Application of LC−QTOF/MS for the validation and determination of organic explosive residues on Ionscan® swabs

The identification and confirmation of trace explosive residues along with potential precursors and degradation products require a comprehensive laboratory analysis procedure. This study presents the determination of organic explosives consisting of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4,6-trinitrotoluene (TNT), 2,4,6,N-tetranitro-N-methylaniline (Tetryl), 1,3,5-trinitrobenzene (1,3,5-TNB) and pentaerythritol tetranitrate (PETN) by a high-resolution liquid chromatography quadrupole time-of-flight mass spectrometry (LC−QTOF/MS). The qualitative information including retention time, collision energy, precursor ions, and characteristic fragmentation pattern of each explosive were collected using an atmospheric pressure chemical ionization (APCI) in negative ion mode. The separation efficiency among five compounds was greatly achieved in this study. Four real explosive samples consisting of TNT, RDX, PETN and Tetryl and 12 Ionscan® quality control swabs from the Royal Thai Army were also tested to validate and verify the viability of the GC–MS method used to validate results from an Ionscan® system. The results showed that LC−QTOF/MS is a powerful technique for the identification and confirmation of thermally unstable organic explosives on Ionscan® swabs compared to a conventional GC−MS technique.     

Comparison of three collection methods for the sodium rhodizonate detection of gunshot residues on hands

The aim of this study was to compare three gunshot residue (GSR) collection methods used in conjunction with chemographic detection applied by different regional Swiss police services. The specimens were collected from the hands of a shooter with either filter paper (Filter method) or adhesive foil. The adhesive foil was then either applied against photographic paper during visualisation (AF Photo method) or coated with a layer of polyvinyl alcohol (AF PVAL method). The experiments involved two conditions of the examined hands, i.e. dry and humidified. The residues were revealed using the sodium rhodizonate test (SRT). Preliminary tests assessing the possibility of conducting a confirmatory Scanning Electron Microscopy coupled to Energy Dispersive X-ray spectroscopy (SEM/EDX) analysis after the chemographic test were performed on a number of specimens by cutting positive spots and mounting them on stubs. Obtained results were compared in terms of effectiveness - number of positive spots, time requirements, quality of subsequent SEM-EDX analysis, ease of use and cost.The Filter method generally yielded a high-quality detection with both dry and humidified hands, as well as a simple, quick and efficient confirmation by SEM/EDX. The AF Photo performed well on dry hands, but not on humidified hands. The AF PVAL method performance was lower compared to the other methods in both examined conditions of the hands. The SEM/EDX analysis showed that the Filter and AF PVAL method provided satisfactory results when a sufficient carbon coating thickness was applied to the cuttings. It was also observed that the thinner the PVAL layer, the better the quality of the spectra and obtained images in SEM/EDX. Furthermore, the surface of the photographic paper did not seem to be conductive, even after the application of a thick layer of carbon.In conclusion, the Filter method gave the best overall results, but its application required slightly more time and expertise than the two other methods.     

基于《中华人民共和国药典》优化丹参中33种禁用农药残留物检测的前处理方法

目的 以丹参为研究对象,比较2020版《中华人民共和国药典》（简称《中国药典》）中3大类前处理方法对33种禁用农药残留物回收率的影响,进一步优化快速样品处理法（quick,easy,cheap,effective,rugged and safe, QuEChERS）,并应用于199批饮片和60批药材的筛查。方法 分别从基质效应和回收率方面比较《中国药典》3类前处理方法,并对QuEChERS法进行研究与优化,样品加水后由 1%醋酸-乙腈提取,依次加入QuEChERS盐包与QuEChERS净化管盐析净化,提取液经浓缩后分别加入水和内标磷酸三苯酯,结合液相色谱-串联质谱法（LC-MS/MS）和气相色谱-串联质谱法（GC-MS/MS）以添加水平为定量限浓度水平测定样品的回收率和RSD。结果 采用《中国药典》前处理方法时,丹参中33种禁用农药（54个单体）在添加水平为定量限浓度水平时,部分农药回收率较低;优化QuEChERS法后,丹参中33种禁用农药（54个单体）在一定浓度下,线性关系良好,r均大于0.990,其回收率为64.43%~127.35%,RSD均<15%;199批饮片和60批药材中共检出2种农药,甲拌磷检出率为3.86%,克百威检出率为1.93%,但残留量均未超过2020版《中国药典》规定限度。结论 优化后的QuEChERS法快速简便,有针对性地对丹参中33种禁用农药残留进行准确检测,对于丹参的生产种植与日常监控具有一定的参考意义。     

常见洗手方式对92式手枪射击残留物检出率的影响

目的研究常见洗手方式对92式手枪射击残留物检出率的影响,为确定犯罪嫌疑人射击与否的推断提供依据。方法实验人员使用92式手枪分别射击1枪和3枪,射击后0．5h内,射击人员的手分别用清水、肥皂和洗手液清洗3遍（对照组为未清洗）,对实验人员的手部进行射击残留物的提取,利用扫描电镜和能谱仪对射击残留物进行检验。结果持枪射击后,射击人的手部会附着大量的射击残留物,用常见的洗手方式进行清洗后,仍然能检测到射击残留物,且不同的洗手方式对射击残留物的检出率的影响差异显著。结论常见洗手方式不能完全清除手部的射击残留物,对涉枪案件犯罪嫌疑人的判定有一定的参考价值。     

A comparative study of gunshot residue originating from 9 mm Luger ammunition from various producers

Following previous work on differentiation between gunshot residue according to the type of ammunition used, a specific investigation was undertaken of traces originating from 9 mm Luger ammunition using SEM-EDX. The aim of this study was to determine whether GSR originating from this type of ammunition is similar, or whether differentiation could be made between particular manufacturers of Luger ammunition. The results were collected in the form of counts of particles in each of seven key elemental classes being combinations of lead, antimony and barium. These were then adjusted to a factor known as frequency of occurrence which allows comparison of the distribution of particles within the classes between samples with differences in absolute particle counts. The relationships between the samples were examined using non-parametric statistical tests: R-Spearman and tau-Kendall rank correlation coefficients. It has been found that most of the studied samples of GSR were similar to each other despite their originating from various manufacturers.     

