초록 ▼

헥사클로로부타디엔(HCBD)는 주로 탄화수소화합물의 제조 공정에서 비의도적으로 발생되며, 산업제조 공정에서 발생되는 염소기체 회수 및 가스체 정화를 위한 세척액으로 주로 사용되어져 왔으나, 2015년 스톡홀름 협약에서 잔류성유기오염물질(POPs, Persistent Organic Pollutants)로 등재되었고, 국내 환경부에서 2018년 POPs로 지정되었다. 최근 발생, 생산 및 사용이 규제된 물질임에도 불구하고 지속적으로 검출이 되었으며, 그 외에도 꾸준히 검출되고 있는 상황이다. 또한, 국제암연구소 (IARC)에서는 HCB

헥사클로로부타디엔(HCBD)는 주로 탄화수소화합물의 제조 공정에서 비의도적으로 발생되며, 산업제조 공정에서 발생되는 염소기체 회수 및 가스체 정화를 위한 세척액으로 주로 사용되어져 왔으나, 2015년 스톡홀름 협약에서 잔류성유기오염물질(POPs, Persistent Organic Pollutants)로 등재되었고, 국내 환경부에서 2018년 POPs로 지정되었다. 최근 발생, 생산 및 사용이 규제된 물질임에도 불구하고 지속적으로 검출이 되었으며, 그 외에도 꾸준히 검출되고 있는 상황이다. 또한, 국제암연구소 (IARC)에서는 HCBD를 Group 3으로 분류하여 인체발암물질로 정의할 수 없다고 하였지만, 미국 환경보호국(US EPA) 및 미국 국립산업안전보건연구원(NIOSH)에서는 발암가능성이 있는 잠재적 발암물질로 분류하고 있다. 따라서 지속적인 HCBD의 모니터링이 필요하다.

기존 식품의약품안전처에서 확립한 POPs 시험법들과 국내·외 HCBD의 연구 자료를 참고하여 본 연구에서 시험법을 확립하였다. 그 과정에서 기기 분석 조건 확립, 추출 조건 검토, 추출 조건 확립, 산 저항성 검토 및 확인, 정제 조건 검토, 회수율 개선 실험, 유효성 검증의 과정을 통해서 HCBD 전처리법 및 GC-MS를 이용한 분석법 개발, 식품군별 대표 품목 선정 후 유효성 확인, 2개 기관과 CRM 교차검증 실시, 확립된 시험법으로 적용성 확인을 하였고 모두 만족한 결과를 도출하였다.

확립된 시험법을 이용하여 유통 식품(농산물, 축산물, 수산물 및 가공식품) 및 건강기능식품 중 HCBD에 대한 오염도 조사를 수행하였다. 총 검사 건수는 86품목(농산물 20품목, 축산물 12품목, 수산물 29품목, 가공식품 24품목, 건강기능식품 1품목) 609건(농산물 140건, 축산물 84건, 수산물 203건, 가공식품 168건, 건강기능식품 14건)을 수행하였다. 검출 건수는 전체 609건 중 254건에서 검출되어 41.7%의 전체 검출률을 나타냈다. 농산물의 검출률은 7.1%(10/140), 축산물 79.8%(67/84), 수산물 50.2%(102/203), 가공식품 40.5%(68/168), 건강기능식품 검출률은 50.0%(7/14)를 나타냈다. 평균 검출량은 건강기능식품(0.25 ng/g w.w.), 축산물(0.15 ng/g w.w.), 가공식품(0.13 ng/g w.w.), 수산물(0.11 ng/g w.w.), 농산물(0.02 ng/g w.w.) 순으로 나타났다.

노출량 평가 시 물질별 불검출 자료에 따른 오염도 적용원칙을 따라 진행한다. HCBD의 경우 전체 식품의 불검출 비율이 58.3%인 것을 고려하여, 불검출률 60%미만 값으로 GEMS/Food 가이드에 따라 모두 1/2LOD(MB)을 적용하여 평균오염도를 산출하였다.

식품 섭취량에 대한 정보는 국민건강영양조사 6기(‘13-’15년), 7기(‘16-18년) 자료를 이용하여 전 국민 1일 평균 및 극단(95th) 섭취량을 산출하였다. 선정된 86 품목 가운데 가공식품 중 크릴오일은 국민건강영양조사를 통해 식품섭취량 정보를 확인할 수 없다. 식품섭취량 정보를 확인할 수 없는 경우 국내 생산량과 수입량 등으로 국내 유통량을 추정하고 이를 총 인구로 나누어 전 국민의 평균 식품섭취량을 산출하여 활용할 수 있다. 2020년 식품 등의 생산실적(식품의약품안전처, 2021)을 바탕으로 국내 판매량을 국민 총 인구수로 나누어 일일 섭취량을 산출하였으며, 연령별로 산출하지는 않았다.

