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1 Printed in the Republic of Korea ANALYTICAL SCIENCE & TECHNOLOGY Vol. 27, No. 4, , Note ( 단신 ) Study on analysis of PAHs in consumer products Moon Hwan Song, Young Dal Cho and Eun Kyung Choe Product Eco-testing and Chemical Analysis Laboratory, Korea Institute of Industrial Technology, Ansan, Gyeonggi , Korea (Received May 20, 2014; Revised July 16, 2014; Accepted July 16, 2014) 공산품함유 PAHs 분석법에관한연구 송문환, 조영달, 최은경 한국생산기술연구원국제환경규제대응기술지원센터유해물질분석실 ( 접수, 수정, 승인 ) Abstracts: Polycyclic aromatic hydrocarbons (PAHs) that are carcinogenic and persistent will be restricted in consumer products from December 27, 2015 by EU REACH regulation. Pretreatment using Soxhlet extraction and quantitative analysis by GC-MS were studied to develop the method for analyzing 18 PAHs in consumer products as well as to detect the amounts and the kinds of PAHs in consumer products such as grips of a bag and a hammer, a cable and a plastic sandal. Linearity and precisions were evaluated by analyses of the standard PAH solutions ranging from mg/l to 5.00 mg of each of 18 PAHs. Linearity of resulting standard curves for all 18 PAHs were obtained with R 2 above Precisions of the retention times and the peak areas were found to be 0.00%~0.05% and 1.16%~.69% of relative standard deviations, respectively. The recoveries for spiked samples were all around 95%~105% after Soxhlet extration using three different solvents such as dichloromethane, hexane and toluene. The limits of quantitation for 18 PAHs in solutions and polymer samples by GC-MS were evaluated to be 0.27 mg/l (Benzo[ghi]perylene)~0.464 mg/l (Acenaphthylene) and 1.65 mg/kg (Benzo[ghi]perylene)~2.2 mg/kg (Acenaphthylene) based upon dilution factor of 5, respectively. Under the developed analytical method, only trace amounts of phenanthrene were detected in three samples while 15 kinds of PAHs including phenanthrene were detected in a grip of hammer with concentrations of maximum 8.4 mg/kg of Phenanthrene and minimum 8.5 mg/kg of Acenaphthylene. Further studies are needed to decrease the quantitation limit and to check the feasibility of decreasing Soxhlet time as well as to demonstrate cases that the clean up is required. 요약 : 발암성및잔류성을갖는다환방향족탄화수소 (Polycyclic aromatic hydrocarbons, 이하 PAHs) 의법적인규제가공산품함유에로확장된현황에서, 본연구에서는속슬렛추출에의한전처리및 GC-MS 분석에의한공산품에함유된 18 종 PAHs의정량분석법을확립하고공산품 4종에서의 18 종 PAHs 함유여부를분석하였다. GC-MS SIM 크로마토그램의머무름시간및피크면적의정밀도는각 0.00%~0.05% 및 1.16%~.69% 의 RSD로측정되었고각 PAH의농도범위 mg/l~5.00 mg/l에서얻은검정곡선 Corresponding author Phone : +82-(0) Fax : +82-(0) ekchoe@kitech.re.kr 201

2 202 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe 은상관계수 R 2 값이 18 종모두 이상으로산출되었다. 본검정곡선을이용한 18 종 PAHs의 GC- MS 기기분석의정량한계는 0.27 mg/l (Benzo[ghi]perylene)~0.464 mg/l (Acenaphthylene) 로산출되었다. 스파이킹에의한 18 종 PAHs의속슬렛추출에의한회수율은 DCM, 헥세인, 혹은톨루엔사용시모두 95%~105% 로측정되었고, 이상의조건에서국내에서유통되는공산품 4종에서 18 종 PAHs를분석한결과, 개시료에서는 Phenanthrene이정량한계근방의소량으로검출되었고, 망치 ( 손잡이부분 ) 시료에서는 Phenanthrene을비롯한 15 종 PAHs가최대 8.4 mg/kg~ 최소 8.5 mg/kg 범위로검출되었다. Key words: polycyclic aromatic hydrocarbons, GC-MS analysis, plastics, grip, consumer products 1. 