생물환경화학과 Distribution Profile of Chiral Organochlorine Pesticides in Ambient Air Jong-Woo Choi, 1 Kum-Hee Kim, 1 Seung-Ryul Hwang 2 and Kyu-Seung Lee 3 ( 1 Environmental Measurement & Analysis Center, National Institute of Environmental research, Environmental Research Complex, Kyungseo-dong, Seo-gu, Incheon, 404-708, Republic of Korea, 2 Chemicals Research division, Environmental Health Research Department, National Institute of Environmental research, Environmental Research Complex, Kyungseo-dong, Seo-gu, Incheon, 404-708, Republic of Korea, 3 Department of Bio-Environmental Chemistry Chungnam National Univercity, Daejon, 305-764, Republic of Korea) Received: 3 September 2012 / Accepted: 18 September 2012 c 2012 The Korean Society of Environmental Agriculture Abstract BACKGROUND: The analysis for the concentration and enantiomeric ratio of OCPs have been performed to confirm the distribution and to emonstrate the pollution characteristics of chiral OCPs in ambient air. METHODS AND RESULTS: In ambient air at coastal and inland sites, concentrations and enantiomer fractions (EFs) of heptachlor (HEPT), eptachlor epoxide (HEPX), trans-chlordane (TC), cis-chlordane (CC), xychlordane (OXY), 2,4'-DDT, 2,4'-DDD with HRGC/HRMS were investigated to understand source and distribution of chiral organochlorine pesticides (OCPs) in ambient air. The mean concentrations of OCPs in ambient air were at the range of 0.027(heptachlor) 1.279 (4,4 -DDT) pg/m 3 and 0.0005 (heptachlor) 0.1043 ng/g d.w. (TC), respectively. The mean EFs of OCPs in ambient air were at the range of 0.73 (HEPX) 0.45 (CC). Both preferential depletions of (+) and (-) enantiomer were observed for CC, indicated by EFs either <0.5 or >0.5, while preferential depletions of (-) enantiomer which mean EFs <0.5 were observed for chiral OCPs except TC and MC-5. 교신저자 (Corresponding author), Phone: +82-42-821-6735; Fax:+82-42-822-5781; E-mail: kslee@cnu.ac.kr CONCLUSION: OCPs in ambient air have been distributed from soil, but some of them such as chlordane, DDT etc. might have been introduced by long-range atmospheric transport, considering EFs by chiral analysis and trajectory analysis. Key Words: Ambient air, EFs, Enantiomer, OCPs 서론 유기염소계농약 (organochlorine pesticides, OCPs) 은 1940년대부터사용되기시작한살충제로서식량생산에크게기여하였으나, 환경중잔류성에의한잠재적위해성과과거수십년동안사용되었기때문에현재도많은관심을가지고있어스톡홀름협약에서도 15종을지정하고있다. OCPs 환경오염에효과적으로대응하기위해서는오염원에서대기의장거리이동에의하여유입되는것인지, 아니면과거의사용에의한잔류인지등에대한환경중이동특성에대한연구 (Tiruponitiura et al., 2003), 특히, 과거에사용한 OCPs가농경지토양으로부터재휘발에의한지역대기로의유입과아직도 OCPs를사용하고있는일부국가로부터장거리이동에의한유입을구별할수있는연구가필요하다 (Kurt-Karakus et al., 2005). 환경중오염물질의동태를해석할수있는다양한방법이있으나, 키랄분석법은키랄화합물의거울상이성질체비율 (enantiomer fractions, EFs) 을이용하여발생원및경로를확인할수있는매우효과적인방법으로알려져있 255

