Direct identification of various copper phthalocyanine pigments in automotive paints and paint smears by laser desorption ionization mass spectrometry

Direct identification of copper phthalocyanine (CuPc) and chlorinated CuPcs in paints for discrimination between blue automobile paints by means of laser desorption mass spectrometry (LDMS) in the absence of a matrix is reported. The models consisted of eight commercially available CuPc pigments applied to a piece of plain white coating paper. The relationship between the peak intensity at m/z 575 of the CuPc, the number of pulsed laser shots, and laser power was compared to optimize laser abrasion. LDMS analysis of the model paints demonstrated that all characteristic components of the CuPc pigments in the paint films were in good agreement with those in the powder pigments. Further, the chlorinated CuPcs in the paint films could be distinguished. A quantity of 42 blue paint films, representing the paints used for painting Japanese domestic trucks, was examined by LDMS analysis. Results indicate that the paints can be classified into four categories based on the chlorinated CuPc components of the paints. Therefore, LDMS spectra of CuPc pigments would be useful for the identification of paints in forensic investigations. Herein, we report the successful identification of the CuPcs in a paint smear on the frame of a bicycle damaged in a hit-and-run accident, using the LDMS spectra.     

Detection of nitro-organic and peroxide explosives in latent fingermarks by DART- and SALDI-TOF-mass spectrometry

The ability of two mass spectrometric methods, surface-assisted laser desorption/ionization-time of flight-mass spectrometry (SALDI-TOF-MS) and direct analysis in real time (DART-MS), to detect the presence of seven common explosives (six nitro-organic- and one peroxide-type) in spiked latent fingermarks has been examined. It was found that each explosive could be detected with nanogram sensitivity for marks resulting from direct finger contact with a glass probe by DART-MS or onto stainless steel target plates using SALDI-TOF-MS for marks pre-dusted with one type of commercial black magnetic powder. These explosives also could be detected in latent marks lifted from six common surfaces (paper, plastic bag, metal drinks can, wood laminate, adhesive tape and white ceramic tile) whereas no explosive could be detected in equivalent pre-dusted marks on the surface of a commercial lifting tape by the DART-MS method due to high background interference from the tape material. The presence of TNT and Tetryl could be detected in pre-dusted latent fingermarks on a commercial lifting tape for up to 29 days sealed and stored under ambient conditions.     

Quantified Explosives Transfer on Surfaces for the Evaluation of Trace Detection Equipment

Trace explosive test surfaces are often required for the evaluation of trace detection equipment to determine the equipment performance. Test surfaces of C‐4, Detasheet, Semtex‐H, TNT, and HMTD were prepared by transferring trace amount of explosive deposited on polytetrafluoroethylene (PTFE) transfer strips onto different surfaces (Kraft paper, hard plastic, woven fabric, and soft vinyl). The amount of explosive transferred was deduced from the amount of explosive remaining on the PTFE strips after transfer, as quantified by direct analysis using tandem mass spectrometry with thermal desorption. From the data set of over 2000 transfers, we experienced lower transfer efficiency for Semtex‐H and Detasheet, and for soft vinyl and hard plastic. However, the rapid quantification mass spectrometric method allowed the transfer efficiency to be determined for all test surfaces used in an evaluation of trace explosive detectors, thereby permitting only the test surfaces with desired transfer to be accepted for the assessment.     

酸性黄显现非渗透性客体上血潜手印初步探究

目的建立一种酸性黄显现非渗透性客体上血潜手印的方法。方法制备白色瓷砖、黑色塑料袋、黑色瓷瓶、易拉罐侧面、深色铁质茶叶盒等为客体的捺印手印,配置以酸性黄作为主要成分的染色剂,对其进行固定、染色、漂洗,在多波段光源下观察。结果在440nm激发光源条件下,通过橙色护目镜观察有很强的黄色荧光特征。结论酸性黄显现法具有操作简单、显现效果明显、能排除深色背景干扰的特点,容易推广使用。     

Fingermarks detection by eosin-blue dye

Eosin-blue (I) dye, along with a phase transfer catalyst, has been used to detect latent fingerprints on a wide range of surfaces, including paper, glass, steel, lamination sheets, polythene, plastic and bakelite.     