서론다환방향족탄화수소 (polycyclic aromatic hydrocarbons, 이하 PAHs) 는석유및석탄에서유래하는 2개 ~7 개의방향족고리로축합구성된 (fused aromatic ring system) 화학물질그룹이다. PAHs는가정난방, 산업공정, 자동차, 음식물의요리, 소각, 발전, 담배연기등에서불완전연소로발생하여대기및수질오염물질로서단독물질보다는혼합상태로존재하며, 보통벤조피렌이 PAHs의마커가되는데, 이들 PAHs는발암성물질이다. 1,2 PAHs는음식조리과정혹은환경오염에의한조리가공하지않은식품에도존재하여식품에서의 PAHs 분석이나, -6 토양, 수질및대기중 PAHs 분포및발생원등에관한연구가활발히진행되어왔다 국제암연구소 (IARC:International Agency for Research on Cancer) 에서는 PAHs 화합물중 Benzo[a]pyrene을발암물질로, Dibenzo[a,h]anthracene을 Group 2A의유력한인체발암물질 (Probably carcinogenic to humans) 로분류하였고 (Table 1), 1 이에더하여유럽신화학물질관리제도 ( 이하 REACH) 에서는안트라센에대한충분한생태독성자료도추가로확보하여 PBT (Persistent, Bioaccumulation and Toxic ( 잔류성, 생물농축성및독성 ) 물질로분류를하였고, 14,15 이로인해안트라센보다벤젠고리수가많은다른 PAHs에대해서도 PBT 물질로의분류가확실시되고있다. 이러한 PAHs에대해미국 EPA에서는 PAHs 16 종을우선순위대상을선정하여관리하고있으며, 12 국내에서도 PAHs를환경보건법의위해성평가실시대상환경유해인자에포함시키고있다. 16 REACH에서신전유 (extender oils) 및이를사용한타이어에대해 8종 PAHs의함유가제한되어온이래 (Table 1), 공산품내에 PAHs 함유는독일 GS 마크 (18 종 PAHs 규제 ), 섬유제품에코라벨인 Oeko-Tex Standard 100(24 종 PAHs 규제 ), Nordic Ecolabelling ( 장난감및자동차타이어 ) 에서규제되어왔으나 강제적인법령은아닌반면, 독일의주도로, 18 유럽화학물질청에서 201년 12월 REACH 부속서17 ( 제한물질 ) 의 PAHs ( 목록 No.50) 를개정하여신전유 (extender oils) 및이를사용한타이어에서의 PAHs 제한이완제품, 즉공산품으로확장됨으로서, PAHs의공산품내함유량제한이강제성을갖는유럽의법령이되어 2015년 12월 27일부터시행예정에있다 (Table 2). 21 따라서, 전기전자제품, 부엌도구, 장난감, 핸들, 자전거 / 가방 / 연장손잡이, 신발, 비치샌달, 스포츠용품, 장갑, 의류등관련제품 의원활한유럽수출을위해서는이들완제품의고무나플라스틱부품에대한 PAHs 검출동향에대한광범위한조사와함께, PAHs-free 혹은 PAHs-reduced 제품생산을위한대응이적시에이루어져야하는시점이다. 토양, 대기, 물시료, 폐수내에서의 PAHs 정량분석에비해, 4-12,22-26 공산품에함유된 PAHs 분석법에대한자료가많지않고상세자료가부족한현황에서 (Table ), 26,27 이연구에서는 18 종 PAHs에대한 GC-MS 분석의유효화자료를확보하고, PAHs 함유가능성이있는시중공산품 4종에서속슬렛을이용한최적전처리방법을확립해보면서공산품에서의 PAHs 분석법개발의향후방향을제안해보고자한다 시약 2. 실험 Dichloromethane ( 이하 DCM), n-hexane, toluene은시약급 (J.T. Baker) 을사용하였고, 헬륨은순도 % 을사용하였다. Table 1의 18 종 PAHs는 o2si smart solution 사에서시약급 ( 표준시약 ) 으로구입하여정제없이사용하였다 (18 종 PAHs 혼합표준용액, 각 2,000 mg/l, DCM). Analytical Science & Technology

3 Study on analysis of PAHs in consumer products 20 Table 1. Summary of the listed PAHs in REACH, US EPA, and German GS mark Substance name CAS No Chemical structure Classification a) REACH US EPA German GS Mark 1 Acenaphthene Acenaphthylene Anthracene Benzo[a]anthracene (BaA) Benzo[b]fluoranthene (BbFA) Benzo[j]fluoranthene (BjFA) Benzo[k]fluoranthene (BkFA) Benzo[ghi]perylene (BgP) Benzo[a]pyrene (BaP) (2012) 10 Benzo[e]pyrene (BeP) Chrysen (CHR) Dibenzo[a,h]anthracene (DBAhA) A 1 Fluoranthene Fluorene Indeno[1,2,-cd]pyrene Naphthalene (2002) 17 Phenanthrene Pyrene Vol. 27, No. 4, 2014 a) Group 1 : Carcinogenic to humans, Group 2A () : Probably (Possibily) carcinogenic to humans Group : Not classifiable as to its carcinogenicity to humans

