초록 ▼

○ 연구개발 목표
- 개발된 기술의 현장 적용으로 수입 농식품 가공원료들의 엄격한 수입관리
- 수출입 농식품의 원료 농산물에 대한 산업계 생산현장에서 적용 용이한 판별기술 수립
○ 연구내용
수출입 농식품 가공제품 및 원료들의 방사선 처리여부 신속 판별기술 개발
- 방사선 조사 여부의 판별을 위한 분석기술 개발(분석기기 및 분석방법 제시)
- 국내에서 허가되지 않은 전자선 등이 처리된 농식품의 판별을 위한 분석 기술 개발
- 농식품의 방사선 조사에 의한 특이 화합물 판별 기술 개발
- 미지

○ 연구개발 목표
- 개발된 기술의 현장 적용으로 수입 농식품 가공원료들의 엄격한 수입관리
- 수출입 농식품의 원료 농산물에 대한 산업계 생산현장에서 적용 용이한 판별기술 수립
○ 연구내용
수출입 농식품 가공제품 및 원료들의 방사선 처리여부 신속 판별기술 개발
- 방사선 조사 여부의 판별을 위한 분석기술 개발(분석기기 및 분석방법 제시)
- 국내에서 허가되지 않은 전자선 등이 처리된 농식품의 판별을 위한 분석 기술 개발
- 농식품의 방사선 조사에 의한 특이 화합물 판별 기술 개발
- 미지 시료의 사전 방사선 조사 여부 확인 기술 개발 및 판별기능 기간 설정
수출입 농식품 가공원료의 방사선 에너지 흡수 선량 예측기술 개발
- 원산지별 marker 무기질 분리 기술, 열발광 특성의 신속 판별 기술 개발
- 미지의 농식품에 대한 방사선 에너지 흡수 선량 예측모델 개발
- 방사선 조사 후 저장 유통 중 판별 가능 기간 설정
○ 연구성과 활용 실적 및 계획
- 다소비 수출입 축삭 식품 및 농식품의 조사처리에 따른 물리적(PSL, TL, ESR), 화학적(GC/MS) 판별마커의 DB화
- 방사선 조사원료의 가공조건(분말화/혼합비율/건조조건/살균처리)에 따른 판별마커 모니터링 및 최적 판별마커 설정
- 저장기간에 따른 마커안정성 확인 및 흡수선량예측을 위한 모델 선정
- 수입 미지시료들의 조사여부 판별관리에서 현행 물리적 확인시험법의 적용성 제고에 활용
- 방사선 처리 농식품의 저장 중 판별마커설정
- 확립된 판별방법을 활용한 방사선 조사식품의 물리적 및 화학적 판별마커 분석기술 교육
- 방사선 조사 농식품의 조사여부 판별기술의 inter-laboratory 검증
- 연구결과의 국내외 학술지 게재로써 판별불석자료 과학적 근거자료로 활용
- 기 수행된 농식품의 결과를 바탕으로 현행 확인시험법의 적용품목확대 건의
- 국가 방사선조사식품 표시제 자료로서 활용

Abstract ▼

IV. Results of the Project and their Applications
Scetion 1. Development of livestock products irradiation judgement technique by chemical detecting method
A. It emitted electron beam for the irradiation or not discrimination of imports and exports livestock products in the sample with the gam

IV. Results of the Project and their Applications
Scetion 1. Development of livestock products irradiation judgement technique by chemical detecting method
A. It emitted electron beam for the irradiation or not discrimination of imports and exports livestock products in the sample with the gamma-ray and the unload discrimination characteristic was confirmed.
B. The chicken, pork, beef, dry whole milk, modified milk powder, baby food, cooking oil, beef powder S(beef jerky), beef powder D(ham), natural cheese, process cheese, and fat of the vienna sausage were extracted and it separated to SPE catridge and the separated hydrocarbons were analyze by GC/MS.