Persistence of cellular material after exposure to water

Disposing of items of forensic relevance in bodies of water is one countermeasure offenders can use to avoid detection. The impact of immersion in water has been explored for blood, saliva, and semen; however, few studies have assessed touch DNA. Here we report on the effect of exposure to water on the persistence of touch DNA over prolonged periods of time. To evaluate the persistence of cells from touch DNA, after water exposure, three substrates and two water types were tested: plastic, metal, and ceramic, submerged into seawater or tap water. Diamond™ Nucleic Acid Dye was used to stain cells deposited by touch. Cell counts before and after water exposure were compared to investigate cell loss over time, ranging from 6 hours to 5 days. A logarithmic increase in the percent of cells lost was observed over time when the data for substrate and water type conditions were combined. Substrate type influenced the persistence of cells, with the metal substrate retaining cells longer than plastic or ceramic. The influence of water type appeared dependent on the substrate, with varied cell persistence on metal whereas plastic and ceramic recorded similar cell loss over time between water types. The ability to visualize cells after exposure to water could assist in triaging evidence within operational forensic laboratories and allow for targeted sampling. This proof-of-concept study demonstrated that greater than 50% of cells can persist on various items submerged in aqueous environments for at least 5 days, highlighting the possibility for downstream DNA testing.     

A Modified Electrostatic Adsorption Apparatus for Latent Fingerprint Development on Unfired Cartridge Cases

Visualization of latent fingerprints on metallic surfaces by the method of applying electrostatic charging and adsorption is considered as a promising chemical‐free method, which has the merit of nondestruction, and is considered to be effective for some difficult situations such as aged fingerprint deposits or those exposed to environmental extremes. In fact, a portable electrostatic generator can be easily accessible in a local forensic technology laboratory, which is already widely used in the visualization of footwear impressions. In this study, a modified version of this electrostatic apparatus is proposed for latent fingerprint development and has shown great potential in visualizing fingerprints on metallic surfaces such as cartridge cases. Results indicate that this experimental arrangement can successfully develop aged latent fingerprints on metal surfaces, and we demonstrate its effectiveness compared with existing conventional fingerprint recovery methods.     

Tape Lift Sampling of Chemical Threat Agents

Commercial‐off‐the‐shelf (COTS) materials were evaluated as surface samplers for the Department of Homeland Security Chemical Forensics Program. The program helps evidence collectors identify trace chemical residues at incident scenes. COTS items are widely available, produced in large lots, and with strict controls. Chemical attribution signatures were collected from common surfaces. Eight tape lift candidates were considered, five were chosen based on performance and tested for analytical interferences and extraction efficiencies with 14 chemicals. Three products (duct tape, print lifters, command strips) were evaluated for uptake from common interior surfaces (glass, tile, ABS plastic). Duct tape provided highest recoveries across all surfaces. Even the most volatile analytes were detected in the ABS plastic samples (nondetections in others), regardless of tape lift material used. The porous plastic substrate provides better target retention than glass and tile surfaces. Forensic field operators should sample surfaces made of ABS plastic (keyboards, remotes, phones, etc.) whenever possible.     

利用CdSe巯基乙酸溶液显现水浸客体表面潜手印

目的研究水浸客体表面潜指纹的显现方法;方法利用CdSe巯基乙酸溶液显现被水浸泡过的黄色封箱胶带、黑色塑料袋、玻璃等常见非渗透性客体上的潜手印,讨论影响水浸非渗透性客体上潜手印显现效果的各种因素,并与传统方法进行比较,初步探讨了CdSe巯基乙酸溶液显现水浸非渗透性客体表面潜手印的方法;结果使用巯基乙酸包覆CdSe纳米复合材料显现潜在手印,使每分子纳米复合材料外表包覆足够数量的羧基,则可以提高它同手印残留物的结合能力,从而得到更高清晰度、更高分辨率的手印显像;结论巯基乙酸包覆CdSe纳米复合材料可以很好的显现水浸塑料、胶带等表面潜指纹。     

