电感耦合等离子体质谱在微量物证检验中的应用
郭洪玲1, 乔婷1, 宋小娇2, 韩星星3, 高婷4, 权养科1, 朱军1
1. 公安部物证鉴定中心,北京 100038
2. 南京森林警察学院,南京 210001
3. 新疆维吾尔族自治区公安厅刑侦总队刑科中心,乌鲁木齐 830094
4. 黑龙江省哈尔滨市公安局,哈尔滨 150010
摘要

法庭科学领域微量物证检验中,元素分析是非常重要的一个方面。通过分析物证中的主要元素和微量元素,可以为物证之间的比对检验和物证溯源提供关键信息。虽然目前有很多微量物证的元素分析方法,但电感耦合等离子体质谱(ICP-MS)技术是在近十年愈益受到关注和应用。相对于常用的元素分析方法,如X射线荧光光谱法、原子吸收光谱法、中子活化分析以及波长(或能量)色散X射线能谱法,ICP-MS分析法有很多优点,比如更适合于微量物证的检验分析,只需要很少的样品量,就可以完成主要元素和微量元素的同时分析;如果配置激光蚀刻进样系统,就不需对样品进行复杂的前处理,可大大节省时间和物力;同时,激光蚀刻进样只需要非常小的样品量,几乎是无损检验,能够避免像X射线荧光光谱对样品表面必须平整的要求。在我们微量物证检验实验室,应用溶液进样和激光烧蚀取样两种模式以ICP-MS分析法进行了很多有价值的工作,本文对相关部分工作进行介绍和总结。通过对重金属中毒检验,通过微波消解-ICP-MS法对死者组织中汞(Hg)、钛(Ti)、铬(Cr)、砷(As)等元素含量的准确分析,帮助推断了死亡原因;对环境污染案件中提取的泥土样品,经微波消解后进行ICP-MS检验,分析了嫌疑排放污物对环境的污染程度;对土壤样品,采用碰撞反应池技术和标准分析模式,定量检验了30余种元素,为泥土样品的比对和地源推断提供了丰富的信息;对小样品量泥土样品,通过激光蚀刻-ICP-MS检验,优化了激光的烧蚀参数。以此为基础,还利用激光蚀刻-ICP-MS法对案件中收集到的假币纸张进行了检验,经数据聚类和主成分分析,使12起案件中的8起得到串并。此外,利用激光蚀刻-ICP-MS法对按主要成分无法区分的细金属丝(铁丝)进行检验,通过其微量元素的种类与含量测定,对金属丝作了进一步的分辨。再有,利用ICP-MS的同位素比值分析方法,对国内主要子弹生产厂家的41枚子弹弹头进行了铅(Pb)元素同位素比分析,既对铅弹头进行了辨识,又通过铅元素同位素比值数据建立了子弹头与生产厂家间的关联。ICP-MS的应用方法在本实验室仍在不断开发中,如对地质样品进行元素分布分析,以及结合激光蚀刻的厚度蚀刻功能,对不同层次的油漆样品作分层检验等。

关键词: 电感耦合等离子体质谱; 激光蚀刻电感耦合等离子体质谱; 微量物证; 元素分析; 同位素比值
中图分类号:DF794.3 文献标志码:A 文章编号:1008-3650(2016)06-0470-06 doi: 10.16467/j.1008-3650.2016.06.010
The Application of Inductively Coupled Plasma Mass Spectrometry in Trace Evidence Examination
GUO Hongling1, QIAO Ting1, SONG Xiaojiao2, HAN Xingxing3, GAO Ting4, QUAN Yangke1, ZHU Jun1
1. Institute of Forensic Science, Ministry of Public Security, Beijing 100038, China
2. Nanjing Forest Police College, Nanjing 210001, China
3. Institute of Forensic Science, Department of Public Security of Xinjiang Uygur Autonomous Region, Urumqi 830094, China
4. Harbin Public Security Bureau, Harbin 150010, China

Author: Guo Hongling(1977—), female, PhD, associate professor, mainly focusing on trace evidence. E-mail:guohongling1234@163.com