4 204 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe Table 2. Current prohibitions on use of PAHs in consumer products Regulation or Certification PAHs 1 German GS mark a) Voluntary 2 Oeko-Tex Standard 100 mark b) REACH regulation (Annex XVII, No.50) Voluntary Compulsory (Jan ) Compulsory (Dec. 27, 2015) Limits for PAH content (mg/kg) Mouthable materials or materials of toys for children under 6 months Materials with long-term skin contact c) Materials with short-term skin contact c) Benzo[a]pyrene not detectable (< 0.2) 1 20 Sum of 18 PAHs not detectable (< 0.2) Textile products for baby Other textile products Benzo[a]pyrene Sum of 24 PAHs d) 5 10 Extender oils Tyres and treads for retreading Benzo[a]pyrene 1 do not contain extended oils Sum of 8 PAHs 10 exceeding the limits in left column Rubber or plastic components e) in articles f) General toys or childcare articles Any of 8 PAHs Updated date a) GS : Safety Tested b) World-recognized textile ecolabel c) Longer than 0 sec / up to 0 sec d) Cyclopenta[c,d]pyrene, Dibenzo[a,e]pyrene, Dibenzo[a,h]pyrene, Dibenzo[a,i]pyrene, Dibenzo[a,l]pyrene, 1-Methylpyrene in addition to 18 PAHs in Table 1 e) Direct as well as prolonged or short-term repetitive contact with the human skin or the oral cavity f) Sport equipment such as bicycles, golf clubs, racquets/household utensils, trolleys, walking frames/tools for domestic use/clothing, footwear, gloves and sportswear/watch-straps, wrist-bands, masks, head-bands Nov Jun. 201 Dec Dec 장비및기기 시료분쇄에는 centrifugal mill (Pulverisette 14, Germany) 을사용하였고, 시료매질로부터 PAHs 추출에는 100~150 ml의속슬렛추출기와 250 ml 둥근플라스크를사용하였다. PAHs의정량분석에는 GC- MS(Gas Chromatography-Mass Spectometry) (HP 6890, 검출기 MS (597N), Agilent) 를사용하였고반복성 (repeatability) 을위하여자동시료채취장치를사용하였다 (Agilent, GC-MS 768 series injector). 시료매질의성분분석에는 Diamond ATR (Attenuated Total Reflectance) 악세서리 (MIRacle, PIKE) 를이용하여 FT-IR (NEXUS, Thermo Nicolet) 을측정하였다. 2.. 표준용액의제조 GC-MS 검량곡선작성을위하여구입한 18 종 PAHs 혼합표준용액 ( 각 2,000 mg/l, DCM) 을이용하여 5.00, 2.50, 1.25, 0.625, mg/l 농도의 PAHs 18 종표준용액을제조한후검량곡선및정밀도측정에사용하였다 시료및시료샘플링시료는 PAHs 함유가능성이높은공산품 4종을시중에서구매하였고각공산품의해당부품의주요매질성분은 ATR FT-IR 을측정하여확인하였다 (Table 6). 시료를대략 5 mm 5 mm로자르고잘섞은후 centrifugal mill을이용하여입자의크기를 500 µm로균일하도록분쇄하였다 가지추출용매를사용한속슬렛전처리분쇄한시료를전자저울을이용하여 2 g 측정후속슬렛용필터 (thimble filter) 안에넣고 100 ml의추출용매를이용하여 60~80 o C에서 16 시간동안속슬렛장치로추출한후실온에서식혔다. 이어회전증발농축기를이용하여증발농축시킨후추출에사용된용매를이용하여녹여내어최종부피를정해진부피 (10 ml) 로맞추었다. 이와같은과정을각각 DCM, hexane, toluene을이용하여수행하였고, toluene의경우 2시간이상소요에도불구하고약 80% 이상부피가남아있어최종부피를다시 100 ml로맞추었다. Analytical Science & Technology

5 Study on analysis of PAHs in consumer products 205 Table. Comparison of existing standards on testing of PAHs in rubber and plastic materials Standard (Latest Rev.) ZEK a) (2011) KS M 6956 Title of standard Harmonized method for determination of Polycyclic Test method for estimating the toxicity of recycled rubber powder Aromatic Hydrocarbons (PAHs) in polymer Scope Polymers (e.g. plastic or rubber material) recycled rubber powder PAHs tested 18 PAHs b) 18 PAHs Size of sample Particles of max 2- mm As recycled powder without further grinding Sample weight 0.5 g 1.0 g Extraction method Ultrasonic extraction with toluene (20 ml), 1 h, 60 o C Soxhlet extraction with hexane or dichloromethane (100 ml), 16 h Clean-up Final volume Calibration solutions Remarks Clean-up column (ca mm) with 4 g silica gel and 1 cm sodium sulphate / elution with 50 ml petroleum ether Concentrated 1 ml / to