烧毁复印纸的提取、显现方法研究

目的建立科学的提取、显现烧毁复印纸的方法。方法制备烧毁复印纸,对比喷雾法、气熏法、涂刷法、水漂法、发胶喷雾法对烧毁复印纸的摊平软化效果;对比夹板固定法和胶带粘取法对烧毁复印纸的固定效果;对比光学检验法、化学显现法对烧毁复印纸文件的显现效果。结果喷雾法摊平软化效果整体上优于其他方法;夹板固定法可适用于大多数烧毁复印纸文件,胶带粘取法适用于打印类复印纸文件;光学检验可以显现出黑笔、蓝笔、红笔、2B铅笔字迹以及指印,化学显现可以更清晰地显现出黑笔、2B铅笔字迹。结论当烧毁复印纸烧毁程度不明确时,摊平软化可选用喷雾法;当烧毁复印纸内容需进一步检验时,固定优选用夹板固定法;显现烧毁复印纸应根据不同显现客体采取合适的方法。     

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS) — Discrimination of ammonium nitrate sources

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures.The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid.Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed.The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material.     

Characterisation of 0.22 caliber rimfire gunshot residues by time-of-flight secondary ion mass spectrometry (TOF-SIMS): a preliminary study

The application of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for the characterisation of gunshot residue (GSR) from 0.22 caliber rimfire ammunition is reported. Results obtained by TOF-SIMS were compared with conventional scanning electron microscopy (SEM) studies. As could be expected, TOF-SIMS exhibited greater elemental sensitivity than SEM equipped with energy dispersive X-ray detection (SEM-EDX), and was also capable of detecting fragments characteristic of inorganic compounds. This preliminary study indicates that TOF-SIMS offers substantial potential for forensic GSR examinations as a complementary technique to SEM-EDX. In addition TOF-SIMS is applicable to the analysis of individual particles in the typical size range encountered in GSR casework.     

Improving the technological readiness of time of Flight-Secondary Ion Mass Spectrometry for enhancing fingermark recovery - towards operational deployment

The processes routinely used by police forces to visualise fingermarks in casework may not provide sufficient ridge pattern quality to aid an investigation. Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) has been proposed as a technique to enhance fingermark recovery. The technique is currently designated a Category C process in the Fingermark Visualisation Manual (FVM) as it shows potential for effective fingermark visualisation but has not yet been fully evaluated. Here the sensitivity of ToF-SIMS on three common exhibit-type surfaces - paper, polyethylene and stainless-steel was compared to standard processes. An adapted Home Office grading scale was used to evaluate the efficacy of fingerprint development by ToF-SIMS and to provide a framework for comparison with standard processes. ToF-SIMS was shown to visualise more fingerprints than the respective standard process, for all surfaces tested. In addition, ToF-SIMS was applied after the standard processes and successfully enhanced the fingerprint detail, even when the standard process failed to visualise ridge detail. This demonstrates the benefit for incorporating it into current operational fingermark development workflows. Multivariate analysis (MVA), using simsMVA, was additionally explored as a method to simplify the data analysis and image generation process.     

Exposing latent fingermarks on problematic metal surfaces using time of flight secondary ion mass spectroscopy

Fingermarks are a key form of physical evidence for identifying persons of interest and linking them to the scene of a crime. Visualising latent (hidden) fingermarks can be difficult and the correct choice of techniques is essential to develop and preserve any fingermarks or other (e.g. DNA) evidence that might be present. Metal surfaces (stainless steel in particular) have proven to be challenging substrates from which to reliably obtain fingermarks. This is a great cause for concern among police forces around the globe as many of the firearms, knives and other metal weapons used in violent crime are potentially valuable sources of fingermark evidence. In this study, a highly sensitive and non-destructive surface science technique called time of flight secondary ion mass spectroscopy (ToF-SIMS) was used to image fingermarks on metal surfaces. This technique was compared to a conventional superglue based fuming technique that was accompanied by a series of contrast enhancing dyes (basic yellow 40 (BY40), crystal violet (CV) and sudan black (SB)) on three different metal surfaces. The conventional techniques showed little to no evidence of fingermarks being present on the metal surfaces after a few days. However, ToF-SIMS revealed fingermarks on the same and similar substrates with an exceptional level of detail. The ToF-SIMS images demonstrated clear ridge definition as well as detail about sweat pore position and shape. All structures were found to persist for over 26?days after deposition when the samples were stored under ambient conditions.     