256 CHOI et al. 다 (Vetter and Schurig, 1997; Wiberg et al., 2001). 스톡홀름협약에서채택된 POPs 중 OCPs 4종 DDT, chlordane, heptachlor(hept), toxaphene 과분해산물 3종 1,1-dichloro- 2,2-bis(4-chlorophenyl)-ethane (DDD), oxychlordane (OXY), haptachlor epoxide (HEPX) 등이키랄화합물이므로키랄분석법은이들의환경매체간이동과오염원추적연구에유용하게활용될수있다. 현재국내대기환경중의 OCPs 잔류농도는많은논문에서보고되었으나 (Lee, 1982; Haglund et al., 1996; Choi et al., 1987; Jung et al., 2001; Yeo et al., 2004) 키랄 OCPs 의 EFs를측정한연구는찾아보기어려우며, 세계적으로도매우제한적인연구가이루어져왔다.(Finizio et al., 1998; Wiberg et al., 2001). 본연구에서는환경중에극미량이잔류하여농도및 EFs 측정이어려운 POPs 중키랄 OCPs 인 o,p'-ddt, cis-chlordane (CC), trans-chlordane (TC), MC-5 및 HEPT와 o,p'-ddt, CC와 TC 및 HEPT의키랄분해산물인 o,p'-ddd, OXY, HEPX의우리나라대기환경중분포현황을파악하기위하여잔류농도와 EFs를 1 pg 이하의감도를가진키랄컬럼을장착한고분해능기체크로마토그래프 (high resolution gas chromatograph, HRGC)/ 고분해능질량분석기 (high resolution mass spectrometer, HRMS) 로측정하였다. 표준물질 재료및방법 대기시료채취국내대기중 OCPs의잔류농도와 EFs를측정하고중국으로부터의장거리대기이동에의한영향을파악하고자서해안지역 1개지점과중부내륙지역 1 개지점을시료채취지점으로선정하였다 (Table 1, Fig. 1). Table 1. Sampling sites and volumes of ambient air Sampling site Sampling date Sampling volumes (m 3 ) A-P-1 2007. 03. 27 1000 Coastal A-P-2 2007. 03. 28 1000 site A-P-3 2007. 03. 29 1000 A-P-4 2007. 03. 30 1000 Inland site A-G-1 2007. 03. 15 1000 A-G-2 2007. 03. 16 1000 A-G-3 2007. 03. 17 1000 대기시료채취는환경부잔류성유기오염물질공정시험기준 (ES 10900.1b, 2011) 에따라하이볼륨에어샘풀러 (Sibata Ltd. model 700F) 를사용하여해안지점과내륙지점에서각각 24시간씩 4회 (4일), 3회 (3일) 시료를채취하였다. 회수율을측정하기위하여, 시료채취전에분석대상물질이 2 4 ng 첨가되도록정제용표준물질인 13 C-OCPs(CIL, ES-5342) 를첨가하였다. 전처리및정제 coastal site + inland site Coastal site -Latitude : N 36 44 03.661 -Longitude : E 126 08 05.381 -Sea level : 12 Inland site -Latitude : N 36 43 41.407 -Longitude : E 127 48 35.066 -Sea level : 172m Fig. 1. Location of air sampling site. 키랄 POPs의정량분석및 EFs 측정을위하여사용한키랄 POPs 검정곡선용표준물질 (calibration standards) 과정제용표준물질 (clean-up spike standards) 은 Cambridge Isotope Laboratories 에서제조한 CIL-ES-5341 과 CIL-ES-5342 를구입하여사용하였다. 실린지첨가용표준물질은 Cambridge Isotope Laboratories에서제조한 13 C로치환된 3 가지 PCB 동질체인 13 C-2,4,4'-trichlorobiphenyl (PCB 28), 13 C-2,3,3',5,5'- pentachloro-biphenyl (PCB 111), 13 C-2,2',3,3',5,5',6-heptachlorobiphenyl (PCB 178) 를구입하여혼합용액을제조하여사용하였다. 대기시료에대한추출, 정제, 농축등전처리는환경부잔류성유기오염물질공정시험기준 (ES 10900.1b, 2011) 에따라회수율을구하기위하여 13 C으로치환된정제용표준물질 (clean-up spike standards, CIL-ES-5342) 200 μl를 QFF에첨가한다음속슬렛으로 16-24시간추출하였고, 농축후플로리실컬럼과알루미나컬럼으로정제하였다. 기기분석대기중키랄 OCPs의잔류농도를측정하기위하여속슬렛추출후플로리실, 알루미나컬럼으로정제한시료는 HRGC (HP6890)/HRMS (Autospec Ultima Premier) 를사용하