a defined volumn with toluene Calibration solutions of 2.5 to 250 µg/l to cover the range of the samples from 0.1 to 10 mg/kg Internal standards : Standard 1: naphthalene-d8 Standard 2: pyrene-d10 or anthracene-d10 or phenanthrene-d10 Standard : benzo(a)pyrene-d12 or perylene-d12 or triphenylbenzene Cartridge column with min. 0.5 g silica/elution with ml of mixed solvent (DCM:hexane=1:1) 1 ml using a rotary evaporator --> further to 200~250 µl using flow of nitrogen --> to a defined volumn with acetonitrile, for ex. Not mentioned (Standard solution : 10 mg/l using acetonitrile, for ex.) ESTD Analytical equipment GC-MS with SIM GC-MS with scan mode Column HT8 25 m 0 m, not specified a) German method for certification of GS mark / b) Still contain the chromatogram of 16 PAHs in ZEK (2008) 각시료당 가지추출용매별로각 회씩전처리를반복하여용매별로추출효율을산정하였다 2.6. GC-MS 분석 GC-MS 분석조건검량곡선작성을위해마련된 2.의표준용액및 2.5의전처리로마련된시료용액을기체크로마토그래피와질량분석법으로분석할때사용된 GC 컬럼, 온도프로그래밍, acquisition mode 등의주요 GC-MS 분석조건을 Table 4에정리하였다. Table 4에정리된각 PAH의 m/z을이용하여선택이온검출법 (SIM, selected ion monitoring) 으로분석하였고, PAHs 외의간섭물질을확인하기위해총이온전류질량분석방법 ( 전주사법 ) 을병행하였다 GC-MS 분석의직선성, 정밀도, 검출한계및정량한계산출 28 PAHs의 GC-MS 정량분석의직선성은 2.에마련된 5 개농도의 18 종 PAHs표준용액을각농도별로 회 측정하여얻은선형회기식 (Y = ax + b) 의상관계수 R 2 값으로가름하였다. 또한 5개농도의표준용액을 GC-MS로 7회반복측정하여피크면적 (peak area) 및머무름시간r(retention time) 에대한상대표준편차 (relative standard deviation, 이하 RSD) 를구해 18 종 PAHs의 GC-MS 분석의정밀도를산출하였다. 직선성및정밀도를위한매측정사이에바탕용액 (blank solution) 을 1회분석하여 QC 관리를하였다. GC-MS 분석법의검출한계 (LOD, limit of detection) 및정량한계 (LOQ, limit of quantitation) 는검정곡선의선형회기식 (Y = ax + b) 을이용하여아래식과같이계산하였고, 희석배수를곱하여고체시료에대한정량한계를산출하였다. 28 LOD =. s/s (1) LOQ = LOD (2) σ : 선형회기식의 y 절편 (b) 의표준편차 S : 선형회기식의기울기 (a) Vol. 27, No. 4, 2014

6 206 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe Table 4. GC-MS chromatographic conditions for 18 PAHs Parameters Column DB-EUPAH (60 m 0.25 mm 0.25 µm) Carrier gas Helium with flow rate of 1.0 ml/min Injection mode Splitless Injector temperature 280 o C Injection volumn 1 µl Initial : 100 o C for 2 min Oven temp. program 10 o C/min up to 200 o C for 0 min 7 o C/min up to 250 o C for 2 min o C/min up to 00 o C for 15 min Conditions Aquisition mode Scan 50~550 amu SIM Selected ions, m/z 1 Naphthalene Chrysen Acenaphthylene Benzo[b]fluoranthene 252 Acenaphthene Benzo[j]fluoranthene Fluorene Benzo[k]fluoranthene Phenanthrene Benzo[a]pyrene Anthracene Benzo[e]pyrene Fluoranthene Indeno[1,2,-cd]pyrene Pyrene Dibenzo[a,h]anthracene Benzo[a]anthracene Benzo[ghi]perylene 시료에함유된 PAHs 함유량계산시료중의 PAHs 18 종함유량은, 18 종 PAHs의각검정곡선에의하여시험용액을측정한결과에희석배수 (dilution factor) 를곱한다음식에따라계산하였다. C V 시료내각 PAH 함유량 (mg/kg) = () W C : 검량곡선에의해측정된시료용액중의각 PAH 농도 (mg/l) V : 시료용액의최종부피 (ml) W: 시료의무게 (g) 각시료별로전처리부터기기분석까지 회반복분석하여함유량평균과표준편차를산출하였다 소량첨가 (spiking) 에의한 PAHs 회수율 산출 28, 의 4종시료중고무망치 ( 손잡이부분 ) 시료를분쇄하여 1 g 무게를정확히측정하여원통형여과지 (thimble filter) 에넣고, 분석대상물질인 PAHs 18 종표준용액 (500 mg/l) 을 1 ml 첨가하여 spiking에의한시료의각 PAH 함유량이 500 mg/kg이되도록하였다. 추출용매 DCM, hexane, toluene 각 종류를이용하 여 2.5에따라전처리하여 GC-MS로정량분석한후, 소량첨가후분석농도를이론농도로나누어각 PAH 의회수율을계산하였다. 이론농도는 spiking된각 PAH의양에, 소량첨가전의시료를동일하게전처리하여분석한각 PAH의양을더한값으로하였으며, 1 개의시료에대하여전처리부터기기분석까지 회반복분석하여회수율평균과표준편차를산출하였다.. 결과및고찰.1. GC-MS에의한 18 종 PAHs 분리공산품에서규제되고있는 18 종 PAHs는 Table 1의구조식에서볼수있듯이벤젠고리 2개가축합된나프탈렌부터최대 6개가축합된 Benzo[ghi]perylene로구성되어있고이들 18 종 PAHs가상용 DB-EUPAH 컬럼을사용하여 Table 4의 GC-MS 분석조건에서모두분리되었다 (Fig. 1(b). 각 PAH의머무름시간 (retention time) 은축합된벤젠고리가증가할수록증가하였는데, 이는벤젠고리가 2, 2.5,,.5, 4, 4.5, 5, 5.5, 6으로증가할수록컬럼과의상호작용및끓는점의증가와연관이있다 ( 축합된고리가다시결합된구조를편의상 0.5로표시함 ). Analytical Science & Technology

