红外光谱结合化学计量学方法在激光打印原装黑色墨粉分析中的应用研究

目的 采用红外光谱比较分析不同原装黑色墨粉（31个样本）的差异,探讨化学计量学方法在墨粉种类识别中的适用性.方法 对打印样本纸张上的黑色墨粉进行烫熨提取后直接分析检测.IR分析条件：显微红外光谱仪,常温透射模式,扫描范围为4 000～400 cm-1,分辨率为16cm-1,累计扫描次数为64次.结果 墨粉树脂主要为聚苯乙烯/甲基丙烯酸甲酯和聚对苯二甲酸/环氧树脂.采用主成分析（Principal Component Analysis,PCA）与系统聚类法（Hierarchical Cluster Analysis,HCA）对不同种类墨粉进行聚类分析与建模预报.基于前两主成分得分值（53.3％）不同树脂成分的墨粉样本聚类效果明显,同时在第三个主成分方向上黑白与彩色激光墨粉样本获得良好区分.结论 红外光谱法结合化学计量学方法用于不同种类树脂及打印类型原装黑色墨粉的聚类分析与建模预报方法可行,结果准确可靠.     

Toner Particles as Forensic Evidence: Microanalytical Characterization of Known Toner and Recognition of Toner in Environmental Samples*†‡

Modern printing toners represent a prime example of subvisible particles that can be easily transferred to hands, clothing, and other surfaces. To explore the potential evidentiary value of toner particles, toner samples were collected from known printer cartridges and characterized by various microanalytical techniques to establish the properties most useful for recognition, identification, and comparison. Environmental samples (i.e., dust) were then collected from various locations at varying distances from toner-based printers, using both tape lifts and carbon adhesive stubs, to assess the possibility of detecting toner. By light microscopy, toner can be recognized on the basis of particle size and shape, as well as color. Further examination of the micromorphology in the field emission scanning electron microscope reveals characteristic morphologies and differences in surface texture and shape among toner sources. Raman spectroscopy provides chemical identification of the pigment (or pigment class) and, in some cases, also permits identification of the polymer component. While black and blue pigment chemistry remained constant among toner varieties that were studied (copper phthalocyanine and carbon black), variation in yellow and magenta pigments was observed. Analysis of dust samples collected from various environments demonstrated that while toner is consistently detectable in close proximity to printers (within 2 feet), it also can be detected in dust collected in nearby rooms. This research demonstrates that toner particles can be located, characterized, and discriminated, using a suite of microanalytical methods that are applicable to forensic casework.     

Characterization of Blue Pigments Used in Automotive Paints by Raman Spectroscopy

Micro‐Raman spectroscopy was applied to forensic identification of pigments in paint chips and provided differentiation between paint samples. Sixty‐six blue automotive paint samples, 26 solid and 40 metallic were examined. It was found that the majority of the collected Raman spectra provided information about the pigments present. However, in some cases, fluorescence precluded pigment identification. Using laser excitation at longer wavelengths or pretreatment to effect photobleaching often resulted in reduced fluorescence, particularly for solid color samples, and allowed pigment identification. The examined samples were compared pairwise taking into account number, location, and intensity of absorption bands in their infrared spectra. The estimated discrimination power ranged from 97% for solid paint samples to 99% for metallic paint samples.     

Neural networks in forensic science.

Neural networks were developed to study and mimic the functioning of the human brain. Humans are good at pattern recognition; the question is how good neural networks are at it, particularly with problems of forensic science interest. Simulation experiments with a type of neural network known as a Hopfield net indicate that it may have value for the storage of toolmark patterns (including bullet striation patterns) and for the subsequent retrieval of the matching pattern using another mark by the same tool for input. Another type of neural network, the back-propagation network (BPN), is useful for applications similar to those for which standard statistical methods of pattern classification can be used. This would be an appropriate approach to the matching of general component patterns, such as gas chromatograms of gasoline, or pyrolysis patterns from materials of forensic science interest, such as paint. The BPN may provide better results than statistical methods, but it is currently necessary to try both to determine which would be best for any given situation.     