Raman spectroscopy and laser desorption mass spectrometry for minimal destructive forensic analysis of black and color inkjet printed documents

Inkjet ink analysis is the best way to discriminate between printed documents, or even though more difficult, to connect an inkjet printed document with a brand or model of printers. Raman spectroscopy and laser desorption mass spectrometry (LDMS) have been demonstrated as powerful tools for dyes and pigments analysis, which are ink components. The aim of this work is to evaluate the aforementioned techniques for inkjet inks analysis in terms of discriminating power, information quality, and nondestructive capability. So, we investigated 10 different inkjet ink cartridges (primary colors and black), 7 from the HP manufacturer and one each from Epson, Canon and Lexmark. This paper demonstrates the capabilities of three methods: Raman spectroscopy, LDMS and MALDI-MS. Raman spectroscopy, as it is preferable to try the nondestructive approach first, is successfully adapted to the analysis of color printed documents in most cases. For analysis of color inkjet inks by LDMS, we show that a MALDI matrix (9-aminoacridine, 9AA) is needed to desorb and to ionize dyes from most inkjet inks (except Epson inks). Therefore, a method was developed to apply the 9AA MALDI matrix directly onto the piece of paper while avoiding analyte spreading. The obtained mass spectra are very discriminating and lead to information about ink additives and paper compositions. Discrimination of black inkjet printed documents is more difficult because of the common use of carbon black as the principal pigment. We show for the first time the possibility to discriminate between two black-printed documents coming from different, as well as from the same, manufacturers. Mass spectra recorded from black inks in positive ion mode LDMS detect polyethylene glycol polymers which have characteristic mass distributions and end groups. Moreover, software has been developed for rapid and objective comparison of the low mass range of these positive mode LDMS spectra which have characteristic unknown peaks.     

Characterization of gunpowder samples using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) was utilized to obtain characteristic mass spectra from three different smokeless powders and six different black powder samples. In these mass spectra, peaks indicative of both the organic and inorganic additive constituents in the gunpowders were observed. TOF-SIMS was able to successfully differentiate between the different black and smokeless gunpowder samples analyzed with the aid of principal components analysis (PCA), a multivariate statistical analysis approach often used to reduce the dimensionality of complex data. TOF-SIMS was also used to obtain information about the spatial distribution of the various additives contained within the gunpowder samples. SIMS imaging demonstrated that that the samples could potentially be characterized by their 2-D structure, which varied from sample to sample. These results clearly demonstrate the feasibility of utilizing TOF-SIMS as a tool for the characterization and differentiation of gunpowder samples for general forensic applications.     

Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks

Stamp pad inks from different manufacturers across India have been analyzed to investigate the feasibility of Raman scattering as a tool for forensic analysis of questioned documents involving stamp inks. Nine different stamping inks were analyzed by both Raman spectroscopic and HPTLC methods. The results demonstrate the effectiveness of these methods in classifying the investigated stamping inks based on their spectral pattern and HPTLC chromatogram. Raman scattering tool was able to determine the sequence of heterogeneous intersection strokes involving a blue stamp pad ink and other writing instruments, such as ballpoint pen ink (red and black), pencil and laser printer toner. However, this method was unable to resolve the exact sequencing for the intersection strokes involving investigated stamp ink and blue ballpoint ink or gel pen ink (all colors).     

