젤펜 획 중에서 분석된 미량 염료성분의 불확도 평가
Evaluation on Measurement Uncertainties of Analyzed Trace Dye Components from Black Gel Pen Inks on Paper
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참고문헌
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초록
젤펜 획에 포함되어 있는 미량 염료 분석에서 체계적인 측정 불확도 평가를 수행하여 측정방법의 신뢰도를 검증하고자 하였다. 젤펜획에서 추출된 염료 중 미량 염료성분은 UPLC-Tandem Mass를 이용한 동시 다성분 정량 분석법을 유효화하였고 측정과정의 불확도 요인을 파악하여 ISO의 측정 불확도 지침에 따라 염료의 측정불확도를 평가하였다. 대표적인 염료인 Crystal violet (CV)와 Methyl violet B base (MVB)를 500 μg/L과 1000 μg/L을 첨가하여 회수율과 반복성올 측정한 결과 상관계수 r2값은 각각 0.9964와 0.9853이었고 회수율은 93% ~ 110%로 나타났다. 샘플에 대한 측정불확도는 CV가 4.5 % ~ 1 3.8%였고 MVB는 5.9%~10.1%의 불확도를 확인하였다. 젤펜획에서의 불확도는 젤펜획 1 mm당 CV가 0.72 μg검출되었을 때 ±0.14 μg로 18.9%, MVB가 0.46 μg 검출되었고 불확도는 ±0.13 μg로 29.2%의 불확도를 확인하였다. 불확도의 요인중 검량선과 반복측정의 불확도가 가장 높게 얻어 졌고 불확도 요인의 구성요인은 저울의 안정성, 분해능, 재현성, 표준물질의 순도, 분자량, 농도, 표준용액 희석, 검량선, 회수율 및 분석기기의 재현성 등이 작용하였다. 이 연구로부터 젤펜획에서 염료의 함량 측정시 측정 불확도의 범위를 가늠할 수 있었으며, 젤펜획중 염료의 측정 결과에 대한 올바른 검증을 가능하게 하는 기준으로 활용될수 있을 것으로 판단된다. 중요문서에 사용되는 필기구류의 특성 파악은 위조수표, 유언장과 같은 범죄의 문서증거물에 많이 사용되는 젤펜에 대한 형태적 또는 성분, 함량 특성의 파악이 중요하기 때문에 이 연구의 결과는 새로운 시험방법의 검증에 중요한 기초 자료로 활용될 수 있을 것이다
Abstract
In this study, we evaluated the uncertainty of measurement in the analysis of trace dye that is included in Black Gel Pen Inks on paper. We verified the reliability of the measurement method by assaying a trace amount of dye extracted from the Black Gel Pen Inks on paper in simultaneous multi-component quantitative analysis using UPLC-Tandem Mass. The uncertainty of measurement was evaluated in accordance with the ISO process. Crystal violet (CV) and Methyl violet B base (MVB) were used as representative dyes. After testing with crystal violet (500 μg/L) and MVB (1000 μg/L), we calculated repeatability and recovery. The correlation coefficients were 0.9964 and 0.9853, respectively, and the recovery was 93% to 110%. The uncertainty of measurement in samples was 4.5% to 13.8% in crystal violet, and 5.9% to 10.1% in MVB. The level of uncertainty in the Black Gel Pen Inks on paper was measured to ±0.14 μg, 18.9% in the case of detection of crystal violet (0.72 μg per 1 mm of Black Gel Pen Inks on paper). MVB was measured to ±0.13 μg 29.2% at a concentration of 0.46 μg in a 1mm sized sample. The level of uncertainty with the calibration curve and repeated measures were the highest values found. The factors of uncertainty were comprised of stability of balance, resolution, reproducibility, purity of standard material, molecular weight, concentration, dilution of standard solution, calibration curve, recovery and reproducibility capabilities of the analysis equipment. From this study, the range of measurement uncertainty can be estimated in the case of measuring the dye content. These results can be used as the standard to verify the dye content measured in the Black Gel Pen Inks on paper. Characterizations of ink and writing instruments (morphology, ingredient and content) are important as they can be used as evidence of crimes, such as forged checks and wills. Therefore, the results of this study may provide important basic data to verify the new test method.
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