대기환경중키랄유기염소계농약의분포특성 257 여정량분석하였다. 환경매질중잔류농도를측정하기위하여 OCPs인 HEPT, CC, TC, o,p'-ddt, p,p'-ddt와분해산물인 HEPX, OXY, o,p'-ddd, p,p'-ddd를정량분석하였으며, bleeding이작은 DB5-MS 컬럼 (30m 0.25mm I.D. 0.25μm film) 을사용한기기분석조건은 Table 2와같다. 동위원소희석법으로정량하기위하여검정곡선용표준물질 (native) 과 13 C 동위원소표지정제용표준물질의정량및확인 (confirmation) 을위한선택이온질량은 Table 3, 4 와같다. Table 2. Condition of quantitative analysis of OCPs using HRGC/HRMS GC condition MS condition Injector temp. 260 SIM(4 function MS mode Magnet Injector mode splitless Switching) Flow rate 1.2 ml/min Resolution >10,000 (He 99.999%) Column (DB5-MS) Interface 260 30m 0.25mm I.D. 0.25μm film Ion source 280 Oven Temp Ion energy 36 ev 80 (5 min) 20 /min 180 Accelerating 8 kv 2.5 /min 280 (5 min) voltage Table 3. Quantitation/confirmation 13 C labelled ions monitored by HRMS POPs(native) Quantitation ion Confirmation ion Ratio HEPT 276.8269 278.8240 100:80 HEPX 362.8778 364.8748 126:100 OXY 396.8388 398.8358 103:100 TC, CC 382.8595 384.8566 100:96.3 o,p'-ddd, o,p'-ddt POPs(native) 247.0484 249.0454 Quantitation ion Confirmation ion 157:100, 100:65 Table 4. Quantitation/confirmation native ions monitored by HRMS Ratio HEPT 271.8102 273.8072 100:80 HEPX 352.8442 354.8413 126:100 OXY 386.8052 388.8023 103:100 TC, CC 372.8260 374.8230 100:96.3 o,p'-ddd, o,p'-ddt 235.0081 237.0058 157:100, 100:65 키랄 OCPs 분석탄소에모두다른 4개의치환기가결합되어있을때비대칭탄소또는키랄중심 (chiral center) 이라하고, 분자에비대칭탄소가있으며거울상이성질체가존재하는화합물을키랄성 (chiral) 화합물 (Fig. 2) 이라하는데, 본연구에서는대기중 7개키랄 OCPs 및대사산물의 (+), (-) 거울상이성질체를분리하기위하여 CSP(chiral stationary phase) 을가지고있는 BGB-172 GC 컬럼과 β-dex 120을사용하였으며분석조건은 table 5와같다. (+) enantiomers of α-hch C 6H 6 6 chiral ( : chiral center) (-) enantiomers of α-hch C 6H 6 6 Fig. 2. Chemical structures of some hexachlorocychlohexane isomers. BGB-172 컬럼 (BGB Analytik AG, Lettenstrasse 97, CH8134 Adliswil, Switzerland) 은 20% tert-butyldimethylsilylβ-cyclodetrin 을 BGB-15 (15% phenyl/85% methylpolysiloxane) 고정상에녹여서제조하며, 키랄 OCPs 중 o,p'-ddt, o,p-ddd, HEPT, OXY, HEPX 5개항목의거울상이성질체를완전히분리하였다. TC과 CC은 BGB-172 컬럼을사용시 (+)TC > (+)CC > (-)CC > (-)TC 순서로용리 (elution) 되나 (-)CC와 (-)TC를완전히분리할수없었기때문에 20% permethylated β-cyclodextrin이 35% phenyl/65% dimethy siloxane (Supelco) 이혼합되어있는 CSP를사용하는 β-dex 120 컬럼 (Supelco) 으로 CC, TC 및 MC-5를 Fig. 3과같이재분리하였다 (Andi et al., 2000; Leone et al., 2001; Wiberg et al., 2001; Kurt-Karakus et al., 2005). 두종류의키랄컬럼을사용하여키랄 OCPs의거울상이성질체를완전히분리한다음 GC 크로마토그램상에서 (+) 와 (-) 거울상이성질체의면적을구하여개별키랄 OCPs의 EFs를구하였다.

258 CHOI et al. Table 5. Condition of chiral compounds analysis of OCPs using HRGC/HRMS GC condition Injector temp. 250 Injector mode splitless Flow rate 1.2 ml/min(he 99.999%) Column (BGB-172 and β-dex 120) 30m 0.25mm I.D. 0.25μm film Oven Temp ㆍBGB-172 90 (1 min) 20 /min 160 2 /min 180 (41 min) 25 /min 225 (23min) ㆍβ-DEX 120 90 (1min) 15 /min 140 1 /min 190 (10min) 20 /min 230 (10min) MS mode MS condition SIM (4 function Magnet Switching) Resolution >10,000 Interface 240 Ion source 250 Ion energy Accelerating voltage 36 ev 8 kv β-dex 120 column TC(+) TC(-) CC(+) CC(-) BGB-172 column CC(+) CC(-) TC(+) TC(-) Fig. 3. Chromatogram of trans-chlordane and cis-chlordane by chiral column (up : β-dex 120, down : BGB-172).