C. In the saturated hydrocarbon including the pentadecane, heptadecane, and etc, since it could be detected from the polution of the solvent, it was 1-tetradecene and derived from the palmitic acid 17-hexadecadiene, derived from the loeic acid 1-heptadecene suitable for the irradiation or not discrimination for the marker.
D. In the chicken, pork, beef, cooking oil, natural cheese, process cheese, and vienna sausage, it was confirmed and that hydrocarbons increased due to the significance the radiation and electron beam inspecion discrimination yes or no was possible.
E. 17-hexadecadiene and 8-heptadecene was confirned as the irregular aspect in the sample which is irradiated in the whole milk, modified milk powder, baby food, and beef powder S and beef powder D according to the dose.
F. That is, in case of being the powder product, it was considered that analysis by the physical detectingmethod was needed since the spectrum of the mixture of the powdered milk and beef powder itself and hydrocarbon overlapped and the analysis by the sim mode was difficult and the problem was in the positive quantity.
G. As to the hydrocarbons analysis by SPE cartridag and LC column, in the case of the cooking oil, the difference of the value of fixed quantity according to the separation method was not confirmed and was determined that method using SPE cartridag for the meat product excluding the powder product confirmed the effectiveness for the hour and solvent saving but the contaminant of SPE cartridge itself including the base line and antioxidant, and etc. was detected and the Instrumental analysis by SIM mode was needed.
H. The detection value which is similar that it gathers in the absorbed dose of the result of comparing and analyze the hydrocarbons generated in the gamma-say and test piece which electron beam is examined gamma-ray and electron beam inspection was displayed. And it emitted electron beam the gamma-ray and difference could not be discovered.
I. When the hydrocarbon type analysis by SPE it follows in the storage periods (3,6,12 months)s cartridge and which LC column was detected as the same tendency irrelative of the storage period and the hydrocarbons were confirmed not to be influenced by the storage period.
J. When mixing 10% in the food containing fat which the ratio is the food containing fat irradiated as 5kGy and 10kGy irradiated and processing, the generated hydrocarbon could be detected.
Section 2. Development of Detection Methods for Irradiated Agricultural Materials and Products
A. Thirty five food items were subjected to discriminate as irradiated or not by Thermoluminescence (TL) methods, to facilitate import/export of agricultural food. All un-irradiated samples showed low intensity TL glow curve after 300℃, but samples, irradiated by γ-ray over 1 kGy showed high intensity of TL glow curve in 150-250℃ range. To increase the accuracy & reliability, TL ratio(TL1/TL2) was used. All un-irradiated samples gave TL ratio less than 0.1 whereas all irradiated were over 0.1, therefore clear discrimination was possible.
Intensity and TL ratio decreased with storage time; however identification was still possible over studied storage period.
B. In Electron Spin Resonance (ESR) analysis, dried spring onion(Allium fistulosum), carrot, pumpkin, lettuce, pistachio, whlnut, soybean, pepper powder, and white ginseng showed signals corresponding to cellulose radical, whereas cabbage, raisin, dried mango, complex seasoning, instant food, and soup powder showed multi-component signal corresponding to crystalline sugar.
Intensities of these signals were dependent on irradiation doses. Cellulose radical was possible to detect during 8-9 months and crystalline sugar radical was possible to detect even after 1 year.
C. Using Photostimulated luminescence (PSL) analysis, screening was possible for lettuce, cabbage, soybean, red bean, pea, curcuma, wheat, raisin, ginseng concentrate, soup powder, instant seasoning, and liquid sauce showed un-irradiated samples under 700 photon counts (PCs) the negative value. However, irradiated samples showed PCs over 5,000 the positive value. But pumpkin, carrot, pistachio, walnut, pepper powder, pepper, rice, shiitake mushroom, oyster mushroom, eried mango showed PCs results in intermediated range (700-5,000) showing inability of PSL method to screen these samples properly.