Abstract

Elemental analysis is important for forensic chemists to examine trace evidence. The analysis of both major and trace element is widely used for forensic comparisons, having successfully provided essential information for evidence provenancing. Although there are several established techniques available to determine elemental composition, the inductively coupled plasma mass spectrometry (ICP-MS) has in the latest decade drawn much more attention from many scientists, including those who are concerned with forensic applications. Compared with other elemental analytic methods, e.g., X-ray fluorescence (XRF), atomic absorption spectrophotometry (AAS), neutron activation analysis (NAA) and energy (or wavelength) dispersive X-ray microanalysis (EDS or WDS), ICP-MS has many advantages, for example, the capability of more suitable to simultaneously measure the abundance of a large suite of elements in small samples; time and resource saving when coupled with laser ablation approach because of its non-necessity of sample preparation, proximity to non-destruction on the sample, avoidance of demand to measure on smooth surfaces required by XRF; and quantitative analysis of major, minor and trace elements in one analytic run. All these advantages help to examine trace evidence more easily and quickly. In our laboratory, ICP-MS has been used to measure the heavy metal (Hg, Ti, Cr, As) contents in human tissues related to poisoning events, the liquids discharged into river or soil to tell if they are harmful to the environment. Moreover, the laboratory also used ICP-MS, combined with the laser ablation approach, to examine the amount-small soil evidence, counterfeit banknote paper and thin metal wires to make them compared and identified. In addition, lead isotope ratio among bullet alloys has been detected to differentiate them and link them with their manufacturers. At present, our on-going application of ICP-MS is under development in aspects such as the elemental mapping of geological evidence and the strata analysis into vehicle paints.

Key words: ICP-MS; LA-ICP-MS; trace evidence; elemental analysis; isotope ratio
1 Introduction

Elements are ubiquitously present in the evidence and their concentration can provide abundant information for the evidence to be compared [1, 2, 3]. The analysis of major and trace element, the so-called “ chemical fingerprinting” , is widely used for forensic evidence provenancing[4]. In forensic science, X-ray fluorescence (XRF) and energy (or wavelength) dispersive X-ray microanalysis (EDS or WDS) are commonly used in elemental analysis[5, 6, 7]. Each technique has advantages and disadvantages in terms of sample size requirements, the range of elements capable of being analyzed, detection limits, convenience of sample preparation, precision and accuracy of results for different elements, cost, and the extent to which the analysis is destructive[8]. Inductively coupled plasma mass spectrometry (ICP-MS) has drawn forensic chemists’ much more attention because of its high sensitivity and outstanding performance in simultaneous multi-element analysis [9, 10]. Institute of Forensic Science under the Ministry of Public Security, a Chinese prestigious forensic science laboratory nationwide, provides scientific solutions of evidence examination to help all level’ s public security organizations in China, meanwhile having done a lot of achievements to investigate the elemental analysis by ICP-MS.

2 Analyses through Solution-based ICP-MS Combined with Microwave Digestion

Solution-based ICP-MS analysis is among the most commonly used choices for forensic purpose to determine the elements’ composition in evidential substances, e.g, bullet alloys and glass fragments[9]. Some scientists conducted experiments to check the method itself [8, 11]. In our laboratory, solution-based ICP-MS, combined with microwave digestion, has been used to measure the heavy metals in human tissues suspected of poisoning of such kind; to determine the trace elements’ concentration in fake and quality-inferior liquors; to test the elements and their concentration present in car’ s plastic headlight shuck for evaluating whether they come from the same source; and to detect the elements like chromium (Cr), zinc (Zn), lead (Pb) in waste water and soils to judge if they are polluted.

2.1 Determination of Heavy Metal in Human Tissues

Although the use of compounds containing heavy metals has decreased due to their toxic and environmental deterioration, traditional Chinese medicine occasionally still uses some of them as active ingredients. The inappropriate intake of these medicines sometimes causes death. In rural areas of China, many a few quack doctors often treat diseases, e. g., psoriasis, with applying a kind of poultice which usually contains several kinds of heavy metals.

Such a case happened in a rural area of northeast China three years before a boy likely died from the application of poultice onto his large part of skin [12]. In order to find his death reason, the boy’ s soft tissues, including heart, liver, kidney, subcutaneous tissue and heart-blood, were digested in a mixture of 6 ml of nitric acid (HNO3) and 2 ml of hydrogen peroxide (H2O2). All the samples were decomposed at the maximum temperature of 200º C in sealed TFM tubes. ICP-MS measurements revealed that the contents of arsenic (As), hydrargyrum (the more acceptable version of this element as “ mercury” ) (Hg) and lead (Pb) were hundreds even thousands times higher in the samples than the normal content in the controlled tissue samples, indicating the fact of poisoning. It is rare that these three heavy metals coexist in one formula of Chinese medicine because of the potential to cause poisoning. According to the contents of the elements in different tissues of the dead boy, these heavy metals were deduced to coordinate in the body and redistribute in different tissues. Arsenic was deposited mainly in liver and kidney while mercury mostly sank in kidney. Lead was metabolized slowly, presenting basically itself in skin and subcutaneous tissues.