SWP荧光剂熏显油脂手印方法的初步研究

目的建立SWP荧光剂熏显油脂手印的新方法。方法选取12中常见客体,根据试验需要分别捺印油脂手印144枚和油汗混合手印100枚,用多功能手印显现柜加热升华SWP荧光剂,熏显渗透性和非渗透性客体上的手印。结果油脂手印显现出了142枚,显出率达到98．6％;油汗混合手印,非渗透性客体共显出100枚,显出率达到100％,渗透性客体共显出95枚,显出率达到95％。结论SWP荧光剂对油脂手印的显现效果良好,可与“502”同时熏显,且不影响茚二酮等其他方法的进一步检验。     

DNA profiling from heroin street dose packages

A large amount of heroin street doses are seized and examined for drug content by the Israel police. These are generally wrapped in heat-sealed plastic. Occasionally it is possible to visualize latent fingerprints on the plastic wrap itself, but the small size of the plastic item and the sealing process makes the success rate very low. In this study, the possibility of extracting and profiling DNA from the burnt edge of the plastic wrap was investigated. The idea was based on the assumption that epithelial cells might be trapped during the sealing process. The results show that there are sufficient quantities of DNA deposited at the "amorphic" burnt edges of sealed street doses for DNA profiling to be carried out. A controlled experiment using a known donor was performed. This subject carried out sealing of "street drug" packages and consequent DNA extractions were performed to show that known DNA profiles could be recovered from such packages, as a result of handling by the "packer." "Square-like" burnt edges did not yield DNA profiles, probably because of differences in the sealing process. It was also shown that DNA could be recovered from the plastic wrap itself and not only from the amorphic burnt edges. As heroin dealers and drug users are often involved in other crimes and run-ins with the law, the effective extraction and addition of their DNA profiles from such items of evidence to the newly established DNA database in Israel provides new avenues in the continued fight against crime and drug traffickers.     

The transference of patterns printed or indented on a sheet of paper to a plastic surface

Experiments have been made in which the image of Xerox-letters printed on a sheet of paper is transferred to a sheet of plastic and developed by dusting. The sheet of paper is sandwiched between two sheets of plastic, which are pressed between two flat metal plates by a mechanical press. After removing the pressure, the sheet of plastic facing the letter-printed surface of the sheet of paper is separated or torn from the paper using electrically insulated forceps. Then by sifting fine alumina powder onto the plastic surface, a dust figure can be obtained. This figure shows the transcribed letters corresponding to the original Xerox-letter on the sheet of paper.By this method, indented letters, or letters drawn with ink on a sheet of paper, or a fingerprint impressed on a sheet of paper can be transcribed onto the surface of a sheet of plastic.     

平面扫描技术在尿渍鞋印提取中的应用研究

目的应用平面扫描技术建立尿渍鞋印的光学无损提取方法。方法通过调整光源入射角度和反射光接收角度等参数,运用3种平面扫描方法提取大理石、地板革和瓷砖等6种客体上遗留的尿渍鞋印。结果基于平面扫描技术的尿渍鞋印提取方法,显著增加了痕迹与承痕客体之间的亮度反差,消除或减弱承痕客体背景干扰。比较筛选得到了大理石、地板革和瓷砖等客体上尿渍鞋印的最佳平面扫描方法。结论平面扫描方法可作为一种光学无损方法用于尿渍鞋印的提取。     

Development of latent fingermarks by aqueous electrolytes

In this work we present our observations on the interaction between metallic (copper, aluminum, iron, brass, zinc) and non-metallic (glass and plastic) surfaces bearing latent fingermarks and several aqueous electrolytic solutions. Good quality fingermarks could be observed on some of the metallic and even on non-metallic surfaces after such treatment. The influence of factors such as time interval from deposition, pH of the electrolytes, wiping the latent marks prior to processing and the presence of a second metal on the quality and permanence of the developed impressions have been studied. As a rule, sebaceous marks provided much better quality impressions on all the surfaces. Initial explanations based on electrochemical processes are suggested.     