The use of an electrostatic detection device to identify individual and class characteristics on documents produced by printers and copiers--a preliminary study

The market is inundated with inkjet printers, laser printers, and photocopiers, which are often used in criminal activities. Many of these office machines are built by various manufacturers, hence they are constructed with different hardware designs (e.g. "rolling" and "grabbing" mechanisms) that have changed over the years due to technological advances. Examinations of printed documents that involve the chemical analysis of ink colorants and the identification of physical machine defects such as trash marks are essential for the forensic examiner, but new techniques are needed to more closely identify a machine model or group of models. An electrostatic detection device (EDD) provide forensic examiners with a nondestructive method to examine indentations on a document. In this work, an EDD is used to detect latent physical markings left on documents by printers and photocopiers. Seventeen inkjet printers, 12 laser printers, and 3 photocopy machines were used to produce test documents. Physical markings were detectable in the large majority of the documents and were reproducible 100% of the time.     

Basic forensic identification of artificial leather for hit-and-run cases

Single fibers retrieved from a victim's garments and adhered to the suspect's automobile have frequently been used to prove the relationship between victim and suspect's automobile. Identification method for single fiber discrimination has already been conducted. But, a case was encountered requiring discrimination of artificial leather fragments retrieved from the victim's bag and fused fibers from the bumper of the suspect's automobile. In this report, basic studies were conducted on identification of artificial leathers and single fibers from leather materials. Fiber morphology was observed using scanning electron microscopy (SEM), color of these leather sheets was evaluated by microspectrophotometry (MSP), the leather components were measured by infrared micro spectrometry (micro-FT-IR) and the inorganic contents were ascertained by micro-X-ray fluorescence spectrometry (micro-XRF). These two methods contribute to other analytical methods too, in the case of utilized single fiber analytical methods. The combination of these techniques showed high potential of discrimination ability in forensic examinations of these artificial leather samples. In regard with smooth surface artificial leather sheet samples, a total of 182 sheets were obtained, including 177 colored sheets directly from 10 of 24 manufacturers in Japan, and five of them were purchased at retail circulation products. Nine samples of suede-like artificial leather were obtained, 6 of them were supplied from 2 manufacturers and 3 sheets were purchased as retailing product. Single fibers from the smooth surface artificial leather sheets showed characteristic for surface markings, and XRF could effectively discriminate between these sheets. The combination of results of micro-FT-IR, color evaluation by MSP and the contained inorganic elements by XRF enabled to discriminate about 92% of 15,576 pairs comparison. Five smooth surface samples form retailing products were discriminated by their chemical composition into four categories, and in addition color information to this result, they were clearly distinguished. Suede-like artificial leather sheets showed characteristic extra-fine fibers on their surface by the observation of SEM imaging, providing high discriminating ability, in regard with suede-like artificial leather sheets were divided into three categories by micro-FT-IR, and the combination of these results and color evaluation information, it was possible to discriminate all the nine suede-like artificial leather sheets examined.     

Identification of Eight Synthetic Cannabinoids,Including 5F‐AKB48 in Seized Herbal Products Using DART‐TOF‐MS and LC‐QTOF‐MS as Nontargeted Screening Methods

Synthetic cannabinoids are sprayed onto plant material and smoked for their marijuana‐like effects. Clandestine manufacturers modify synthetic cannabinoid structures by creating closely related analogs. Forensic laboratories are tasked with detection of these analog compounds, but targeted analytical methods are often thwarted by the structural modifications. Here, direct analysis in real time coupled to accurate mass time‐of‐flight mass spectrometry (DART‐TOF‐MS) in combination with liquid chromatography quadruple time‐of‐flight mass spectrometry (LC‐QTOF‐MS) are presented as a screening and nontargeted confirmation method, respectively. Methanol extracts of herbal material were run using both methods. Spectral data from four different herbal products were evaluated by comparing fragmentation pattern, accurate mass and retention time to available reference standards. JWH‐018, JWH‐019, AM2201, JWH‐122, 5F‐AKB48, AKB48‐N‐(4‐pentenyl) analog, UR144, and XLR11 were identified in the products. Results demonstrate that DART‐TOF‐MS affords a useful approach for rapid screening of herbal products for the presence and identification of synthetic cannabinoids.     