D. In comparison, based upon origin and varieties of agricultural raw materials, no specific discrimination characteristics were found for TL & PSL method with exception of luminescence intensity. It represents PSL, TL and ESR methods have wide application regardless of origin and carieties. In result of ESR analysis, intensity of cellulose signal in fresh irradiated ginseng increased with the growing period showing importance of cellulose for ESR analysis.
E. PSL and TL analysis were employed to test the presence of γ-ray irradiated sample in different mixing ration (0.1%~10% irradiated sample in non irradiated one). PSL result of 1 kGy irradiated samples showed negative value when mixed at the rate of under 0.5%, intermediate at 0.5~9%.
10 kGy irradiated samples showed negative value at 0.1% mixing and intermediate, positive values at over 0.1%. TL analysis gave TL ratio for the all mixed samples under 0.1, but glow curve showed clear difference between irradiated and un-irradiated and un-irradiated samples.
F. Effect of erying conditions (spray drying, vacuum drying) was also monitored for 4 different kinds of irradiated seasoned food ingredients (beef powder, soybean paste powder, broth seasoning, & soybean powder). In PSL analysis, photon counts of irradiated samples before drying were 4542~13149556 PCs, but after frying greatly decreased to 297~7619471 PCs.
Especially PSL result of 5 & 10 kGy irradiated spray dried beef and soybean powder showed negative value, showing inability of PSL method to screen these samples. TL analysis, before and after drying, of 5 and 10 kGy irradiated samples gave glow curve between 150~250℃ range. Like PSL results, TL intensities of spray dried samples were also less than that of vacuum dried samples, showing potential decreasing effect of spray drying on luminescence characteristics.
G. Irradiated garlic powder, mixed in ratio of 0.5~3% with food ingredient and processed (steam sterilized, 85℃), was investigated for 2 different kinds of liquid sauces (bul-gogi, ssam-jang). In result, shape of glow curve ( in range of 150~250℃ for irradiated & after 280℃ for un-irradiated), was only way to evaluate the possible treatment because all TL ratio wereunder 0.1. The luminescence intensity appeared differently for different sample depending upon theamount of contaminated minerals, so difference caused by dose and mixing ratio were not clear.
Section 3. Distinguishing Techniques on the Irradiated food of Agricultural Foods by Electron Spin Reronance(ESR)
A. Establishment of most suitable cond
B. R² value was more than 0.95, dose estimation could be applied by regressional analysis.
C. There was not differences in the ESR spectrum according to the radiation source between the Gamma-ray and electron beam
D. The ESR signal of Glucose, lactose and infant formula were not greatly changed in the storage period, on the other hand, weaning food and whole milk powder were decrease. Fourty-two kinds of the seventy-nine tested livestock products could be distinguished by the ESR method although this changes.
E. Heating method for sample dry could induce radical change of sample, therefore frozen drying method was best for the pre-treatment.
F. Most of crystallized glucose and synthetic additives were easily distinguished between non-irradiated samples and irradiated samples in the low dose less than 1 kGy.
G. Most samples were could be distinguished in the conditions of ingredient contents more than 5~10%, exception for the case of crystallized glucose in the 1%.
H. Most final meat products couldn't be distinguished by ESR signal, but the most agricultural ingredients could be.
Section 4. Development of Detection Methods for E-beam Irradiated Agricultural Materials and Products
A. An investigation is done by PSL that is rapid screening methods for determining of whether E-beam irradiated or not, and is reported as a standard method for spice and dried vegetable.
The analysis on 12 food items showed that photon counts for none-irradiated samples such as cabbage, carrot, soybean, a red-bean, black pepper, ginger, wheat, sesame, perilla and shiitake mushroom indicated under 700, but those for irradiated samples showed over 5000 that means a positive value. The photon counts are increased in a irradiation dose-dependent manner. But, pistachio and walnut showed intermediated value (700-5000 photon counts) regardless of irradiation, so PSL can't be applicable to those.