7 Study on analysis of PAHs in consumer products 207 Fig. 2. Precision of retention times and peak areas (n = 7) of each PAH in the concentration range of to 5.00 mg/l using the GC-MS system in this study. Fig. 1. GC-MS total ion chromatograms of standard solution of 18 PAHs with different columns. 18 종 PAHs 는 EPA 에서규제하는 16 종 PAHs(EPA- PAHs) 와비교할때 Benzo[j]fluoranthene과 Benzo[e] pyrene이더포함되는데, 이두개물질의머무름시간은연이어분리되어나오는 Benzo[b]fluoranthene (4.5), Benzo[j]fluoranthene (4.5), Benzo[k]fluoranthene (4.5), Benzo[a]pyrene (5), Benzo[e]pyrene(5) 5 개물질중 2 번째 5번째에위치한다. EPA-16 PAHs 분리에사용되던컬럼을사용할경우, 벤젠고리수가같은 Benzo[b] fluoranthene(4.5), Benzo[j]fluoranthene(4.5), Benzo[k]fluoranthene(4.5) 의 개물질이분리가되지않았고 (Fig. 1(b)) 따라서 DB-EUPAH 컬럼을이용하여 18 종 PAHs가모두분리되는분석조건을확립하였다. 독일공산품인증인 GS-Mark에사용되는시험법의최근개정판인 ZEK (Table ) 에는분석대상물질은 18종 PAHs인데, PAH 16 종의 GC 크로마토그램이실려있는현황이다 종 PAHs GC-MS 분석의직선성및정밀도 본연구의 GC-MS 시스템을이용하여각 PAH 의 농도범위 mg/l~5.00 mg/l에서얻은검정곡선은상관계수 R 2 값이 18종 PAHs 모두 이상이되어 method validation의허용기준 (R 2 > 0.99) 0 을만족하였다. 검정곡선상의 5개농도에서각 7번의 GC-MS 분석을반복하여얻은머무름시간및피크면적의정밀도는각 RSD로산출한결과, 18 종 PAHs의머무름시간의 RSD는 0.00%(10종 PAHs)~0.05% 로측정되어머무름시간에대한반복성이매우정밀함을알수있었다 (Fig. 2(a)). 18 종 PAHs의각물질별및각농도별피크면적의 RSD는최소 1.16% 에서최대.69% 로측정되어 (Fig. 2(b)) method validation의허용기준 (RSD < 15%) 0 을만족하였고농도에비례하여커지는경향을보여주었다...18종PAHs 정량분석의검출한계및정량한계 18 종 PAHs 용액의 GC-MS 기기분석의검출한계는검정곡선자료로부터식 (1) 에의해산출한결과, mg/l (Benzo[ghi]perylene)~0.15 mg/l (Acenaphthylene) 범위였고정량한계는 배를곱한 0.27 mg/l~0.464 mg/l 이다. 고체샘플에서의정량한계는 100% 회수율을가정할경우, 본실험조건의희석배수 5( 시료 2 g, 최종부피 10 ml) 를곱하면, 18 종 PAHs별로 1.64 mg/kg~2.2 mg/kg가된다 (Table 5). 유럽 REACH 법령에의한일반공산품의 PAH 규제치 (Table 2) 인 1 mg/kg을정량하기에는적합하지만, 장난감이나어린이용품규제치 (0.5 mg/kg) 는검출정도만가능하다. 이의해결책으로는시료량을늘이고최종부피를줄여야함이제안되는한편, 저농도정량용검정곡선을 Vol. 27, No. 4, 2014

8 208 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe Table 5. LOD and LOQ in GC-MS analysis of 18 PAHs in consumer products Substance Conc. range (mg/l) a, slope Y=aX+b Standard deviation of b R 2 Measurement in solution LOD (mg/l) LOQ (mg/l) Measurement in solid material LOQ a) (mg/kg) 1 Acenaphthene 1,718,601 7, Acenaphthylene 2,796,2 129, Anthracene 2,50,26 101, Benzo[a]anthracene 2,415,67 91, Benzo[b]fluoranthene 2,562,022 99, Benzo[j]fluoranthene 2,842, , Benzo[k]fluoranthene 2,997, , Benzo[ghi]perylene 2,910,086 95, Benzo[a]pyrene 2,472,47 89, ~ Benzo[e]pyrene 2,512,2 90, Chrysen 2,508,058 90, Dibenzo[a,h]anthracene 2,71,181 90, Fluoranthene 2,75, , Fluorene 1,812,22 79, Indeno[1,2,-cd]pyrene 2,54,462 99, Naphthalene,290,212 10, Phenanthrene 2,449,72 11, Pyrene 2,740, , a) In case of dilution factor = 5 (sample : 2 g, final volume 10 ml (DCM, hexane) 별도로작성하여정량한계를얼마만큼낮게확보할수있는지에대한추가연구가필요하다..4. 