대기환경중키랄유기염소계농약의분포특성 259 QA/QC 환경부잔류성유기오염물질공정시험기준 (ES 10900.1b, 2011) 에따라정량분석결과의 QA/QC는회수율 40 120%, 동위원소존재의비율이이론값의 ±15% 범위내있는값만허용하였다. 키랄 OCPs의거울상이성질체를키랄 GC 모세관컬럼으로분리하여정확도와정밀도가높은 EFs를측정하기위하여가장중요한사항은피크의확인과피크면적측정이다. EFs 값측정의 QA (quality assurance)/qc (quality control) 를위하여두종류의컬럼 BGB-172와 β-dex 120으로각각 7가지키랄 OCPs 및분해산물과 TC과 CC의라세미표준물질을 7번측정하였다. 결과및고찰 유기염소계농약의잔류농도우리나라대기중에잔류하는 OCPs의분포현황과특성을조사하고장거리대기이동에의한영향을살펴보기위하여해안지점과농업지역인내륙지점에서각각 4일, 3일동안키랄 OCPs 및분해산물의잔류농도를 HRGC/HRMS 로조사한결과는 Table 6, 7과같았다. 해안지점의검출농도는 0.044 (HEPT) 2.460 (p,p'-ddt) pg/m 3 범위였으며, 내륙지점의검출농도는 0.014 (HEPT) 1.666 (TC) pg/m 3 범위였다. 이는 1999 2000년도대기중 OCPs 의잔류농도측정결과가도심지역서울은 1.2 (HEPT) 39 (DDT 류 ) pg/m 3, 농경지역안성은 3.7 (CC) 62.0 (DDT 류 ) pg/m 3 범위로보고된것 (Lee et al., 2001; Yeo et al., 2004) 과비교하면매우낮은수준임을알수있다. 해안지점의 3일농도평균은 0.052 (HEPT) 1.279 (p,p'- DDT) pg/m 3 이었으며, 내륙지점의 4일농도평균은 0.027 (HEPT) 1.055 (TC) pg/m 3 이었다. 조사대상해안지점과내륙지점에서모두 HEPT가가장저농도로검출되었으며, 해안지점에서는 p,p'-ddt, 내륙지점에서는 TC이가장고농도로검출되었다. Table 6. Concentrations of chiral OCPs in ambient air of coastal site HEPT HEPX TC CC OXY o,p'- o,p'- p,p'- p,p'- Sample DDT DDD DDT DDD (pg/m 3 ) A-P-1 0.044 0.176 0.5020.367 0.110 0.792 0.223 0.953 0.282 A-P-2 0.062 0.317 0.9060.593 0.257 1.150 0.358 0.935 0.347 Coa A-P-3 0.053 0.730 0.9461.362 0.366 1.082 0.281 0.768 0.282 stal area A-P-4 0.050 0.253 0.6230.657 0.153 1.354 0.392 2.460 0.610 Average 0.052 0.369 0.7440.745 0.222 1.095 0.314 1.279 0.380 RSD(%) 14.4 67.1 29.1 57.7 51.6 21.2 24.3 61.9 41.1 Sampling method : Japanese method (reference 58) This sample was affected yellow sand AVE : average, RSD : relative standard deviation Table 7. Concentrations of chiral OCPs in ambient air of inland site HEPTHEPX TC CC OXY o,p'- o,p'- p,p'- p,p'- Sample DDT DDD DDT DDD (pg/m 3 ) A-G-1 0.014 0.273 0.732 0.471 0.065 0.235 0.047 0.367 0.081 A-G-2 0.030 0.587 1.666 0.861 1.274 0.473 0.113 0.493 0.135 Inla A-G-3 0.038 0.481 0.767 0.782 0.377 0.404 0.096 0.462 0.085 nd AVE 0.027 0.447 1.055 0.705 0.572 0.371 0.085 0.441 0.100 RSD(%) 44.7 35.7 50.2 29.3 109.7 33.0 40.2 14.9 30.0 Sampling method : Japanese method (reference 58) AVE : average, RSD : relative standard deviation 해안지점에서는 p,p'-ddt, o,p'-ddt, CC, TC의순서로높게검출되었으며, 내륙지점에서는 TC, CC, OXY, HEPX 의순서로높게검출되었다. 특히 o,p'-ddt, o,p'-ddd, p,p'-ddt, p,p'-ddd는전부해안지점에서내륙지점보다평균 2.9 3.8 배높게검출되었으며, OXY, TC, HEPX는내륙지점에서해안지점보다평균 1.2 2.6배높게검출되었다 (Fig. 4). 