Determining Line-Crossing Sequences Between Laser Printing and Writing Pen Using Coaxial Light

Determining the application sequence of hand-written pen ink and printer toner lines has attracted significant interest in questioned document examination. This study uses coaxial light to determine line-crossing sequences, with intersections observed under a VSC600 forensic document workstation and a Leica M205A Stereo-microscope. Results show that reflected light at intersections and color contrast between intersections and nonintersections was observed when a hand-written ink line passes over a toner line, while a toner line passing over a written line appeared dull, with no color contrast. The procedure was tested under a range of conditions, such as types of writing pens and laser printers, the writer, and writing pressure, with the latter playing an important role in the evaluation. To validate the results, a 90% detection rate and 98% accuracy rate were achieved from 50 samples of blind testing, which is more effective than optical microscopy.     

裂解气相色谱-质谱法和红外光谱法对红色汽车油漆的比较分析

目的应用裂解气相色谱-质谱法（Py-GC/MS）和红外光谱法（IR）鉴别3种红色汽车油漆,通过二者的比较,考察Py-GC/MS法在微量物证油漆鉴定中的适用性。方法取适量固体样品直接检测。IR检测条件：红外显微镜,透射模式,光阑尺寸100μm×100μm,检测范围为4000-675cm-1。Py-GC/MS检测条件：裂解温度：550℃,裂解时间：0.20min。HP-5MS色谱柱,分流比80∶1;升温程序：起始温度为40℃,保持1 min,然后以8℃/min升至300℃,保持1 min。质谱采用EI源,扫描范围：29~350 amu。结果 3种红色汽车油漆的红外光谱、裂解图谱均能相互区分。通过裂解产物,能获得更多油漆主要成膜物质的成分信息。结论在样品量许可的条件下,应在红外光谱的检测基础上,进一步使用裂解气相色谱-质谱方法来对汽车油漆进行检测,通过互相验证,获得更准确、可靠的油漆鉴定结果。     

Comparative analysis of synthetic polymers using combinations of three analytical methods

The use of three analytical techniques for forensic investigation of synthetic polymers is described. These techniques are: pyrolysis infrared spectrometry (PyIR), pyrolysis gas chromatography (PyGC) and energy dispersive X-ray micro probe analysis (EPMA). Whereas the first two methods have been described previously, the microanalytical procedure is new. It may be used in combination with one of the other two techniques for the discrimination between polymer samples.     

线聚焦显微激光拉曼光谱技术区分激光打印墨粉

目的利用Renishaw InVia激光显微拉曼光谱仪对打印墨粉进行区分。方法用785nm激发波长,采取线聚焦模式,50倍物镜条件下,测定了惠普等8个品牌25种硒鼓型号的30份激光打印机打印墨迹样品的拉曼光谱。结果 30种样品墨迹的谱图进行了分析,根据拉曼的异同,可将30种样品分为5大类。结论线聚焦显微激光拉曼光谱可用于区分不同种类激光打印墨粉。     

The effect of ionizing gamma radiation on natural and synthetic fibers and its implications for the forensic examination of fiber evidence

Circumstances of criminal activities involving radioactive materials may mean fiber evidence recovered from a crime scene could have been exposed to materials emitting ionizing radiation. The consequences of radiation exposed fibers on the result of the forensic analysis and interpretation is explored. The effect of exposure to 1-1000 kGy radiation doses in natural and synthetic fibers was noticeable using comparative forensic examination methods, such as optical microscopy, microspectrophotometry, and thin-layer chromatography. Fourier transform infrared spectroscopy analysis showed no signs of radiation-induced chemical changes in any of the fiber structures. The outcome of the comparative methods highlights the risk of "false negatives" associated in comparing colors of recovered fibers that may have been exposed to unknown radiation doses. Consideration of such results supports the requirement to know the context, including the environmental conditions, as much as possible before undertaking a forensic fiber examination.     