海洛因毒品中残留有机溶剂的检测方法与结果分析

目的建立固体海洛因毒品中残留有机溶剂的顶空-气相色谱和顶空-气相色谱-质谱联用检测方法。方法采用干法和湿法处理42份样品,密封后90℃加热振荡20min,抽取顶空气体用气相色谱法（DB-WAX毛细柱,30m×0.25mm,0.25μm）和气相色谱-质谱联用法（HP-5MS毛细柱,30m×0.25mm,0.25μm）检测,以已知17种有机溶剂外标法定性。在样品中加水后检测,根据峰高估算5种共有成分的含量。结果在42份海洛因毒品中检出乙酸、乙醚、乙醇、乙酸乙酯、乙醛、三氯甲烷等12种有机溶剂成分,5种主要共有成分相对含量有差别。结论本研究建立的检测方法快速、简便,定性可靠,可用于固体海洛因毒品的来源与批次分析。     

The detection of metallic residues in skin stab wounds by means of SEM-EDS: A pilot study

The morphological analysis of stab wounds may often not be accurate enough to link it with the type of wounding weapon, but a further evaluation may be performed with the search for metallic residues left during the contact between the instrument and the skin. In this study, Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS) was applied to the study of cadaveric stab wounds performed with kitchen knives composed of iron, chromium and nickel, in order to verify the presence of metallic residues on the wound's edge. Two groups of 10 corpses were selected: group A, including victims of stab wounds and a control group B (died of natural causes). Samplings were performed on the lesions and in intact areas of group A, whereas in group B sampling were performed in non-exposed intact skin. Samples were then analysed with optical microscopy and SEM-EDS. In group A, optical microscopic analysis showed the presence of vital haemorrhagic infiltration, while SEM-EDS showed evidence of microscopic metal traces, isolated or clustered, consisting of iron, chromium and nickel. Moreover, in two cases organic residues of calcium and phosphate were detected, as a probable sign of bone lesion. Control samples (group A in intact areas and group B), were negative for the search of exogenous material to optical microscopy and SEM-EDS. The results show the utility and possible application of the SEM-EDS in theidentification of metallic residues from sharp weapons on the skin.     

Pyrotechnic reaction residue particle analysis

Pyrotechnic reaction residue particle (PRRP) production, sampling and analysis are all very similar to that for primer gunshot residue. In both cases, the preferred method of analysis uses scanning electron microscopy to locate suspect particles and then uses energy dispersive x-ray spectroscopy to characterize the particle's constituent chemical elements. There are relatively few times when standard micro-analytical chemistry performed on pyrotechnic residues may not provide sufficient information for forensic investigators. However, on those occasions, PRRP analysis provides a greatly improved ability to discriminate between materials of pyrotechnic origin and other unrelated substances also present. The greater specificity of PRRP analysis is the result of its analyzing a large number of individual micron-sized particles, rather than producing only a single integrated result such as produced using standard micro-analytical chemistry. For example, PRRP analyses are used to demonstrate its ability to successfully (1) discriminate between pyrotechnic residues and unrelated background contamination, (2) identify that two different pyrotechnic compositions had previously been exploded within the same device, and (3) establish the chronology of an incident involving two separate and closely occurring explosions.     

Desorption electrospray tandem MS (DESI-MSMS) analysis of methyl centralite and ethyl centralite as gunshot residues on skin and other surfaces

Abstract:  A direct and sensitive method for the detection of methyl centralite (MC) and ethyl centralite (EC) as gunshot residues (GSRs) has been developed. This method uses desorption electrospray ionization (DESI)-tandem mass spectrometry and directly desorbs and detects analytes from surfaces without any sampling process. Typical transitions for MC and EC, m/z 241 to m/z 134 and m/z 269 to m/z 148, respectively, were used to improve the assay sensitivity. It has been shown that MC and EC can be detected on various surfaces, with detection limits of 5–70 pg/cm². Interferences, detection time after shooting and the number of times hands were washed after shooting were also evaluated. None of the materials interfered with the results and the detection window for organic GSRs was up to 12 h and hands could be washed at least six times. Further samples were analyzed to confirm the reliability of this method, and showed that it could discriminate shooters from nonshooters. This method should be of significance in forensic science, especially in analyzing GSRs, because of its simplicity, high throughput, and the direct detection of MC and EC on suspects' hands, clothes, and hair.     

92式手枪射击距离与射击残留物分布密度相关性的研究

目的研究92式手枪射击距离与射击残留物分布密度的相关性,为射击距离的推断提供依据。方法选择92式手枪,在带皮的猪肉上覆盖白色棉布,设计了0m,0．1m,0．2m,0．5m,1．0m,1．5m,3．0m,5．0m,10m,15．0m,20．0m,25．0m共12个距离进行射击,提取白棉布上的弹孔圆周和距弹孔2cm的圆周上的射击残留物,利用扫描电镜／能谱仪对不同射击距离遗留在白棉布上的射击残留物进行检验。结果白棉布上射击残留物分布密度与射击距离呈负相关的关系。结论根据棉布上射击残留物的分布密度,能够推断射击距离,对涉枪案件中射击距离的判断有一定的参考价值。