해안지점과농업지역인내륙지점의대기중평균잔류농도를비교하면 OXY, TC, HEPX의농도가농업지역인내륙지점에서높게검출된것은예측가능한결과이다. 그러나, DDT류의농도가농경지역인내륙지점보다해안지점에서훨씬높게나타난것은예상과다른결과이며이는해안지점이서해안에위치하고있어서궤적분석결과중국의대기가우리나라서해로이동해오는사실과관련하여현재에도 DDT로오염되어있는디코폴타입 DDT를사용하는중국의영향때문으로판단할수있다 (Qiu et al., 2005; Jun et al., 2006). Fig. 4. Concentration of ambient air of coastal and inland sites. 대기중에잔류하는 OCPs의오염원을파악하기위하여조사대상 OCPs과분해산물의평균검출농도를비교하면 (Yeo et al., 2004; Shen et al., 2005) HEPT와 HEPX의경우, HEPT의농도는해안지점에서 0.052 pg/m 3, 내륙지점에서 0.027 pg/m 3 으로내륙보다해안지점에서높게조사된반면, HEPX는해안지점에서 0.369 pg/m 3, 내륙지점에서 0.447 pg/m 3 으로내륙지점에서높게조사되었다. 해안지점에서 HEPX 의농도는 HEPT보다 7.1배높게검출되었으며 HEPT의 %RSD는 14.4%, HEPX의 %RSD는 67.1% 로 HEPX의농도변화가크게나타났다. 내륙지점에서 HEPX의농도는 HEPT의 16.5배높게검출되었으며 HEPT의 %RSD는 44.7%, HEPX의 %RSD 35.7% 로두항목모두농도변화

260 CHOI et al. 에큰차이가없었다. HEPT는광분해와같은비키랄과정이나미생물에의한키랄과정을거쳐더안정한 HEPX로빠르게분해되어환경중에오랫동안잔류하는것으로알려져있다 (Harner et al., 1999; Wiberg, 2001; Shen et al., 2005). HEPT와 HEPX의대기중농도가해안가에서는 HEPT가내륙에서는분해산물인 HEPX가더높게나타났는데, 이는내륙토양중의 HEPX가휘발이나대기에영향을주고있다는것을시사하고있다 (Harner et al., 1999; Shen et al., 2005). 그러나, 보다명확한판단을위해서는 HEPX 자체가장거리이동되어국지적으로대기의잔류농도에영향을줄수도있기때문에대기와토양간의퓨가시티분율을계산하는연구등의추가연구가필요하다고본다. TC, CC, OXY 의검출농도평균을살펴보면 CC과 TC의농도는해안지점에서각각 0.745 pg/m 3, 0.744 pg/m 3, 내륙지점에서각각 0.705 pg/m 3, 1.055 pg/m 3 으로 TC만내륙지점에서높게조사되었으며, OXY 은해안지점에서 0.222 pg/m 3, 내륙지점에서 0.572 pg/m 3 으로내륙지점에서높게조사되었다. 해안지점에서 CC과 TC의 %RSD는각각 57.7%, 29.1% 이었으며, OXY의 %RSD는 51.6% 이었다. 내륙지점의 CC과 TC의 %RSD는각각 29.3%, 50.2% 이었으며, OXY의 %RSD는 109.7% 이었다. CC과 TC은모두잔류성분해산물인 OXY 으로분해된다 (Wiberg, 2001). 해안지점과내륙지점에서모두모화합물인 CC과 TC의평균농도합이 OXY에비하여 6.7배, 3.1배로높게검출되었다. 이는우리나라대기중 CC과 TC 그리고 OXY은과거오염에의하여오염된토양에서휘발되어대기로부하되는양보다는현재사용에의한오염이영향을주고있음을나타내고있다. DDT는독성이더크고안정한 DDD로미생물에의하여분해된다 (Harner et al., 1999). 우리나라대기중모화합물인 DDT와분해산물인 DDD의농도를비교해보면해안지점과내륙지점에서모두모화합물의농도가높은것으로나타나우리나라대기중에잔류하는 DDT류의오염원또한최근에사용된 DDT에의한것임을암시하고있다. 키랄유기염소계농약의거울상이성질체비율대기중키랄 OCPs의 EFs 및분포현황을파악하기위하여조사대상인해안지점 (4일) 과내륙지점 (3일) 의대기중 HEPT 등 8종의키랄 OCPs 및분해산물에대한 EFs를측정하였으며그결과는 Table 8, 9와같다. 기존의연구결과에따르면, 생물학적과정의영향을받지않은키랄오염물질은라세미혼합물로존재하며 EFs는 0.5에근접하지만, 미생물분해와같은생물학적과정에노출되면키랄오염물질은선택적분해가진행된다. (-) 거울상이성질체가선택적으로제거되면 (+) 거울상이성질체가축적되어 EFs > 0.5를나타내며, (+) 거울상이성질체가선택적으로제거되어 (-) 거울상이성질체가축적되면 EFs < 0.5를나타내는것으로알려져있다 (Finizio et al., 1998; Harner et al., 2000; Bidleman et al., 1999; Hung et al., 2002). 해안지점의대기중항목별평균 EFs는 TC, CC, MC-5의 3가지키랄클로르단류는 0.5 이하, HEPX, OXY은 0.5 이상으로나타났다. 