微束X射线荧光分析法鉴别激光打印机墨粉的研究

目的利用微束X射线荧光分析法（μ-XRF）研究激光打印机用墨粉的鉴别。方法利用μ-XRF对9台不同型号激光打印机用墨粉、对应的打印字迹、提取的字迹墨粉所含元素进行定性、半定量的分析。结果根据检出元素种类的不同,可将9台不同型号激光打印机用墨粉、对应的打印字迹、提取的字迹墨粉分成7类、4类、4类,区分率分别为94.4%、75%、69.4%。结论本研究所建立的μ-XRF鉴别激光打印机墨粉方法具有微区、原位无损检验等优点,对提高激光打印文件检验水平具有现实意义。     

A Two‐Level Model for Evidence Evaluation in the Presence of Zeros*

Abstract: Likelihood ratios (LRs) provide a natural way of computing the value of evidence under competing propositions. We propose LR models for classification and comparison that extend the ideas of Aitken, Zadora, and Lucy and Aitken and Lucy to include consideration of zeros. Instead of substituting zeros by a small value, we view the presence of zeros as informative and model it using Bernoulli distributions. The proposed models are used for evaluation of forensic glass (comparison and classification problem) and paint data (comparison problem). Two hundred and sixty‐four glass samples were analyzed by scanning electron microscopy, coupled with an energy dispersive X‐ray spectrometer method and 36 acrylic topcoat paint samples by pyrolysis gas chromatography hyphened with mass spectrometer method. The proposed LR model gave very satisfactory results for the glass comparison problem and for most of the classification tasks for glass. Results of comparison of paints were also highly satisfactory, with only 3.0% false positive answers and 2.8% false negative answers.     

A comparative analysis of Cannabis material

Extracts of 100 plant-like or resinous materials were analyzed for CBD, CBC, delta 9-THC, and CBN by GC using two different column packings and by GC-MS. Our independent identification of these cannabinoids confirmed those of other forensic science analysts who used microscopic examination, the Duquenois-Levine color test, and TLC for their analyses of the same samples. The identifications of cannabinoids by forensic acience analysts using TLC were corroborated by GC-MS analysis of hexane extracts of appropriate chromatogram spots.     

Impurities,adulterants and cutting agents in cocaine as potential candidates for retrospective mining of GC-MS data

Cocaine is one of the most widely used illicit drugs worldwide. Cocaine powders seized by the Police may contain numerous other substances besides the drug itself. These can be impurities originating from the coca plant or the production process, or be purposely added to the drug formulation as adulterants and cutting agents. In forensic laboratories, identification of cocaine is routinely done through GC-MS analysis, but other components are often ignored even if the method allows for their detection. Yet, they can provide valuable insight into the history of a seizure and its potential connection to other samples. To explore this idea, an extensive review of common impurities and adulterants encountered in cocaine is presented. Based on their incidence, concentration in the end product and compatibility with GC-MS methods, their overall usefulness as candidates for the statistical investigation of existing forensic data is evaluated. The impurities cis- and trans-cinnamoylcocaine, tropacocaine, norcocaine and N-benzoylnormethylecgonine as well as the adulterants lidocaine, procaine, tetracaine, benzocaine, caffeine, acetylsalicylic acid, phenacetin, ibuprofen, levamisole, hydroxyzine and diltiazem are promising candidates to provide additional forensic intelligence. Future research on optimized routine GC-MS methods, signal reproducibility, comparison, statistics and databases is suggested to facilitate this concept. Ultimately, such an approach may significantly advance the amount of information that is extracted from routine casework data, elucidate developments in the cocaine markets in the past and facilitate Police work in the future. Preliminary assessment of existing data from the forensic laboratory of the Amsterdam Police has been included to show that the detection of the identified target impurities is feasible, and that small adjustments to the analysis method could significantly increase the detectability of these analytes in prospective drug screenings. Forensic intelligence based on retrospective data mining of cocaine containing casework samples may thus be realized with minimal additional laboratory efforts by using already available instrumentation, samples and data.     