Stable isotope profiling of burnt wooden safety matches

Arson is a significant problem around the world, and is a crime which results in a low number of convictions. The scene of an arson can be varied, commercial, residential or national park, and recently cases have been identified which were initiated by a lit match. Matches can be recovered from a scene, usually in a burnt condition. The benefit of analysing unburnt matches has been researched previously [1,2]. In most cases, burnt matches are recovered from scenes, and therefore the research was extended to investigate the potential of using IRMS to analyse burnt matches. This includes samples which have been exposed to petrol, and various fire extinguishing chemicals.Matches were sectioned to reveal central unburnt portions of wood and analysed by isotope ratio mass spectrometry (IRMS). The stable isotope profile (SIP) of the wooden matchstick samples was unaffected by the presence of both petrol and a variety of fire extinguisher chemicals. Any changes seen could be attributed to the natural variability of isotopic composition encountered in a natural material such as wood. These findings were confirmed by the isotope analysis of 19 matchstick samples placed in mock fire training scenarios. The data was examined using a paired t-test and Hotellings T² test for a single sample.     

Democratic Legitimacy in the Bund or ‘Federation of States’: the Cases of Belgium and the EU

Carl Schmitt developed the concept of the ‘federation of states’ (Bund) in order to characterise intermediate constitutional systems which are integrated beyond the level of a confederation (Staatenbund) without, however, acquiring the level of integration of an actual federal state (Bundesstaat). In this paper we analyse the constitutional specificity of the ‘federation of states’ and present three normative principles for assessing the democratic legitimacy of the decision‐making procedures within such a federation. We argue that both the European Union and Belgium can be analysed as instances of such a federation of states and show how this characterisation improves our understanding of the evolutionary dynamics of both polities and the constitutional and democratic challenges they are facing.     

Differentiation of bullets by spark source mass spectrometry.

A study has been made to demonstrate the capability of spark source mass spectrometry (SSMS) for differentiating bullets on the basis of elemental composition. Twenty-six elements are commonly found in bullet lead at the 0.1-ppm level and above. Only twelve of these prove to be generally useful for quantitative characterization. The precision of analysis with SSMS using photographic detection is about 10% relative standard deviation. The accuracy obtained in this study is considerably worse than this, about 30% average error. In spite of such large errors, SSMS is shown to be far superior to the more precise method of neutron activation analysis. The reason, of course, is the large number of elements determined by SSMS. Bullets do not have uniform elemental compositions within a box or lot. Instead, there are usually two or three distinct groups of bullets within a given box. Three Winchester boxes representing lots manufactured a few weeks apart showed common groups among them. All other boxes had unique groups of bullets, indicating that the method is a promising alternative to the conventional method of identifying bullets by physical markings.     

Classification of black powder toners on the basis of integrated analytical information provided by Fourier transform infrared spectrometry and X-ray fluorescence spectrometry

Differentiating between black powder toners used in laser printers and copiers can be challenging for forensic examiners. One hundred and sixty-two samples from 82 different types of cartridges produced by 21 manufacturers that are currently available on the Polish market were studied using Fourier transform infrared spectrometry (FT-IR) and energy-dispersive X-ray fluorescence spectrometry (XRF). The spectra obtained by these two methods were classified into 14 groups and 28 groups using FT-IR and XRF, respectively. These classifications served as a basis for the development of an analytical scheme for differentiating black powder toners. This scheme can be used with any two methods that supply different information about an examined sample. The research will show that if two samples are similar in polymer composition (e.g., FT-IR spectra), additional quantitative elemental composition from XRF analyses may provide more discrimination. It was possible to differentiate 82.5% pairs of examined samples using only FT-IR, 90.8% pairs of examined samples using only XRF, and 95.8% pairs of examined samples using these two methods. Obtained spectra and all the available information could be used to create/build a database. The results obtained confirm the multiplicity and compatibility of toners. Additionally, it was stated that not all the samples were original (OEM).     