B. To analysis and make database for physical identification marker of E-beam irradiated agricultural raw materials, TL method was done using cabbage, carrot, pistachio, walnut, soyboean, a red-bean, black pepper, ginger, wheat, sesame, perilla and shiitake mushroom. Exceptpistachio, all irradiated samples showed the first TL glow curve in a range of 150~250℃ and showed TL ratio (TL1/TL2) over 0.1. Therefore, all irradiated samples were discriminated whether irradiated or not by TL method except pistachio.
C. To analysis and make database for ESR identification marker of E-beam irradiated agricultural raw materials, ESR method was done using same twelve agricultural items. Signal intensity showed significant increasing levels in irradiated samples by comparison with non-irradiated those, and increased in a irradiation dose-dependent manner. Signal of single line that was estimated for polyphenol was detected in cabbage, walnut, adzuki bean, black pepper, ginger, sesame, and perilla regardless of irradiation. That signal was increased in irradiated sample, but it also existed a little bit in non-irradiated sample. Therefore, those samples can't be discriminated whether irradiated or not by ESR. Signal derived from crystalline suger was detected in carrot and wheat, and signal of triplet line derived form cellulose was detected in pistachio. Therefore carrot, wheat, and pistachio can be discriminated whether irradiated or not by ESR.
D. When the agricultural products were analysed by PSL method, the photon counts showed under 700 in non-irradiated raisin, red pepper powder and soup, and showed over 5000 in irradiated samples. Therefore, those can be discriminated whether irradiated or not by PSL. However, non-irradiated instant seasoning showed intermediated value (700-5000 photon counts).
E. Four agriculture products were subjected to distinguish whether irradiated or not by TL methods.
All irradiated samples showed TL glow curve in a range 150~250℃ and TL ratio (TL1/TL2) is over 0.1. All non-irradiated samples showed under 0.1 of TL ratio. Therfore those can be discriminated whether irradiated or not by TL.
F. Four agriculture products were subjected to distinguish whether irradiated or not by electron spin reconance (ESR) anlysis. Signal intensity showed significant increasing levels in irradiated samples by comparison with non-irradiated those, and increased in a irradiation dose-dependent manner. Multi-component signal derived from crystalline sugar was detected in irradiated raisin, and signal of triplet line derived from cellulose was detected in irradiated red pepper powder, and signal derived from crystalline sugar was detected in irradiated instant seasoning. All samples can be discriminated whether irradiated or not not by ESR.
G. The chemical identification (hydrocarbon analysis, GC/MS) method was done using high fat-agricultural materials such as walnet, soybean, and sesame. In all irradiated by E-beam and γ-ray, 1,7-hexadecadiene and 8-heptadecene that are markers for irradiation were detected and increasde in a irradiation dose-dependent manner. Those marker were not detected in non-irradiated sampels. Therefore, those can be discriminated whether irradiated or not by GC/MS.
H. Physical and Chemical methods were done using carrot, walnut, soybean, red pepper powder, wheat, sesame, and instant seasoning according to storage time(0, 6, 12 month). In PSL method, the photon counts were decreased in a time-dependent manner. In the case of soybean, wheat(3, 5 kGy), sesame, and instant seasoning, PSL method can be used for irradiation detection after 12 month storage time, but in the case of carrot, walnut, pepper powder, and wheat(1 kGy), PSL method cannot be used. In all irradiated samples except walnut and soybean, TL ratio showed over 0.1. Therefore those can be used for irradiation detection after 12 month by TL.
In the case of pepper powder and instant seasoning, signal derived from cellulose and crystalline sugar respectively detected in ESR method after 12 month. Therefore, those can be used for irradiation detection after 12 month by ESR. Walnut, soybean, and sesame can bel used for irradiation detection after 12 month by GC/MS due to detection of 1,7-hexadecadiene and 8-heptadecene.