내륙지점의경우항목별평균 EFs는 TC, CC, MC-5의 3가지키랄클로르단류는 0.5 이하, HEPX, OXY은 0.5 이상으로해안지점과유사하였으나, o,p'-ddt와 o,p'-ddd는각각해안지점은 0.50, 0.51, 내륙지방은 0.53, 0.62로나타나 o,p'-ddd는지점간에큰차이가있었으며, 해안지점의 EFs가훨씬낮게나타나이는두지점의오염원이서로상이함을나타내며시료채취기간동안발생한황사의영향으로추정된다. 미국, 북극등다른지역의대기중키랄 OCPs의 EFs는지역에따라큰차이가있으나일반적으로 HEPX의경우 EFs가 0.5 보다크고키랄 OCPs이나분해산물중가장큰값을나타내며 (Aigner et al., 1998; Hites, 1998; Bidleman et al., 2002; Shen et al., 2005), TC은 0.5 보다작으며, CC 은 0.5 보다큰값으로보고되고있다. 따라서, 우리나라대기중 EFs 값도유사한경향을보이고있으나 CC은 0.5보다낮은값으로다른경향을보여주었다. 이러한결과는 OCPs은주로장거리대기이동이나오염된토양에서거울상선택적으로분해된다음휘발되어대기로유입되기때문에지역적차이를반영하는것으로판단된다. 대기중 OCPs의잔류농도분석결과 Table 8, 9에서보는바와같이 HEPT의잔류농도가 0.014 0.062 pg/m 3 로매우낮아서 (+), (-) 거울상이성질체를분리할수없었기에 EF 값을구할수없었다. Table 8. EF of chiral OCPs in ambient air of coastal site Sample HEPTHEPX TC CC MC-5 OXY o,p'- DDT o,p'- DDD A-P-1-0.74 0.50 0.46 0.48 0.50 0.51 0.51 A-P-2-0.69 0.48 0.48 0.49 0.58 0.50 0.51 A-P-3-0.71 0.47 0.40 0.52 0.55 0.50 0.50 A-P-4-0.70 0.49 0.46 0.46 0.54-0.51 AVE - 0.71 0.48 0.45 0.49 0.54 0.50 0.51 SD - 0.02 0.01 0.04 0.02 0.03 0.01 0.00 This Sample was affected by yellow sand AVE : average, SD : standard deviation Table 9. EF of chiral OCPs in ambient air of inland site Sample HEPT HEPX TC CC MC-5 OXY o,p'- DDT o,p'- DDD A-G-1 - - 0.50 0.49 0.48 - - - A-G-2-0.74 0.48 0.46 0.50 0.63 0.57 0.62 A-G-3-0.71 0.46 0.49 0.49 0.56 0.50 - AVE - 0.73 0.48 0.48 0.49 0.60 0.53 0.62 SD - 0.02 0.02 0.02 0.01 0.05 0.05 AVE : average, SD : standard deviation 이는대기중 HEPT 는빠르게광분해되어 (Aigner et al., 1998; Shen et al., 2005) 주된광분해산물은포토헵타클로

대기환경중키랄유기염소계농약의분포특성 261 르를생성하며일부 HEPT로분해된다 (Wiberg, 2001). 그러므로, 대기중 HEPX의 EFs가 0.5 보다큰것은대기중 HEPX는 HEPT의광분해가아닌토양이나수질중의 HEPX가미생물에의하여거울상선택적으로분해된다음대기중으로휘발되어유입되는것으로볼수있다 (Aigner et al., 1998; Shen et al., 2005). 황사발생시 Air Mass 의궤적분석동아시아 9개국이참여하는 POPs 모니터링사업에서 POPs의장거리이동경로를추적하고자 METEX 프로그램중 3D-wind model과 NCEP 재분석데이터를이용하여시료채취시기의대기에영향을준기단 (air mass) 의이동궤적 (trajectory) 를분석한결과 Fig. 5, 6과같이해안지점과내륙지점의시료채취시기에우리나라는대부분중국지역에서이동해온기단의영향을받고있다. 해안지점의시료채취시기에는 Fig. 5와같이중국과몽고의사막지역에서부터발 원한 Air Mass와함께황사가이동해왔으며, 내륙지점의시료채취시기에는 Fig. 6과같이중국과몽고를거쳐동해상공을통과하는궤적을보여주고있다. 즉, 시료채취일자에따라우리나라에영향을준발생원이다르지만우리나라는중국, 몽고, 북한과같이최근에도 OCPs를사용할가능성이있는국가들의상공을거쳐장거리이동한대기의영향을받고있는것으로나타났다. HEPT는사용이중단되었고, 클로르단은중국일부지역에서흰개미방제를위하여불법으로아직도사용되고있으며 DDT는 dicofol 타입으로계속사용하고있다.(Qiu et al., 2005; Jun et al., 2006). 