스파이킹한샘플의추출용매별 PAHs 회수율 PAHs 18 종에대한국내외인증표준물질 (CRM, certified reference material) 혹은표준물질 (RM, reference material) 확보가어려워표준에서제시하는소량첨가 (spiking) 방법을이용하여 28-29,1 속슬렛추출용매별 (DCM, n-hexane, Toluene) 로회수율을산출하였다. 공산품 4종시료중함유된 PAHs 종류및함유량이많았던망치시료 (No.4) 를선택하여이시료에 18 종 PAHs를각 500 mg/kg이되도록스파이킹하였다. 독일에서 PAHs 함유가능성이큰공산품 5,00 종에서 6종 PAH를분석할결과, 함유량의범위가미검출, 혹은 1 mg/kg 이하에서부터 Benzo[a]pyrene 1,200 mg/kg, 6 종총량은 25,400 mg/kg이최대 PAH 함유량으로측정되었고 18 이를참조로, 스파이킹하는양을 500 mg/kg으로하였다. 속슬렛추출한결과 18 종각 PAH별로 DCM의경우 95.2%~104.9%, 헥세인의경우 95.2%~104.2%, 톨루엔의경우 95.6%~102.8% 회수율을보여 종용매가모두분석법유효화 (method Fig.. Recovery ratios of 18 PAHs from the spiked sample according to different Soxhlet-extraction solvents (The sample is hammer grip made of polyethylene with the spiked amount 500 mg/kg of each PAH). validation) 의회수율허용기준 (95%~105%) 1 을만족하였다 (Fig. )..5. 공산품 4 종의 PAHs 함유량분석.5.1. PAHs 함유량분석 본연구에서는 PAHs를함유할가능성이있는공산품인가방 ( 손잡이부분 ), 케이블, 슬리퍼, 망치 ( 손잡이 Analytical Science & Technology

9 Study on analysis of PAHs in consumer products 209 Fig. 4. GC-MS chromatograms of toluene extract from the sample No. 4 (hammer grip) with different acquisition mode. 부분 ) 를국내시장에서수집하여 18 종프탈레이트함유여부를분석한결과 개시료에서는 Phenanthrene 이소량혹은정량한계이하로검출되었고, Naphthalene 이슬리퍼시료에서정량한계이하로검출되었다. 망치 ( 손잡이부분 ) 시료에서는수십 mg/kg 범위의 15 종 PAHs가함유되어있었고검출된 15 종 PAHs의 GC- MS SIM 크로마토그램은 Fig. 4(a) 와같다. 15 종 PAHs는최대 8.4 mg/kg(phenanthrene)~ 최소 8.5 mg/ kg (Acenaphthylene) 범위로검출되었다 (Table 6). PAHs는석유계신전유 (extender oils) 에불순물로자연적으로존재하여, 신전유가고무및플라스틱가공에첨가됨으로인해타이어는물론, 고무및플라스틱로만들어지는다양한완제품, 즉전기전자제품, 부엌도구, 장난감, 핸들, 카트 / 보행보조기 / 가방손잡이, 연장의자루, 자전거, 골프채, 라켓등의스포츠용품, 의류, 신발, 비치샌달, 장갑, 시계줄, 손목밴드, 헤어밴드등에검출될수있다 따라서, 국내생산되는완제품 ( 피부와구강에직접적접촉뿐만아니라장기 Table 6. Samples and their contents of PAHs as measured in this study Sample No. Samples Major component of matrix a) PAHs detected Amount measured b) (mg/kg) Extraction with DCM (DF = 5) Extraction with hexane (DF = 5) Extraction with toluene (DF = 50) 1 Bag grip Polyamide Phenanthrene.9±0.12.2±0.11 ND 2 Cable Polyhexyl methacrylate Phenanthrene 0.9 c) ± c) ±0.0 ND Sandal Polyvinyl chloride 4 Hammer grip Polyethylene Phenanthrene 2.4 c) ± c) ±0.05 ND Naphthalene 0.6 c) ± c) ±0.0 ND Acenaphthylene 10.0± ± ±0.69 Fluorene 15.0± ± ±0.89 Phenanthrene 82.5± ± ±1.69 Anthracene 27.5± ± ±1.12 Fluoranthene 8.5± ± ±1.88 Pyrene 72.0± ± ±1.74 Benzo[a]anthracene 7.0± ± ±1.96 Chrysene 8.5± ±1.5 8.±1.09 Benzo[b]fluoranthene 59.5± ± ±2.26 Benzo[J]fluoranthene 61.7± ± ±2.01 Benzo[k]fluoranthene 56.5± ± ±1.84 Benzo[a]pyrene.0± ± ±1.49 Benzo[e]pyrene 5.9± ± ±1.71 Indeno [1,2,-cd]pyrene 1.5±1.6.5± ±1.7 Benzo[ghi]perylene 29.0± ± ±1.85 a) Confirmed by FT-IR library match (sample No.1, 2,, 4 : 78, 86, 82, 81 % library match, respectively) / b) Standard deviation (n=) c) Detected as trace with LOQ (Phenanthrene) = 2.25 mg/kg and LOQ (Naphthalene) = mg/kg in case of dilution factor=5 Vol. 27, No. 4, 2014

