常见炸药的稳定同位素比值分析方法研究进展

doi:10.3724/SP.J.1123.2020.09015

摘要/Abstract

摘要：

炸药的深度比对与溯源对于爆炸案事件的侦破具有重大意义,以不同地域来源的原料或不同生产工艺生产的炸药,其组成元素的稳定同位素比值具有差异,因而稳定同位素比值可作为炸药深度比对与溯源的重要指标。稳定同位素比值质谱法(IRMS)作为一种高精度的稳定同位素比值测量手段,已逐渐发展成熟,与元素分析仪、气相色谱仪、液相色谱仪等仪器联用,在食品安全、环境保护、法庭科学等领域应用广泛。IRMS在炸药比对与溯源上亦发挥了重要作用,自1975年IRMS被应用于区分不同国家生产的三硝基甲苯(TNT)以来,IRMS已成功用于多种炸药的分析。但目前尚未见有文献系统地总结常见炸药的稳定同位素比值分析研究进展。该文介绍了稳定同位素比值分析的相关原理、仪器组成及特点,分别总结了硝酸铵、黑火药、TNT、太恩、黑索金等常见炸药的稳定同位素比值分析方法,汇总了文献报道的不同国家生产的硝酸铵、黑火药、TNT等炸药的稳定同位素比值。文章就不同炸药的稳定同位素比值差异、炸药生产、存储过程中相关因素对同位素比值的影响,爆炸前后稳定同位素比值的变化情况等内容进行了分析。本文还指出了目前炸药的稳定同位素比值分析研究中存在的问题,对可能的解决办法进行了讨论,对未来的发展方向提出了建议。

关键词: 稳定同位素比值质谱, 同位素比值, 炸药, 溯源

Abstract:

The ratio of stable isotopes of the elements in explosives differs depending on the raw materials obtained from different geographical sources or the production processes adopted. Hence, this ratio can be used as an important index for the comparison and trace of explosives. Isotope ratio mass spectrometry (IRMS), a high-precision method for the analysis of stable isotope ratios, has evolved into a mature tool in this regard. In combination with elemental analysis, gas chromatography, liquid chromatography, etc., IRMS is widely used in food safety, environmental protection, forensic science, and other fields. IRMS also plays an important role in the comparison and trace of explosives. Since its application to distinguish trinitrotoluene (TNT) produced in different countries in 1975, IRMS has been successfully used in the analysis of various explosives. However, there is no systematic summary on the research progress on the stable isotope ratio analysis of common explosives. This paper provides a brief description of the related principle, instrumental composition, and characteristics of stable isotope ratio analysis. Methods for the stable isotope ratio analysis of common explosives such as ammonium nitrate, black powder, TNT, pentaerythritol tetranitrate (PETN), and cyclotrimethylene trinitroamine (RDX) are reviewed. The bulk stable isotopic ratio analysis method was used in most of the studies to determine the total isotope ratio of the sample. A compound-specific isotope analysis method was also employed to determine the isotope ratio of organic explosives in a complex matrix. The reported stable isotope ratios of explosives such as ammonium nitrate, black powder, and TNT produced in different countries are summarized. The discrimination ability of the stable isotope ratio for explosives is discussed. Based on the stable isotope ratio, explosives from different sources can be distinguished effectively. By combining the results of elemental analysis with the ICP-MS results, the discrimination efficiency of different samples could be further improved. The influence of relevant factors on the isotope ratio during the production and storage of explosives are collated. There is a strong correlation between the stable isotope ratios of explosives and raw materials. The stable isotope ratios of TNT, PETN, and other explosives are related to that of nitric acid used in the production. The stable isotope ratios of nitrogen and oxygen in the explosive are relatively stable and almost unchanged within one year of production. The complexity of the environmental matrix at the explosion site and the low concentration of explosive residues make the stable isotope analysis of explosive residues challenging. However, the changes in the stable isotope ratio before and after the explosion are discussed. Since there is no information on the application of stable isotope analysis to the traceability of explosives, the paper mentions that the standardized explosive sample pretreatment, stable isotope analysis method, collection and analysis of large amounts of explosive samples, and explosive stable isotope database are the basis of explosive traceability. This paper also outlines the existing challenges in the analysis of the stable isotope ratios of explosives, including the small number of explosive samples, lack of a stable isotope explosive analysis database, and difficulty in the stable isotope analysis of explosive residues. Possible solutions to these problems are proposed, followed by suggestions for the future development of the stable isotope ratio analysis of common explosives. The suggestions include establishing an effective extraction and enrichment method for explosive residues, combining IRMS with GC or LC for analyzing explosives, establishing a comprehensive process for the analysis of the stable isotope ratios of inorganic and organic explosives, and comparison and analysis of the stable isotope analysis data using statistical methods.