따라서, 우리나라에서 DDT류는과거사용에따른토양의잔류농도는사용금지된기간이 30년이상지났기때문에 ppb 이하의극미량이잔류하고있는데비하여, 대기중잔류농도가해안가지점에서최고 2.5 pg/m 3 수준까지검출되는것은현재사용하고있는지역대기가장거리이동함에따라직접적인영향을미친것으로추정된다. Back trajectory mode : Simulation period (21 Mar. to 28 Mar.)Forward trajectory mode : Simulation period (28 Mar. to 4 Apr.) Fig. 5. Trajectory analysis of ambient air collected at coastal site. Back trajectory mode : Simulation period (8 Mar. to 15 Mar.)Forward trajectory mode : Simulation period (15 Mar. to 22 Mar.) Fig. 6. Trajectory analysis of ambient air collected at inland site.

262 CHOI et al. 결론 국내 OCPs의잔류농도및 EFs의분포현황을파악하기위하여해안지점과내륙지점의대기중에잔류하는키랄 OCPs 및분해산물인 HEPT, TC, CC, MC-5, o,p'-ddt, HEPX, OXY, o,p'-ddd 와비키랄 OCPs p,p'-ddt, 4,4'-DDD의잔류농도및 EFs을비키랄컬럼과키랄컬럼을사용한 HRGC/HRMS ( 분해능 >10,000) 로측정한결과, 대기중 OCPs의잔류농도는해안지점에서는 DDT류, 내륙지점에서는 HEPX와클로르단류의농도가높았다. 대기중키랄 OCPs의 EFs는 2 지점모두 HEPX의평균 EFs이가장높은것으로조사되었으며클로르단류를제외하면 EFs이전부 0.5 이상으로 (-) 거울상이성질체가우선적으로분해되는것으로나타났다. 우리나라대기는일반적으로서쪽에위치한중국대기의영향을받고있는것으로나타난궤적분석결과와함께대기중검출농도및 EFs를고려해보면, 일부 OCPs는주로최근에사용한지역의 OCPs가대기의장거리이동과정을거쳐우리나라로유입될가능성을배제할수없는것으로나타났다. 참고문헌 Aigner, E.J., Leone, A.D., Falconer, R.L., 1998. Concentrations and Enantiomeric Ratios of Organochlorine Pesticides in Soils from the U.S. Corn Belt, Environ. Sci. Technol. 32, 1162-1168. Andi, D.L., Elin, M.U., Colleen, E.B., Renee, L.F., Ronald, A.H., 2000. Organochlorine pesticide concentrations and enantiomer fractions for chlordane in indoor air from the US cornbelt, Atmos. Environ. 34, 4131-4138. Bidleman, F.T., Falconer, R.L., 1999. Enantiomer ratios for apportioning two sources of chiral compounds, Environ. Sci. Technol. 33(13), 2299-2301. Bidleman, F.T., Jantunen, L.M.M., Helm, P.A., Brorstrom- Lunden, E., Juntto, S., 2002. Chlordane Enantiomers and Temporal Trends of Chlordane Isomers in Arctic Air, Environ. Sci. Technol. 36, 539-544. Bidleman, F.T., Leone, D.A., 2004. Soil-air exchange of organochlorine pesticides in the Southern United States, Environ. Pollut. 128, 49-57. Choi, J.W., Lee, K.S., Lee, J.K., No, K.B., 1987. Residue Levels of Organochlorine Pesticides on Paddy Field Soils in the Chungnam Area, Korean J. environ. Agric. 6, 12-21. Finizio, A., Bidleman, F.T., Szeto, S.Y., 1998. Emission of chiral pesticides from an agricultural soil in the Fraser Valley, british columbia, Chemosphere 36, 345-355. Haglund, P, Wiberg, K., 1996. Determination of the gas chromatographic elution sequences of the (+)-and (-)-enantiomers of stable atropisomeric PCBs on Chirasil-Dex, J. High Resolut. Chromatogr. 