10 210 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe 간혹은단기간의반복적인접촉을하는완제품 21 에서의 PAHs 검출현황에대한체계적인연구를시작으로관련된산업계의대응이필요한시점이다 최적전처리조건.4. 에서논의된바와같이시료를속슬렛추출시에 DCM, 헥세인, 톨루엔중어느용매를사용하던지 18 종 PAHs의회수율이 95%~105% 사이에서거의동일하였다. 그러나, 톨루엔을사용할경우비등점이높아속슬렛추출후용매증발이매우비효율적이다. 구체적으로, 진공하에회전증발을 2시간이상하여도용매가전체부피의 20% 정도만증발되어시간이많이소용될뿐만아니라희석배수가커져검출및정량한계값이역시크게증가하게된다. 추출에사용했던용매의증발에 0 분이하로소요되었던 DCM 및헥세인과비교하면톨루엔은희석배수가 10 배커졌고, 따라서검출및정량한계값도 10 배증가한다. 공산품시료분석결과, 가방손잡이 ( 시료 No. 1), 케이블 ( 시료 No. 2), 샌달 ( 시료 No. ) 에서 Phenanthrene이검출혹은정량한계값범위의극소량 (trace) 검출되었는데 (DCM 혹은헥세인사용결과 ), 톨루엔을사용하여전처리한시료에서는미검출로측정되었다 (Table 6의음영부분 ). 이는톨루엔사용시 DCM 혹은헥세인사용시보다희석배수가 10 배증가하여극소량검출범위에있는 Phenanthrene이측정되지않음을보여주는좋은실례라사료된다. 따라서, 속슬렛추출용매로는톨루엔을배제한 DCM 혹은헥세인이최적임을검증하였고, 최적속슬렛추출시간에대한향후연구가필요하다. 정량한계를 1 mg/kg( 유럽일반공산품규제치 ), 0.5 mg/kg( 유럽장난감이나어린이용품규제치 ) 그리고현재가장엄격히운영되는독일의규제치인 0.2 mg/kg를맞추기위해서는현재의전처리방법에사용했던희석배수의감소, 즉시료량을늘이고최종부피를줄여야함이제안된다. 시료량을 2 g에서 5 g으로늘리고최종부피를 10 ml에서 2 ml로맞추는것이조작가능함을확인하였고더이상의농축은조작이불가능하였으며, 이조건에서는고체시료에함유된 PAHs 를 0.1 mg/ kg(benzo[ghi]perylene)~0.18 mg/kg (Acenaphthylene) 까지정량할수있다. 18 종 PAHs를스파이킹한망치시료 (No.4) 를톨루엔으로추출한용액을 SIM 모드및스캔모드로분석한결과 (Fig. 4(b) 및 4(c)) 를비교해보면, 공산품시료에 DMP, DEHP, DNOP 및지방족탄화수소등이존 재함을알수있으나, baseline에영향없이 SIM mode로 PAHs의정량분석이가능함을확인할수있다. 스캔모드 ( 총이온 ) 분석으로부터이들물질들과 18 종 PAHs의피크가겹치는부분이있는지를살펴보면, Fluoranthene, Pyrene의두물질이간섭물질인지방족탄화수소와약간겹치지만, SIM 모드분석시에영향을받지않았다. Table 에의하면필요시실리카컬럼을이용하여추출된시료용액을정제하게되어있는데, 본실험에서시도한바에의하면 Fig. 4(c) 에측정된방해물질들이정제되는것은아닌것으로확인하였다. PAHs가함유된매질인고분자물질이같이용출될경우이의정제에는효율적이라사료되며, 본실험에서시도된 4개공산품시료는정제가필요하지않은경우였다. 속슬렛추출에비해초음파추출은시간이단축되는전처리방법으로 26,27 이의효율및장단점을비교해보는향후연구가필요하다. 4. 결론수십년전부터발암성및잔류성을갖는 PAHs의대기, 수질, 토양, 음식물에대한오염에우려가집중되어온이래, 유럽신화학물질관리제도 (REACH) 에의해타이어함유규제를시작으로최근공산품함유에대한법적인규제로확장된현황이다. 이에본연구에서는공산품에함유된 18 종 PAHs의정량분석법을개발하여공산품 4종을분석한결과로부터다음과같이결론및향후추가연구방향을제안해보았다 : 종 PAHs를 DB-EUPAH 컬럼으로분리하여 GC-MS SIM 모드로정량하는분석조건을확립하였고, 머무름시간의정밀도는 0.00%~0.05% 그리고피크정밀도는 1.16%~.69% 의 RSD 측정되었다. 18 종각 PAH의농도범위 mg/l~5.00 mg/l에서얻은 18 개검정곡선은상관계수 R 2 값이모두 이상으로산출되었다. 2. 스파이킹에의한 18 종 PAHs의속슬렛추출결과 DCM, 헥세인, 혹은톨루엔사용시각 95.2%~ 104.9%, 95.2%~104.2%, 95.6%~102.8% 회수율이측정되었고, 톨루엔의경우높은비등점으로농축이어려워 DCM 및헥세인이최적추출용매임을확인하였다.. 18 종 PAHs 용액의 GC-MS 기기분석의정량한계는검정곡선자료로부터 0.27 mg/l (Benzo[ghi] Analytical Science & Technology

11 Study on analysis of PAHs in consumer products 211 perylene)~0.464 mg/l( Acenaphthylene) 로산출되었다. 본연구전처리에서사용한희석배수 5를기준으로고체시료에서의정량한계는 1.65 mg/kg (Benzo[ghi] perylene)~2.2 mg/kg (Acenaphthylene) 이며, 정량한계를감소하기위한시도로, 시료량을 2.5 배인 5 mg으로증가하고최종부피를 10 ml에서 2 ml로감소하는것이조작가능한최대농축임을확인하였고, 이조건에서 0.1 mg/kg(benzo[ghi]perylene)~0.18 mg/ kg(acenaphthylene) 까지정량할수있다. 4. PAHs 함유가능성이있는국내에서유통되는공산품 4종에서 18 종 PAHs를분석한결과, 개시료에서는 Phenanthrene이정량한계근방의소량으로검출되었고, 망치 ( 손잡이부분 ) 시료에서는 Phenanthrene 을비롯한 15 종 PAHs가최대 8.4 mg/kg~ 최소 8.5 mg/kg 범위로검출되었다. 5. 향후, 1) 농축과관련한분석용액조작에무리가없이 0.2 mg/kg~1 mg/kg 의규제치를정확히정량하는조건의확립이필요한데, 0.1 mg/l 농도이하의표준용액으로작성된저농도검정곡선의사용에의해정량한계를감소할수있는지여부의확인과 2) 속슬렛추출시간의단축가능여부및 ) 초음파추출시의정제필요성에대한여부를검토해야할것으로사료된다. 감사의글본연구는산업통상자원부 글로벌전문기술개발 ( 청정생산기반 ) 으로수행된결과이며연구비지원에감사드립니다. 참고문헌 1. UBA Background Paper, Polycyclic Aromatic Hydrocarbons, UBA(German Federal Environment Agency, Dessau-Roβlau, Annex XV restriction report, cm/20/pak_annex_xv_restriction_report_proposal_for_ a_restriction.pdf, Assessed 8 April J. Ha, D. Shin, J.-B. Hwang, H.