Key words: stable isotope ratio mass spectrometry (IRMS), isotope ratio, explosive, traceability

中图分类号:

O658

胡灿, 梅宏成, 郭洪玲, 孙振文, 刘占芳, 朱军. 常见炸药的稳定同位素比值分析方法研究进展[J]. 色谱, 2021, 39(4): 376-383.

HU Can, MEI Hongcheng, GUO Hongling, SUN Zhenwen, LIU Zhanfang, ZHU Jun. Recent advances in stable isotope ratio analysis of common explosives[J]. Chinese Journal of Chromatography, 2021, 39(4): 376-383.

图/表 4

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Number of samples	Sample source	δ¹⁵N		δ¹⁸O		Reference
Number of samples	Sample source	Reference materials	Measured value/‰	Reference materials	Measured value/‰	Reference
103	Europe	IAEA-N-1, IAEA-N-2	-1.6-+4.8	USGS34, USGS35	+16.8-+24.8	[23]
13	Europe	IAEA-N-1, IAEA-N2, IAEA-NO-3	-6.1-+2.1	IAEA-CH-3	+16.5-+24.4	[27]
4	France	atmospheric N₂	-2.4-+0.8	SMOW	+21.6-+23.3	[28]
2	Spain	atmospheric N₂	-0.7-+2.5	SMOW	+18.0-+25.1	[29]

Number of samples	Sample source	δ¹⁵N		δ¹⁸O		Reference
Number of samples	Sample source	Reference materials	Measured value/‰	Reference materials	Measured value/‰	Reference
103	Europe	IAEA-N-1, IAEA-N-2	-1.6-+4.8	USGS34, USGS35	+16.8-+24.8	[23]
13	Europe	IAEA-N-1, IAEA-N2, IAEA-NO-3	-6.1-+2.1	IAEA-CH-3	+16.5-+24.4	[27]
4	France	atmospheric N₂	-2.4-+0.8	SMOW	+21.6-+23.3	[28]
2	Spain	atmospheric N₂	-0.7-+2.5	SMOW	+18.0-+25.1	[29]

Number of samples	Sample source	δ¹⁵N		δ¹⁸O			δ¹³C			Reference
Number of samples	Sample source	Reference materials	Measured value/‰	Reference materials		Measured value/‰	Reference materials	Measured value/‰		Reference
33	Switzerland, Germany, France	IAEA-N1, IAEA-N2, IAEA-N3	-28.0-+2.9	IAEA-CH-3	+15.0-+24.2		IAEA-USGS2, IAEA-CH-6, IAEA-CH7		-28.6--26.4	[27,30]
20	Japan	USGA-40	-0.7-+10.8	-	-		NBS-22		-28.3--25.9	[32]

Number of samples	Sample source	δ¹⁵N		δ¹⁸O			δ¹³C			Reference
Number of samples	Sample source	Reference materials	Measured value/‰	Reference materials		Measured value/‰	Reference materials	Measured value/‰		Reference
33	Switzerland, Germany, France	IAEA-N1, IAEA-N2, IAEA-N3	-28.0-+2.9	IAEA-CH-3	+15.0-+24.2		IAEA-USGS2, IAEA-CH-6, IAEA-CH7		-28.6--26.4	[27,30]
20	Japan	USGA-40	-0.7-+10.8	-	-		NBS-22		-28.3--25.9	[32]

Number of samples	Sample source	Method	δ¹⁵N/‰	δ¹⁸O/‰	δ¹³C/‰	Reference
7	UK, USA, Israel, Italy, Canada,	DI-IRMS	-	-	-30.93--24.53	[20]
	Yugoslavia, Hungary
14	Montenegrin, France	EA/IRMS	-8.7-+3.5	+16.5-+19.2	-29.9--23.5	[28]
5	USA, Croatia	GC/ITMS/IRMS	-5.36-+9.64	-	-26.42--22.21	[34]