Dating of Seals Produced with Stamp‐Pad Ink Using Gas Chromatography Method

Seals are often placed on important documents, and determining the date when a seal was affixed can be important to assess the authenticity of a document. In this study, thirty‐seven different brands of stamp‐pad inks and three different types of paper were used to make diachronic samples of the seals. The volatile components of stamp‐pad ink were determined, and the stamp‐pad ink was classified by gas chromatography with a flame ionization detector. Calibration curves were created to show the relationship between the content of volatile stamp‐pad ink components and the age of stamp‐pad ink entries stored under natural aging, UV‐induced aging, and heating aging conditions. The experimental results showed that GC was useful in the analysis of stamp‐pad ink and applicable for determining the relative age of stamp‐pad ink entries in some cases where the seal was placed on the document within 3 months.     

Preliminary Studies on the Absorbance Ratio Method Used to Determining the Age of Stamp‐pad Ink Seal

Stamp‐pad ink seals are often placed on important documents, and determining the dating of stamp‐pad ink seal is important to assess the authenticity of a document. In this study, 20 different brands and types of stamp‐pad inks were classified by ultraviolet visible spectrophotometer. Six different brands and types of papers were classified by micro‐Fourier transform infrared spectrometer and visual spectral comparator 6000. Three different brands of stamp‐pad inks and two different types of paper were used to make diachronic samples of the seals. A method was employed to date the stamp‐pad seals by comparing absorbance ratios and inks of known age. Curves were created to show the relationship between the absorbance ratio of ink and the age of the seals. The experimental results showed that the absorbance ratio method was applicable for the relative dating of stamp‐pad ink seals in some cases where the seal was placed on the document within 10 weeks.     

Dating of Inkpad Seals Using the Extraction Rate Method: Preliminary Findings

Inkpad seals are often placed on important documents, and determining the date when a seal was affixed can be important to assess the authenticity of a document. In this study, three different brands of inkpads and four different types of paper were used to make diachronic samples of the seals. A double‐solvent extraction method was employed to date the inkpad seals by comparing extraction rates with inks of known age. Cyclohexane was selected as a weak solvent, and chlorobenzene was selected as a strong solvent. After testing, curves were created to show the relationship between the extraction percentage of ink and the date of the seals. The experimental results showed that the extraction rate method was applicable for the relative dating of inkpad seals in some cases where the seal was placed on the document within 6 months.     

Extraction, derivatization, and analysis of vegetable oils from fire debris

Vegetable oils have the ability to spontaneously heat under certain conditions, which may lead to spontaneous ignition. While the oils are not often encountered in forensic casework, they may be suspected in some fire cases. As these oils are not effectively analyzed using traditional fire debris analysis methods, a protocol must be established for extracting vegetable oils from fire debris. In this study, a protocol was developed for the extraction, derivatization, and analysis of vegetable oils from fire debris. Three derivatization methods were compared to establish an optimal derivatization procedure to convert the fatty acids found in vegetable oils to the fatty acid methyl esters (FAMEs) used in analysis. Three different gas chromatograph columns and programs were examined to determine which was best suited for the separation and analysis of FAMEs. The procedure was tested and refined using a variety of neat and burned vegetable oils, in addition to extractions from oils burned on commonly encountered fire debris materials. The findings of this research will serve as a starting point for further understanding and research of vegetable oils in fire debris.     

The Effects of Burning and Mold Growth on the Chemical Composition of Firelog Fuels

Firelogs consist of a cellulosic material, such as sawdust or wood particles, and a combustible binder (fuel). Historically, the fuel typically consisted of a petroleum‐based (paraffin) wax; however, some manufacturers now include vegetable oils in their firelog fuels. To determine fuel composition, fuels from various brands of firelogs were extracted and analyzed by high‐temperature gas chromatography–mass spectrometry (HTGC‐MS) and a GC‐MS with a polar column specific for the analysis of fatty acid methyl esters (FAMEs). Firelogs were also burned, allowed to grow mold, and analyzed by GC‐MS to determine the effects that burning and mold growth have on firelog fuel composition. Mold did not tend to preferentially degrade any of the fatty acids. Burning caused a decrease in the relative amount of all of the fatty acids present in the vegetable oil fuel, with a greater effect on unsaturated fatty acids than saturated ones.     