2.2 Measurement of Trace Elements in Fake and Quality-inferior Liquors

There are many Chinese famous brands of liquors which are expensive. For to profit, some people are increasingly manufacturing and selling the fake and/or quality-inferior liquors on market. Usually, the GC/MS is employed to analyze the alcohols and ketones. Yet, ICP-MS measurement is a better alternative to fulfill this task for identification of trace elements in the liquors whose reality needs to be verified. Although the microwave digestion is usually used to treat the samples with nitric acid, it is inadequate for the liquor to receive the very same treatment because of the high content of alcohol. In our laboratory, 21 different brands of liquors suspected of faked ones were volatilized and then added 2ml of nitric acid (ultra-pure) to dissolve the samples and transferred to 25 ml volumetric flask with deionized water for ICP-MS measurement [13], leading to be measured of elements of lithium (Li), potassium (K), vanadium (V), copper (Cu), arsenic (As), strontium (Sr) and lead (Pb). The concentration of element potassium (K) is generally higher than other elements. Copper (Cu) is relatively lower in concentration but changes dramatically among different liquor samples. Arsenic (As) is higher with its concentration of 32 ng/ml in one kind of liquor than the other samples where their As concentrations are low and no obvious difference amid them. Lithium (Li) and vanadium (V) are relatively low of content in the samples, varying little in different ones of them. Lead (Pb), a heavy metal element harmful to human health, is very low of content in the samples. With determination and measurement of all the elements plus their concentrations by ICP-MS, different brands of liquor samples have been differentiated thoroughly and totally.

2.3 Comparison of Car’ s Plastic Headlight Shucks

Cars are becoming even more involved in different kinds of cases, mainly the traffic accidents in China. Headlights of cars are easily broken and left over at the scenes. Plastic, instead of glass, is commonly used into automobiles’ headlights now. In many cases, plastic headlight shucks are necessarily compared to determine whether they come from the same source. In forensic science, plastic is typically identified by the way of infrared spectroscopy to define its type and/or by X ray dispersive spectrometry (EDX) to conduct elemental analysis for deciding if there are any additive elements. But for the plastic of car headlight shuck, its types of fabricating material are almost same, resulting in the impossibility to differentiate them by the infrared spectroscopy and/or EDX. Since trace amounts of additives can improve the physical and chemical properties of the headlight shuck during the manufacture process, ICP-MS, able to differentiate the elemental ingredients, is used to find out the additives and their amount present in the plastic samples. Such information can help make the comparison to disclose their provenance. In one experiment conducted in our lab, 33 different plastic samples of headlight shuck were collected and analyzed by ICP-MS. With the parameter optimization for microwave digestion, the contents of boron (B), sodium (Na), magnesium (Mg), calcium (Ca), potassium (K), titanium (Ti), scandium (Sc), chromium (Cr), lead (Pb), manganese (Mn), strontium (Sr), ferrum (iron) (Fe), hydrargyrum (mercury) (Hg) were measured along with their Euclidean distances. Taken together of the 528 pairs of comparison between different samples, the differentiating rate is about 92.8 %, demonstrating that ICP-MS, when combined with the Euclidean data processing, is reliable to compare the plastic samples of headlight shuck.

2.4 Heavy Metal Determination in Environmental Samples

Chinese government rules that the releasing of fluids or gases into the environment must be strictly controlled. Yet, there are lots of illegal factories, who are engaged in, e. g., electroplating and have no post-disposing devices, often directly discharging the waste water into soils. The waste water and polluted soil samples are often brought to our lab to test if the concentrations of some heavy metals are higher than the blank sample. Once, the elements of zinc (Zn), chromium (Cr) and lead (Pb) were examined in more than ten cases. Waste water was usually diluted and subjected to direct analysis by ICP-MS. For the soil samples controlled with its blank specimen, they were commonly digested with the mixture of nitric acid (HNO3), hydrochloric acid (HCl) and hydrofluoric acid (HF) at the volume ratio of 6:5:1.5 under 210º C for 20 minutes. The elements of zinc (Zn) and chromium (Cr) were measured with the cell collision, together with the lead (Pb) being determined with the standard mode by ICP-MS.

3 Examinations by ICP-MS with Laser Ablation (LA-ICP-MS)

Solution-based ICP-MS is more suitable for liquid other than solid samples to have them analyzed because the solid ones have to be dissolved beforehand. This is time consuming and requires strong acids such as the hydrofluoric acid, a chemical reagent which can not only give rise to the matrix-based interference but also cause the contamination. In contrary, ICP-MS, when combined with the direct solid introduction by laser ablation (LA-ICP-MS), requires minimum sample preparation. LA-ICP-MS provides good means for such evidence which requires to be analyzed nondestructively and/or the tiny evidence, for instance, that of small fragments. LA-ICP-MS also plays its role upon the samples difficult to digest. As such, LA-ICP-MS has been applied to many kinds of evidence like glass fragments and automobile paints [14, 15].