건강기능식품을 포함한 86품목 609건의 인체 노출량(평균섭취자, 전 연령)은 0.93 ng/kg b.w. per day를 나타냈다. 농산물(0.2212 ng/kg b.w. per day). 축산물(0.3045 ng/kg b.w. per day), 수산물 (0.0692 ng/kg b.w. per day), 가공식품(0.3292 ng/kg b.w. per day), 건강기능식품(0.0008 ng/kg b.w. per day)의 인체 노출량을 나타냈다. 축산물의 경우 알류의 노출기여율이 52%, 수산물의 경우 해양어류의 노출기여율이 80%로 가장 높았다. 가공식품은 커피류의 노출기여율이 27%이며, 다음으로는 김치류가 15%로 높은 노출기여율로 나타냈다.

인체노출안전기준 대비 식품섭취를 통한 HCBD의 위해도를 산출하였다. ‘21년 유해물질 인체노출 안전기준 설정을 위한 전문가 회의를 통해 HCBD 인체노출안전기준 검토를 하였으며, 최종독성값 NOAEL 0.2 mg/kg b.w. per day 사용 및 불확실성계수 100(종간 차이 10, 개체간 차이 10)을 적용하여 인체노출안전기준 TDI 2 ㎍/kg b.w/day로 결정되었다. 각 식품별 HCBD의 위해도는 농산물(0.011%), 축산물(0.015%), 수산물(0.004%), 가공식품(0.017%), 건강기능식품(0.00004%)으로 나타났으며, 전체 86품목 609건의 평균 섭취를 통한 전체 HCBD 위해도의 합계는 TDI 대비 0.05%로 인체에 위해우려 없는 수준으로 평가되었다.

(출처 : 요약문 4p)

Abstract ▼

Hexachlorobutadiene (HCBD) is mainly unintentionally generated in the manufacturing process of hydrocarbon compounds and has been mainly used as a cleaning solution for chlorine gas recovery and gas purification generated in industrial manufacturing processes, but was designated as Pops (Persistent

Hexachlorobutadiene (HCBD) is mainly unintentionally generated in the manufacturing process of hydrocarbon compounds and has been mainly used as a cleaning solution for chlorine gas recovery and gas purification generated in industrial manufacturing processes, but was designated as Pops (Persistent Organic Pollutants) in 2018. Recent studies have shown that most of the HCBD contamination detected in foods surveyed in the UK in 2019 is below the detection limit, but it has been continuously detected despite the fact that occurrence, production, and use are regulated substances. In addition, the International Institute of Cancer (IARC) classified HCBD as Group 3 and said it could not be defined as a human carcinogen, but the USEPA and the National Institute of Occupational Safety and Health (NIOSH) classified it as a potential carcinogen. Therefore, continuous monitoring of HCBD is required.

The analysis method was established in this study by referring to the existing POPs test methods established by the Ministry of Food and Drug Safety and research data from domestic and foreign HCBD. In the process, device analysis conditions were established, extraction conditions were reviewed, acid resistance was reviewed, purified conditions were reviewed, recovery rate improvement experiments, and validation were developed using HCBD pretreatment and GC-MS, validation after selecting representative items for each food group, and satisfactory results. In addition to GC-MS, GC-MS/MS and GC-HRMS test methods were established.

After adding 13C-HCBD as an internal standard to 5 g of the homogenized sample, fat was extracted using ASE (accelerated solvent extractor), fat was acid-decomposed with 30% H2SO4 silica, and purified using a composite filler column. All analyses were performed using GC-MS from Agilent, and DB-5MS (30 m x 0.25 mm x 0.25 μm) was used as the analysis column.

The developed test method was validated in accordance with the guidelines of the International Food Standards Commission. The correlation coefficient showed good linearity of 0.999 or more, and a specific chromatogram with no obstruction peak around the peak of the analyte was obtained. The accuracy of pork was 91.76 to 112.4%, with 69.19 to 98.6% mackerel, 93.55 to 110.2% rice, and 85.93 to 104.0% milk. The precision within the day was 4.64 to 6.1% of pork, 5.55 to 11.0% of mackerel, 3.16 to 6.8% of rice, and 11.27 to 15.1% of milk. The daily accuracy was 87.72 to 111.2% for pork, 72.22 to 100.6% for mackerel, 90.92 to 111.1% for rice, and 82.18 to 108.8% for milk. The precision within the day was 5.57 to 6.4%, mackerel 6.44 to 10.2%, rice 4.80 to 6.5% and milk 8.97 to 10.7%. Both daily and daily accuracy and precision ranges met the accuracy range of 40-120% and precision of 44%, which is the standard of the International Food Standards Commission guideline.