19, 373-376. Harner, T., Wiberg, K., Norstrom, R., 2000. Enantiomer fractions Are preferred to enantiomer ratios for describing chiral signatures in environmental Analysis, Environ. Sci. Technol., 34(1), 218-220. Harner, T., Wideman, J.L., Jantunen, L.M.M., Bidleman, F.T., Parkhurst, W. J., 1999. Residues of organochlorine pesticides in Alabama soils, Environ. Pollut. 106, 323-332. Hites, R.A., 1998. Enantiomeric Ratios of Chlordane-Related Compounds in Air near the Great Lakes Ulrich, Environ. Sci. Technol. 32, 1870-1874. Hung, H., Halsall, C.J., Blanchard, P., Li, H.H., Fellin, P., Stern, G., Rosenberg, B., 2002. Temporal trends of organochlorine pesticides in the canadian arctic atmosphere, Environ. Sci. Technol., 36(5), 862-868. Jung, Y.P., Choi, M.K., Yeo, H.K., Chum, M.Y., 2001. Seasonal Variations in the Concentration of Persistent Organochlorine Pesticides in Atmosphere, Korean J. environ. Agric. 20, 79-85. Kurt-Karakus, P.B., Bidleman, T.F., Jones, K.C., 2005. Chiral Organochlorine Pesticide Signatures in Global Background Soils, Environ. Sci. Technol. 39, 8671-8677. Lee, K.T., Tanabe, S., Koh, C.H., 2001. Distribution of organochlorine pesticides in sediments from Kyeonggi Bay and nearby areas, Korea, Environ. Pollut. 114, 207-213. Lee, S.R., 1982. Overall Assessment of Organochlorine Insecticide Residues in Korean Food, Korea J. Food Sci. Technol. 14, 82-93. Leone, A.D., Amato, S., Falconer, R.L., 2001. Emission of Chiral Organochlorine Pesticides from Agricultural Soils in the Cornbelt Region of the U.S., Environ. Sci. Technol. 35, 4592-4596. Li, J., Zhang, G., Qi, S., Li, X., Peng, X., 2006. Concentrations, enantiomeric compositions, and sources of HCH, DDT and chlordane in soils from the Pearl River Delta, South China, Sci. Total Environ. 372, 215-224. Qiu, X., Zhu, T., Yao, B., Hu, J., Hu, S., 2005. Contribution of Dicofol to the Current DDT Pollution in China, Environ. Sci. Technol. 39, 4385-4390. Shen, L., Wania, F., Lei, Y.D., Teixeira, C., Muir, D.C.G., Bidleman, T. F., 2005. Atmospheric Distribution and Long-Range Transport Behavior of Organochlorine Pesticides in North America, Environ. Sci. Technol. 39, 409-420.

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