Analysis of tetrodotoxin

Law enforcement personnel interdicted an illegal shipment of a chemical suspected to be an illicit drug. However, literature within the package indicated that the substance was actually tetrodotoxin, a potent marine neurotoxin. Analyses of the questioned samples by gas chromatography–mass spectrometry revealed no evidence for the presence of illicit drugs, but this technique was ineffectual for the identification of tetrodotoxin. Direct-inlet-probe mass spectrometry was likewise unable to characterize the chemical identity of the subject material. Electrospray-ionization mass spectrometry was implemented to successfully identify the interdicted substance as tetrodotoxin.     

Some Examples of Applications of a Microthermal Desorption Device in the Forensic Laboratory

Abstract:  Several applications of a microthermal desorption device for analysis of small forensic samples are presented. The method uses a solid phase microextraction holder with the fiber removed. In addition to samples of inks on paper, this device was successfully used for analysis of toners, various stains on bank notes, and lipstick stains on paper. Other small items encountered in a forensic science laboratory were also analyzed: particles of smokeless powder, particles of coffee, and automotive clear topcoat layer. The desorbed compounds were analyzed by gas chromatography with a flame ionization detector or by gas chromatography–mass spectrometry. This device can be used in connection with any kind of gas chromatograph. By selection of different injector temperatures, fractionated thermal desorption of samples is achieved. The procedure was demonstrated on samples of ballpoint pen ink of various age.     

Statistical discrimination of black gel pen inks analysed by laser desorption/ionization mass spectrometry

Pearson correlation coefficients were applied for the objective comparison of 30 black gel pen inks analysed by laser desorption ionization mass spectrometry (LDI-MS). The mass spectra were obtained for ink lines directly on paper using positive and negative ion modes at several laser intensities. This methodology has the advantage of taking into account the reproducibility of the results as well as the variability between spectra of different pens. A differentiation threshold could thus be selected in order to avoid the risk of false differentiation. Combining results from positive and negative mode yielded a discriminating power up to 85%, which was better than the one obtained previously with other optical comparison methodologies. The technique also allowed discriminating between pens from the same brand.     

Determining the order of deposition of natural latent fingerprints and laser printed ink using chemical mapping with secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) chemical mapping was used to investigate the order of deposition of natural latent fingerprints and laser printed ink on paper. This feasibility study shows that sodium, potassium and C₃H₅ positive ions were particularly abundant endogenous components of the natural fingerprints and also present in the paper examined, but were mostly absent in the laser printed ink. Mapping of these ions enables the observation of friction ridges from latent prints on the ink surface, only when a fingerprint was deposited above the layer of ink. As a demonstration of proof of concept, blind testing of 21 samples from three donors resulted in a 100% success rate. The sensitivity of this technique was investigated within this trial through the examination of up to fifth depletion fingerprints and ageing of up to 28 days. Migration of fingerprint and paper components to the ink surface, although observed with increased ageing time, was not found to compromise determination of the deposition sequence.     

液相电喷雾离子质谱技术在法医DNA中的应用

生物质谱技术是近年来发展较为迅速的生物分析技术之一,在对大分子生物质量测定中,其以快速、准确、灵敏等优点受到研究者的青睐。其中,液相电喷雾离子电离质谱(LC-ESI-MS)在法医DNA分析中对STR以及SNP遗传标记的检测具有独特的应用价值和广阔的应用前景。本文对ESI-MS的现状和在法医DNA分析中的应用等方面进行了综述,分析了LC-ESI-MS技术在法医学DNA分析中的优缺点,以促进其在国内法医DNA分析中的应用与发展。