I. PSL and TL methods were done using E-beam irradiated beef powder, soybean paste powder, and roasted garlic seasoning according to drying conditions(spray and vacuum drying). In PSL method, the photon counts were decreased by drying treatment. Especially, in the case of spray dried beef powder and soybean paste powder, the photon counts showed under 700. In TL method, all irradiated samples can be used for irradiation detection regardless of drying conditions.
J. To discriminate the irradiated garlic powder in mixed(0.5~5.0%) products(bul-gogi, SSam-jang), TL method was used. Before analysis, the mixed products were sterilized by steam(85℃). In both mixed products containing irradiated garlic powder, grow curve was detected in a range of 150~250℃. In the case of non-irradiaed garlic powder, glow curve wasn't detected. Though TL ratio showed under 0.1 in all samples, mixed products containing irradiated ingredient can be used for irradiation detection by TL method according to TL glow curve.
Section 5. Development of Detection Methods for irradiated livestock food using TL and PSL
A. 28 Items including raw ingredients and finished products of baby food, dried whole milk and formulated milk powder had been studied for possibility of applying methods of thermoluminescence, TL, and photostimulated luminescence, PSL. As a result, 13 raw ingredients of dried whole milk and formulated milk powder, and 4 out of 16 baby foods are supected to lose mineral during the testing process. Therefore, using TL and PSL testing methods are not adequate for these tests. However, 12 out of 16 raw ingredients of baby food and finished products of dried whole milk can be detected with TL, PSL method.
B. Those materials which can be detected with TL and PSL methods (12 ingredients of baby food and 2 finished products of baby food and dried whole milk) can be analyzed both qualitatively and quantitatively since radiation level and photon count value are proportional to each other as photon count value increase in segment of 1, 3, 5, 7kGy. Import/export food are considered to have long period of logistic time. In order to simulate this in the lab, test samples are stored in period of 3, 6, 9, 12 months. As a result, there were no significant change in reading, and radiation can be read even after period of 1 year.
C. Among raw ingredient of individual test of physical testing, 3 groups of test sample have made in different ratio of mix according to product recipe. These samples were irradiated with gamma ray and electron beam, and detection limit test were performed. As a result PSL analysis were not possible, however, TL test could detect up to 3% of limit detection of irradiated material among the finished products.
D. 28 ingredients consisting finished products of sausage and dried meats and processed sausages and dried meat were tested for possibility of applying TL, and PSL tests. As a result, 9 out of 15 sausage ingredients and 4 out of 12 ingredients of dried meat loses mineral during the processiong process. Therefore, these items are inadequate for TL, PSL test. However, 6 out of 15 ingredients of sausage products, 8 out of 12 of dried meat products can be tested with Gamma ray and electron beam irradiation.
E. Those processed food which can be detected with TL, PSL methods (2 meat products - sausage and dried meat and 14 ingredients) can be analyzed both qualitatively and quantiatively, since radiation level and photon count value are proportional to each other as photon count value increase in segment of 1, 3, 5, 7kGy. Import/export food are considered to have long period of logistic time to reach consumer. In order to simulate this in the alb, test samples are stored in period of 3, 6, 9, 12 months. As a result, there were no significant change in reading and radiation can be read even after period of 1 year.
F. Bill of ingredients of the certain sausage products were obtained from project cooperating companies. Among these ingredients, high ratio ingredient sample was selected (Mixed Seasoned Food, About 3.5%) and tested with maximum irradiation level of Gamma ray permitted in Korea (10KGy). The content of testing ingredient was varied in percentage of 0.5%, 1%, 2%, 3.5% and 5%. Also these testing sample products were manufactured in actual plant to be made identical to the actual product (150g). As a result, TL test can check the irradiation and value can increase proportion to content of the 1 item of testing ingredients varied from 5%, 3, 5%, 2%, and 1%. In case of 1% content, sometimes 150g of sample could not obtain the repetitive results, however in case of 300g sample, repetitive test result could be obtained.