激光显微共聚焦拉曼光谱仪对红色墨迹的研究

目的利用激光显微共聚焦拉曼光谱仪对文书中常见的红色墨迹材料进行表征,研究该方法对红色墨迹材料的区分能力。方法在785nm激发波长,50倍物镜条件下,对49种红色印文,以及9种彩色喷墨打印和13种彩色激光打印的红色墨迹材料进行拉曼光谱表征。结果通过对71种墨迹样品的谱图进行分析,可以发现,红色印文墨迹、喷墨打印红色墨迹及激光打印红色墨迹的拉曼光谱间均存在差异,同时,拉曼光谱可将这三种墨迹材料分别进一步区分。结论显微共聚焦激光拉曼光谱可对红色墨迹材料进行有效表征和区分。这一方法可对红色印文墨迹进行识别,并且可实现对伪造印文文件的鉴别。     

A review of the analysis of vegetable oil residues from fire debris samples: analytical scheme, interpretation of the results, and future needs

This paper reviews the literature on the analysis of vegetable (and animal) oil residues from fire debris samples. The examination sequence starts with the solvent extraction of the residues from the substrate. The extract is then prepared for instrumental analysis by derivatizing fatty acids (FAs) into fatty acid methyl esters. The analysis is then carried out by gas chromatography or gas chromatography-mass spectrometry. The interpretation of the results is a difficult operation seriously limited by a lack of research on the subject. The present data analysis scheme utilizes FA ratios to determine the presence of vegetable oils and their propensity to self-heat and possibly, to spontaneously ignite. Preliminary work has demonstrated that it is possible to detect chemical compounds specific to an oil that underwent spontaneous ignition. Guidelines to conduct future research in the analysis of vegetable oil residues from fire debris samples are also presented.     

Practical Aspects of Analyzing Vegetable Oils in Fire Debris*

Abstract: Vegetable oils undergo burning, self‐heating, and spontaneous ignition, resulting in their presence in fire debris. As these processes can affect the fatty acid content of vegetable oils, it is important that debris be properly handled in order to obtain reliable and informative data. This research investigated changes in vegetable oil content as a result of storage conditions and different types of burning. Material spiked with vegetable oils and burned was stored under various long‐term conditions, and debris was tested by heating overnight using passive headspace concentration. Results indicated that refrigeration is ideal for fire debris samples suspected of containing vegetable oils and that including passive headspace concentration in the analytical scheme would not affect oils. Spontaneous ignition experiments were conducted to compare the effects of various burning processes on vegetable oil content. Vegetable oils that experienced nonpiloted ignition, self‐heating, and spontaneous ignition produced noticeably different chromatograms from those that underwent piloted ignition.     

Development of a Protein‐based Human Identification Capability from a Single Hair

Shed human hair (lacking root nuclear DNA) frequently contributes important information to forensic investigations involving human identification. Detection of genetic variation observed in amino acid sequences of hair proteins provides a new suite of identity markers that augment microscopic hair analysis and mitochondrial DNA sequencing. In this study, a new method that completely dissolves single hairs using a combination of heat, ultrasonication, and surfactants was developed. Dissolved proteins were digested and genetically variant peptide (GVP) profiles were obtained for single hairs (25 mm) via high‐resolution nanoflow liquid chromatography‐based mass spectrometry and a novel exome‐driven bioinformatic approach. Overall, 6519 unique peptides were identified and a total of 57 GVPs were confirmed. Random match probabilities ranged between 2.6 × 10^?2 and 6.0 × 10^?9. The new bioinformatic strategy and ability to analyze GVPs in forensically relevant samples sizes demonstrate applicability of this approach to distinguish individuals in forensic contexts.     

Analysis of Ecstasy Tablets Using Capillary Electrophoresis with Capacitively Coupled Contactless Conductivity Detection

A method for the identification of 3,4‐methylenedioxymethamphetamine (MDMA) and meta‐chlorophenylpiperazine (mCPP) was developed employing capillary electrophoresis (CE) with capacitively coupled contactless conductivity detection (C⁴D). Sample extraction, separation, and detection of “Ecstasy” tablets were performed in <10 min without sample derivatization. The separation electrolyte was 20 mm TAPS/Lithium, pH 8.7. Average minimal detectable amounts for MDMA and mCPP were 0.04 mg/tablet, several orders of magnitude lower than the minimum amount encountered in a tablet. Seven different Ecstasy tablets seized in Rio de Janeiro, Brazil, were analyzed by CE‐C⁴D and compared against routine gas chromatography‐mass spectrometry (GC‐MS). The CE method demonstrated sufficient selectivity to discriminate the two target drugs, MDMA and mCPP, from the other drugs present in seizures, namely amphepramone, fenproporex, caffeine, lidocaine, and cocaine. Separation was performed in <90 sec. The advantages of using C⁴D instead of traditional CE‐UV methods for in‐field analysis are also discussed.     