3.1 Soil Examination

Trace elements in soil sample are usually measured by solution-based ICP-MS. Nevertheless, LA-ICP-MS method is preferred when the sample’ s amount is less than 0.1 g. In one of our experiments, the soil samples were sieved and pressed for measurement [16]. In order to better ablate the soil samples with laser, the parameters including the laser spot size, energy level, pulse and the frequency, were to be optimized. It was found that two Chinese standard soil samples got good results by the raster mode setting with the laser spot of 150 μ m and energy level at 100 %. The data analyzed were close to those labeled. The soil samples, unable to be differentiated by XRF that is eligible for major elemental composition, were further discriminated by LA-ICP-MS choice.

3.2 Thin Wire Examination

Metal wires are often found to truss dead bodies and/or other objects in crime scenes. These wires are usually thin and their main components generally tend to be same, thereby making the inter-sample comparison difficult and even impossible. LA-ICP-MS provides a perfect way to solve this kind of problems. In a case where the metal wires taken from the corpse and the suspect were required to be compared, both wires are of iron and their diameter is only about 1.2mm [17]. In our experiment, the cross sections were fresh created to undergo the LA-ICP-MS analysis. With presence of the elements nickel (Ni), cobalt (Co) and copper (Cu) plus their different concentrations measured in the evidence, these two ferreous wires were eventually differentiated. Necessary to mention, absolute counts per second of each element were often suggested to record and compare directly because of the frequent unavailability towards the standards of similar matrix to the evidence.

3.3 Counterfeit Banknote Paper Examination

The counterfeit currency is one of the most serious problems in the world, having been bothering authorities of many countries since the appearance of currency. China is not immune from these problems and has suffered from them for over years. The most widely used and effective way to examine counterfeit banknotes is by visual and physical comparison. However, for the stuff that makes counterfeit notes, such as the paper, printing ink or toner together with those semi-finished samples that have had yet none of characteristic additional imitations of security features, better strategies should be used to acquire enough information to identify if they come from the same source by which to make cases linked. LA-ICP-MS is one of the best ways to examine paper samples, capable of meeting the fast analysis and nondestructive to the trace paper or paper with ink on it. In our lab, LA-ICP-MS was ever utilized to analyze 21 special paper samples that were seized from 12 different cases involving with counterfeit banknotes in different provinces[18]. The data were processed by multivariate calculation of cluster and principle-component analyses. All these paper samples were mainly classified into three groups from which eight separate cases were successfully linked together. The results were confirmed by the suspects who bought this kind of paper and used them to make counterfeit notes.

4 Lead Isotope Ratio Measurement in Bullet

Isotope ratio measurement plays an important role in comparing and sourcing the evidence. The analysis of lead (Pb) and strontium (Sr) isotope ratio by ICP-MS has been done in many research fields. In clinical applications, isotope abundance ratio measurement is relevant to monitoring the occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic researches [19, 20]. Researches of lead (Pb) isotope ratio have also been conducted in bullet and gun-shot residue analysis [21, 22, 23]. Similarly, the lead isotope ratio analysis has been still adopted for forensic purpose with the introduction of ICP-MS into the forensic labs in China.

Recently, 41 bullets were collected of different batches from three companies and measured by quadrupole ICP-MS (ICP-QMS) [24]. Factors of the concentration of element lead (Pb), dead time, sweeps and dwell time were optimized. It is found that the dead time has an obvious effect on the accuracy of isotope ratio. The measurement of precision (RSD %) is about 0.1 %. Although the measurement of precision attainable by ICP-QMS may not be adequate for all applications [25] when compared with the thermal ionization mass spectrometry (TIMS) and/or multicollector (MC) ICP-MS which are both based on the relatively wide span of isotopic compositions of lead (Pb) in bullets, our ICP-QMS manipulation had well-categorized these 41 bullets into 3 groups, just corresponding to the three manufacturers. Bullets of different batches from the same manufacturer were also differentiated by the lead (Pb) isotopic compositions. Promisingly, more information about the lead linking with bullet will be provided upon the acquisition of lead isotopic ratio from bullets and the raw materials of lead ores.

ICP-MS has been bringing into important play in forensic laboratories worldwide. Our lab is about to plan the elemental mapping, a measurement to unveil the element distribution in corpse tissues for discovery of the metabolizing mechanism of some poisons. Definitely, ICP-MS will help us to solve more problems.

The authors have declared that no competing interests exist.

作者已声明无竞争性利益关系。The authors have declared that no competing interests exist.

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