-Y. Seo, M. Ito and H. Nakagawa, Anal. Sci. Technol., 24(4), (2011). 4. S. Hu, S. Jin, K. Lee and D. Choi, Anal. Sci. Technol., 2(2), S. Hu, S. Park, S. Jin and D. Choi, Anal. Sci. Technol., 22(1), (2009). 6. S. Hu, N. S. Oh, S. Y. Kim and H. Lee, Anal. Sci. Technol., 19(5), (2006). 7. H.-S. Pyo, J.-E. Hong, K.-J Lee, S.-J. Park and W. Lee, Anal. Sci. Technol., 1(4), (2000). 8. J. S. Park, S. K. Yoon and W. K. Bae, Anal. Sci. Technol., 2(), M. S. Calln, J. M. Lpez, A. Iturmendi and A. M. Mastral, Environ. Pollut., 18(12), (201). 10. S Dai, L. Zhang and T. Zhu, Anal. Sci. Technol., 8(4), (1995). 11. W. Lee, J.-E. Hong, S.-J. Park, H.-S. Pyo and I.-W. Kim, Anal. Sci. Technol., 11(5), 21-1 (1998). 12. H. K. Bojes and P. G. Pope, Regul. Toxicol. Pharm., 47(), (2007). 1. Agents classified by the IARC monographs, monographs.iarc.fr/eng/classification/index.php, Assessed 8 April Candidate list of substances of very high concern for authorisation, Assessed 8 April Member State Committee Document, Anthracene as a Substrate of Very High Concern, European Chemicals Agency, Helsinki, Ministry of Environment Notification No ( ), Republic of Korea. 17. Regulation (EC) No 1907/2006( ), the European Parliament and the Council of the European Union. 18. German Proposal for the Restriction of PAHs in Consumer Products, baua(federal Institute for Occupational Safety and Health), Dortmund, BfR Opinion Nr. 02/2010, Carcinogenic Polycyclic Aromatic Hydrocarbons in Consumer Products to Be Regulated by the EU, BfR(Federal Institute for Risk Assessment), Berlin, Oeko-Tex Standard 100, 4th Ed, Oeko-Tex International, Zrich, Commission Regulation (EU) No 1272/201 ( ), the European Parliament and the Council of the European Union. 22. ISO 18287, Soil Quality-Determination of Polycyclic Aromatic Hydrocarbons-Gas Chromatographic Method with Mass Spectrometric Detection(GC-MS), ISO 1799, Water Quality-Determination of 15 Polycy- Vol. 27, No. 4, 2014

12 212 Moon Hwan Song, Young Dal Cho and Eun Kyung Choe clic Aromatic Hydrocarbons in Water HPLC with Fluorescence Detection after Liquid-Liquid Extraction, ISO 1877, Soil Quality-Determination of Polynuclear Aromatic Hydrocarbons-Method using High-Performance Liquid Chromatography, EPA method 610, Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater, ZEK , Harmonized Method for Determination of Polycyclic Aromatic Hydrocarbons in Polymer, KS M 6956, Test Method for Estimating the Toxicity of Recycled Rubber Powder, ICH Harmonized Tripartite Guideline, Validation of Analytical Procedures:Text and Methodology Q2(R1), Current step 4 version, International Conference on Harmonization, Korea Agency for Technology and Standards Notification No ( ), Republic of Korea. 0. UN Document ID Number ST/NAR/41, Guidance for the Validation of Analytical Methodology and Calibration of Equipment used for Testing of Illicit Drugs in Seized Materials and Biological Specimens, United Nations, New York, I. Taverniers, M. De Loose and E. Van Bockstaele, Trends Anal. Chem., 2(8), (2004). Analytical Science & Technology