公章抗辩的类型与处理

公章的意义在于使特定的意思表示与特定的主体相联结,是书面法律行为的重要标识方式。因经济活动中存在真公章无权使用和假公章冒用等现象,公章名义人因此或借此对公章真假及使用效力提出抗辩。但实践中对公章效力的判定却常有偏差,其重要原因之一就是对公章抗辩缺乏系统有效的处理规则。公章抗辩包括公章确认抗辩和公章效力抗辩,公章效力抗辩又可分为真公章效力抗辩和假公章效力抗辩。不同类型的公章抗辩在抗辩事由、举证责任等方面,均有不同的规则内容与处理要点。实务中对公章抗辩的处理与认定,应当有效把握不同公章抗辩类型的基本规则与特殊情形,并妥当辨识及运用公章效力与表见代理或表见代表之间的互证关系。     

同源激光雕刻橡塑印章印文的鉴别方法

目的找出同源激光雕刻橡塑印章印文之间的特征差异,建立检验鉴定此类印章印文的鉴别方法。方法制作14枚同源激光雕刻橡塑印章,借助文件仪、显微数字分析仪等仪器观察分析其盖印的印文样本。结果找出了各种细节特征差异。结论同源性激光雕刻橡塑印章因其规格性特征符合很好,检验鉴定要以细节特征比对为主。     

Effect of Extraction Procedure and Gas Chromatography Temperature Program on Discrimination of MDMA Exhibits

Analysis of impurities in seized MDMA tablets can be used to determine the synthesis method used and to identify links among exhibits. However, no standardized method exists to generate impurity profiles, limiting comparisons among different laboratories. This research investigated the effect of extraction procedure and gas chromatography temperature program on the resulting impurity profiles. Five exhibits were extracted using liquid–liquid extraction (LLE) and headspace solid‐phase microextraction (HS‐SPME), then analyzed using two different temperature programs. Profiles were statistically assessed using principal components analysis. While LLE was more reproducible, more compounds were extracted using HS‐SPME, thus providing more informative chemical profiles. The longer temperature program (53 min vs. 36 min) allowed greater discrimination of exhibits, due to improved precision as a result of an extended hold time (12 min). This research further highlights the need for standardized extraction and analysis procedures to allow comparison of chemical profiles generated in different laboratories.     

Analysis and classification of common vegetable oils

The analysis of fatty acids from common vegetable oils was investigated for application to forensic casework. A base-catalyzed transesterification of the fatty acids to fatty acid methyl esters using tetramethylammonium hydroxide was simple, rapid, straightforward and inexpensive. Canola, corn, olive, peanut, safflower, soybean and sunflower oils were able to be classified based on their fatty acid methyl ester profiles. Using gas chromatography-mass spectrometry, the detection limits for canola, corn, olive, peanut and safflower oils were determined to be 0.4 mg/mL or less and 0.2 mg/mL or less for soybean and sunflower oils.     

Comparison of motor oils using high-temperature gas chromatography-mass spectrometry

The analysis of motor oils has wide applications in the forensic science field from comparing lubricants transferred between an automobile and a victim or crime scene to differentiating the compositions of plastic explosives. In this study, 40 unused motor oils were analyzed and compared by high-temperature gas chromatography-mass spectrometry to determine the potential for oil individualization. Oil samples were also collected from the crankcase dipsticks of 30 cars. Twenty-six of these oils could be differentiated from each other based on visual comparisons of the unresolved envelope (baseline rise due to incomplete separation) and the resolved hydrocarbons in the raw total ion chromatograms (TICs) and smoothed TIC data. Four of these oils were analyzed as unknowns and were correctly related to the corresponding vehicle. The use of extracted ion profiles (EIPs) was explored as a means to further discriminate between the indistinct samples based on the polycyclic aromatic hydrocarbon (PAH) content. The research discussed in this paper demonstrated that differentiation of motor oils was possible by examining the TIC, smoothed TIC, and EIP data.     

Factors affecting the forensic examination of automotive lubricating oils

Lubricating oil comparisons impact a variety of forensic investigations, including cases where oil was transferred from a suspect vehicle to the crime scene or victim. In this study, high-temperature gas chromatography/mass spectrometry was used to examine the influence of oil mixtures and oil changes over time on the comparison of known and questioned lubricating oils. Varying concentrations of oil mixtures were prepared and showed the potential for identifying individual components. Motor oils from 18 automobiles monitored over a 2-month period did not demonstrate significant changes in the chromatographic data. Chemometric analysis of motor oil mass spectral data provided little information regarding differentiation of, or changes in, the samples. Power steering fluid (PSF) from a naturally occurring leak collected from several locations was consistent with the PSF in the automobile's reservoir, and the PSF composition did not change over time.     