合成大麻素类新精神活性物质4F-MDMB-BICA的检测

目的 建立基于红外光谱(fourier transform infrared,FT-IR)、气相色谱-质谱联用(gas chromatography-mass spectrometry,GC-MS)、高分辩质谱(high resolution mass spectrometer,HRMS)和核磁共振波谱(nuclear...     

The use of microspectrophotometry for the identification of pigments in small paint samples

The visible reflectance spectra of a number of common pigments are presented. These were measured between 380 nm and 900 nm in paint films using the Nanospec 10S Microspectrophotometer. This data can be used in combination with a computer program based upon simple Kubelka-Munk theory to identify the pigments in paint samples. The use of this approach in forensic science is illustrated by examples from recent cases.     

Determination of the sequence of intersecting lines from laser toner and seal ink by Fourier transform infrared microspectroscopy and scanning electron microscope / energy dispersive X-ray mapping

The aim of this study was to verify that the combination of Fourier transform infrared microspectroscopy and scanning electron microscope / energy dispersive X-ray mapping could be applied to line intersection problems. The spectral data of red seal ink, laser toner and their intersections, such as peak location and peak intensity, were described. Relative peak height ratios of different chemical components in intersecting lines were used to distinguish the sequences. Energy dispersive X-ray mapping characteristics of intersecting areas were also detailed. The results show that both the laser toner and the seal ink appear on the surface of intersections, regardless of the sequence. The distribution of the two inks on the surface is influenced not only by the sequence of heterogeneous lines but also by diffusion. Fourier transform infrared microspectroscopy and scanning electron microscope/energy dispersive X-ray mapping are able to explore the chemical components and the corresponding elemental distribution in the intersections. The combination of these two techniques has provided a reliable method for sequencing intersecting lines of red seal ink and laser toner, and more importantly, this method may be a basis for sequencing superimposed lines from other writing instruments.     

The characterization of automobile body fillers

Body fillers are sometimes encountered with paint evidence from hit-and-run accidents. Little forensic research has been conducted and published on the subject since 1986. The objective of this study was to determine if chemical and physical differences in body fillers from various manufacturers existed and could be identified. Thirty-three samples of light-weight automobile body fillers and spot putties were obtained. The fillers and putties were compared using light microscopy, infrared spectroscopy, scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDX), and pyrolysis gas chromatography (pyGC). Results from fourier transform infrared spectroscopy analysis placed the samples into five groups and differentiated six samples. Light microscopy placed the samples into one of five color groups. PyGC placed the samples into three groups and differentiated one sample. SEM-EDX placed the samples into four groups and differentiated 13 samples. Using these analysis methods, 19 of the 33 samples could be discriminated. The best discriminatory tool was found to be SEM-EDX.     

Determination of the Chronological Order of a Laser Printing and Gel Pen Writing Without any Crossing Strokes

Laser printers and writing instruments are being exploited by the forgers to produce fabricated documents. They often produce such documents by appending genuine signature on a blank sheet and later printing on it. Often these fabricated documents do not contain intersection of strokes and may pose a difficulty to forensic document examiners in analyzing cases related to such documents. Keeping in mind the limited research work done on nonintersecting strokes, the present study has been conducted with an aim to determine the sequence of nonintersecting strokes of gel pens and laser printers. Three hundred samples of nonintersecting strokes of gel pen ink and laser printing were prepared. Of these 300, 150 had laser-printed text below the gel pen strokes and the remaining 150 were prepared with gel pen stokes below the laser-printed text. The samples have been analyzed using Nikon SMZ 800N stereomicroscope. Three micro-conformation features, that is, pattern of toner distribution, ink distribution, and fiber distribution have been observed in the samples. The results demonstrate the successful establishment of sequence of nonintersecting strokes in case of gel pen and laser-printed documents by the determination of micro-conformation features.     