As a result of performing CRM with two inspection agencies specializing in residual pollutants for cross-testing, both of them fell within the range of certification values, and their precision was also 2.8%, satisfying the International Food Standards Commission's standards. In addition, to confirm the applicability of the established test method, items of a class other than the representative matrix used for validation were selected and tested by adding standard substances to eggs, apples in agricultural products, squid, and coffee in processed foods.

The detection amount of HCBD among distributed foods (agricultural products, livestock products, marine products, and processed foods) and health functional foods was investigated using the established test method. The total number of tests was 86 (20 agricultural products, 12 livestock products, 29 marine products, 24 processed foods, 1 health functional food) and 609 (140 agricultural products, 84 livestock products, 203 marine products, 168 processed foods, and 14 health functional foods). The number of detection cases was detected in 254 out of 609 cases, showing a total detection rate of 41.7%. The detection rate of agricultural products was 7.1% (10/140), 79.8% (67/84), 50.2% (102/203), processed foods 40.5% (68/168), and the detection rate of health functional foods was 50.0% (7/14). The average detection amount was found in the order of health functional foods (0.25 ng/g w.w.), livestock products (0.15 ng/g w.w.), processed foods (0.13 ng/g w.w.), aquatic products (0.11 ng/g w.w.) and agricultural products (0.02 ng/g w.w.).

When evaluating the exposure amount, pollution according to the non-detection data for each substance was also carried out according to the principle of application. Considering that the non-detection ratio of all foods of HCBD was 58.2%, the pollution level was evaluated by applying 1/2LOD (MB) in accordance with the GEMS/Food guide with a non-detection rate of less than 60%.

Information on food intake was calculated by using data from the 6th National Health and Nutrition Survey ('13-'15') and 7 ('16-18) to calculate the average daily intake and extreme (95th) of all citizens. Among the 86 selected items, in the case of maintaining the content of krill oil and health functional foods, EPA and DHA, among processed foods, information on food intake cannot be confirmed through the National Health and Nutrition Survey. If the information on food intake cannot be confirmed, domestic distribution can be estimated by domestic production and import, and the average food intake of the entire nation can be calculated and used by dividing it by the total population. Accordingly, based on the production performance of 2020 Food and Drug Administration (Ministry of Food and Drug Safety, 2021), maintaining EPA and DHA content and domestic sales of fish were confirmed, and daily intake was calculated by dividing domestic sales by the total population.

The human exposure (average inhaler, all ages) of 609 cases in 86 items, including health functional foods, was 0.93 ng/kg b.w.per day. Agricultural products (0.2212 ng/kg b.w.per day). The human exposure of livestock products (0.3045 ng/kg b.w.per day), fisheries products (0.0692 ng/kg b.w.perday), processed foods (0.3292 ng/kg b.w.perday), and health functional foods (0.0008 ng/kg b.w.perday) was shown.per day). In the case of livestock products, the exposure contribution rate of egg was 52%, and in the case of marine products, the exposure contribution rate of marine fish was the highest at 84%. Processed foods showed a high exposure contribution rate of 27% for coffee, followed by 15% for kimchi.
Agricultural products did not review the exposure contribution rate because there was no sword in the detected item.

HCBD risk was calculated for each food through food intake compared to human exposure safety standards. Prior to calculating the risk, HCBD human exposure safety standards were reviewed through expert meetings to establish human exposure safety standards for harmful substances in ‘21, and the final toxicity value NOAEL 0.2 mg/kg b.w. / day use and uncertainty coefficient 100 (difference 10 between species and individuals) was applied to TDI was decided as 2 μg/kg b.w. /day. The risk of HCBD for each food was found to be agricultural products (0.011%), livestock products (0.015%), fisheries products (0.004%), processed foods (0.017%), and health functional foods (0.00004%), and it was confirmed that the risk of HCBD through 609 intake of 86 items was very low compared to TDI.

(source : Summary 6p)

목차 Contents

• 표지 ... 1
• 최종보고서 ... 2
• 국문 요약문 ... 4
• Summary ... 6
• 목차 ... 9
• 연구개발과제 연구결과 ... 10
• 제1장 연구개발과제의 개요 ... 10
• 제2장 연구개발과제의 국내·외 연구개발 현황 ... 42
• 제3장 연구개발과제의 연구수행 내용 및 결과 ... 51
• 제4장 연구개발과제의 연구결과 고찰 및 결론 ... 141
• 제5장 연구개발과제의 목표달성도 및 관련분야에의 기여도 ... 146
• 제6장 연구개발과제 연구개발 결과 활용계획 ... 148
• 제7장 참고문헌 ... 150
• 제8장 첨부서류 ... 157
• 끝페이지 ... 158