Initial Study for the Determination of the Sequence of Intersecting Lines between Gel Pens and Seals by Optical Coherence Tomography*

Determining the sequence of intersecting lines is a significant issue in the forensic document examination that can reveal the fraud or distinguish between different allegations. Optical coherence tomography (OCT) is a high-resolution cross-sectional imaging technique that has been introduced into forensic science field recently. The potential of OCT as a novel method to determine the sequence of intersecting lines was examined for the first time. In this study, a spectral-domain OCT system with a center wavelength of 900 nm was employed to perform nondestructive examination on determining the sequence of 18 heterogeneous intersecting line samples produced using three types of gel pens and three brands of stamp pad ink seals. Two-dimensional (2D) cross-sectional, and three-dimensional (3D) volumetric images of the intersecting lines were obtained by the OCT system. Several features were noted and analyzed to successfully determine the sequence of all the 18 samples. Blind tests were also conducted to demonstrate the effectiveness of OCT technique. The results illustrate that OCT technology can provide an effective and accurate method for sequencing intersecting lines of gel pen ink and seal ink, which may complement the conventional methods used in the examination of questioned documents.     

Ultrafast Amplification of DNA on Plastic Microdevices for Forensic Short Tandem Repeat Analysis

The majority of microfluidic devices used as a platform for low‐cost, rapid DNA analysis are glass devices; however, microchip fabrication in glass is costly and laborious, enhancing the interest in polymeric substrates, such as poly (methyl methacrylate) (PMMA), as an inexpensive alternative. Here, we report amplification in PMMA polymerase chain reaction (PCR) microchips providing full short tandem repeat profiles (16 of 16 loci) in 30–40 min, with peak height ratios and stutter percentages that meet literature threshold requirements. In addition, partial profiles (15 of 16 loci) were generated using an ultrafast PCR method in 17.1 min, representing a ~10‐fold reduction in reaction time as compared to current amplification methods. Finally, a multichamber device was demonstrated to simultaneously amplify one positive, one negative, and five individual samples in 39 min. Although there were instances of loci dropout, this device represents a first step toward a microfluidic system capable of amplifying more than one sample simultaneously.     

DNA Typing for the Identification of Old Skeletal Remains from Korean War Victims*

Abstract: The identification of missing casualties of the Korean War (1950–1953) has been performed using mitochondrial DNA (mtDNA) profiles, but recent advances in DNA extraction techniques and approaches using smaller amplicons have significantly increased the possibility of obtaining DNA profiles from highly degraded skeletal remains. Therefore, 21 skeletal remains of Korean War victims and 24 samples from biological relatives of the supposed victims were selected based on circumstantial evidence and/or mtDNA‐matching results and were analyzed to confirm the alleged relationship. Cumulative likelihood ratios were obtained from autosomal short tandem repeat, Y‐chromosomal STR, and mtDNA‐genotyping results, and mainly confirmed the alleged relationship with values over 10⁵. The present analysis emphasizes the value of mini‐ and Y‐STR systems as well as an efficient DNA extraction method in DNA testing for the identification of old skeletal remains.     

Preliminary efficiency evaluation of development methods applied to aged sebaceous latent fingermarks

Latent fingermarks are important trace evidence found in crime scenes mainly used for identification purposes. Once deposited, the composition of samples changes over time influencing the efficacy of latent fingermark development methods. In this sense, the aims of this work were to characterize the fatty acid (FA) profile of sebaceous latent fingermarks by GC–FID and to preliminarily evaluate the development efficiency of enhancement methods (powder dusting, iodine fuming and silver nitrate method) in a 30-day period of aging under controlled parameters of temperature, photoperiod and humidity. Results showed that myristic (7.51 ± 0.76% − 13.39 ± 1.26%), palmitic (35.91 ± 1.07% − 40.81 ± 2.52%), stearic (6.67 ± 0.36% − 9.13 ± 0.36%) and oleic (18.08 ± 0.25% − 20.93 ± 0.26%) acid varied significantly (p < 0.05) over the 30-day period of analysis. Regarding development efficiency, fluorescent orange powder and the silver nitrate method also increased their efficacy to develop latent fingermarks over time while the iodine fuming method decreased its efficiency. Silver black powder had constant efficacy in the tested period. Changes in the constitution of sebaceous marks possibly influenced the development efficiency of enhancement techniques. This knowledge is important to better understand the kinetic of aging and its influence on the development method.