自主合成标准物质鉴定缴获物中的新精神活性物质ADB-FUBINACA

目的新精神活性物质在世界范围内蔓延迅速,但相关标准物质的短缺制约着其分析方法的研究和案件检验。本文以我国首次出现的N-(1-氨甲酰基-2,2-二甲基丙基)-1-(4-氟苄基)吲唑-3-甲酰胺(ADB-FUBINACA)制毒案件为例,介绍在无法及时获得商业化标准物质的情况下,不得不通过自主合成制备标准物质解决案件检验难题,建立该新精神活性物质检验的方法。方法建立气相色谱-质谱检验方法,分析条件:色谱柱为Aglient DB-5MS石英毛细管柱(30.00m×0.25mm×0.25μm);初始柱温60℃,按15℃/min升至300℃,保持15min;载气为氦,流速1.0mL/min,分流进样,进样量1.0μL,分流比20∶1;进样口温度280℃;电子轰击(EI)离子源,电子能量70eV,离子源温度230℃,四级杆温度150℃,传输线温度280℃,质量扫描范围m/z 40~500amu,全扫描模式(SCAN)采集总离子流图,溶剂延迟3.0min。案件缴获的送检未知样品经甲醇提取,超声、离心后,取上清液以GC-MS分析;将所得主要质谱特征碎片峰(m/z)通过NIST质谱库、SWGDRUG质谱数据库以及相关文献进行检索,初步确定待测目标物。采用有机合成技术制备ADB-FUBINACA标准物质,合成路线为:吲唑-3-甲酸甲酯与4-氟苄溴发生取代反应,生成1-(4-氟苄基)-1H-吲唑-3-甲酸甲酯;取代产物在碱性条件下经水解反应得到有机酸1-(4-氟苄基)-1H-吲唑-3-甲酸;在催化剂作用下,有机酸与L-叔亮酰胺发生酰化反应,制得化合物ADB-FUBINACA。经气相色谱-质谱(GC-MS)、液相色谱-离子阱-飞行时间质谱(LCMS-IT-TOF)、核磁共振(NMR)等分析,合成化合物的结构得以确证;同时采用超高效液相色谱-二极管阵列检测器(HPLC-PDA)进行分析,对其归一化纯度进行测定。将案件未知样品和合成标准物质分别用甲醇提取,超声、离心后,再行上清液GC-MS分析。结果经GC-MS分析,案件未知样品(RT=19.818min)的质谱特征碎片峰(m/z)信息为109.0(基峰)、253.1、338.1、309.1和145.0,经与合成标准物质的保留时间及质谱图检测比对,证实为N-(1-氨甲酰基-2,2-二甲基丙基)-1-(4-氟苄基)吲唑-3-甲酰胺;通过查阅相关资料,对上述质谱特征碎片峰的产生机制进行了推断,并对1H-NMR、13C-NMR和DEPT-135等一维核磁谱图的信号进行了归属分析。结论本文报道的新精神活性物质ADB-FUBINACA其GC-MS分析方法,可用于实际案件检验鉴定;合成化合物的结构表征方法也可用于固体ADB-FUBINACA的定性分析。基于有机合成技术的新精神活性物质制备与案件检验方法,可缓解有关标准物质短缺制约该类案件检验鉴定的现状。     

Isotope ratio mass spectrometry as a tool for forensic investigation (examples from recent studies).

The versatility of isotope ratio mass spectrometry is demonstrated by reference to diverse case studies. Variations in the natural isotopic composition of non-biological, organic materials are compared as a means by which samples may be associated or discriminated. These techniques may be used to augment or compliment conventional forensic methodologies. delta13C analysis was used to demonstrate that different masking tape had been recovered in two, apparently similar cases, involving the smuggling of money. Visually similar ecstasy tablets were compared by consideration of the delta13C and delta15N composition of MDMA extracted from the tablets. Although only a limited number of tablets were analysed, the isotopic similarity between two different seizures was sufficient to induce a guilty plea from a person suspected of possessing both. A combination of delta2H, delta13C, delta15N and delta18O together with GC-MS analyses were applied to small samples of seized heroin. Although GC-MS analysis indicated differences between the chemical composition of two of the heroin samples, isotopic analysis suggested similarities, which were confirmed by further delta2H, delta13C and delta18O isotopic analysis of the clingfilm in which the samples were wrapped.