A comparison of multi-metal deposition processes utilising gold nanoparticles and an evaluation of their application to 'low yield' surfaces for finger mark development

This paper reports a comparison of the effectiveness and practicality of using different multi-metal deposition processes for finger mark development. The work investigates whether modifications can be made to improve the performance of the existing process published by Schnetz. Secondly, we compare the ability of different multi-metal deposition processes to develop finger marks on a range of surfaces with that of other currently used development processes. All published multi-metal deposition processes utilise an initial stage of colloidal gold deposition followed by enhancement of the marks with using a physical developer. All possible combinations of colloidal gold and physical developer stages were tested. The method proposed by Schnetz was shown to be the most effective process, however a modification which reduced the pH of the enhancement solution was revealed to provide the best combination of effectiveness and practicality. In trials comparing the modified formulation with vacuum metal deposition, superglue and powder suspensions on surfaces which typically give low finger mark yields (cling film, plasticised vinyl, leather and masking tape), the modified method produced significantly better results over existing processes for cling film and plasticised vinyl. The modified formulation was found to be ineffective on both masking tape and leather. It is recommended that further tests be carried out on the modified multi-metal deposition formulation to establish whether it could be introduced for operational work on cling film material in particular.     

Recovery efficiencies of anthrax spores and ricin from nonporous or nonabsorbent and porous or absorbent surfaces by a variety of sampling methods*

The 2001 anthrax letter cases brought into focus the need to establish the most effective environmental sampling procedures. Results are presented from two studies aimed at establishing the best procedures for everyday surfaces likely to be contaminated after the release of environmentally stable bioaggressive agents, as exemplified by anthrax spores and ricin. With anthrax spores, contact plates, with mean retrieval rates of 28-54%, performed better than other methods by a wide margin for flat nonporous, nonabsorbent surfaces. They also proved best on flat porous, absorbent materials, although recoveries were low (<7%). For both agents, dry devices (swabs, wipes, Trace Evidence Collection Filters) had universally poor retrieval efficiencies with no significant differences between them. Among moistened devices (wipes, swabs, and Sample Collection and Recovery Devices), wipes were generally best, albeit with considerable cross-over among individual readings (highest mean recoveries for anthrax spores and ricin 5.5% and 2.5%, respectively, off plastic).     

Evaluation of iodine-benzoflavone and ruthenium tetroxide spray reagents for the detection of latent fingermarks at the crime scene

The performance of two spray reagents, iodine-benzoflavone and ruthenium tetroxide (RTX), was evaluated and compared with the conventional technique currently used at the crime scene, that is, powdering. Neither the spray techniques nor powdering were shown to be suitable for all surfaces and ages of marks tested. On some surfaces such as glass and treated wood, powdering was still the superior technique, whereas the spray techniques produced better development on wallpaper, vinyl, and brick. Sequencing work showed that RTX was incompatible with powdering and cyanoacrylate (with a rhodamine 6G stain). Iodine-benzoflavone can be used successfully either before or after powdering in a sequence; however, it was incompatible with cyanoacrylate. Two non-CFC formulations of iodine-benzoflavone using HFC4310mee and HFE7100 solvents were tested and shown not to be as effective as the original Arklone (CFC-113) formulation; however, the HFC4310mee solvent is recommended as the most suitable replacement solvent. Due to the expense of the commercial RTX spray, attempts at formulating a more cost-effective version were also carried out. A formulation was developed that gave comparable development to the commercial version but at a much cheaper cost, and with a shelf life of up to two months. Recommendations are presented for which techniques are suitable for different surfaces and ages of marks. Powdering was shown to be the best technique on all ages of marks tested on treated wood, glass, and also on marks aged three days and older on paint. Iodine-benzoflavone was the best technique on wallpaper, vinyl, brick, and raw wood. RTX was the best detection technique for fresh marks and marks aged up to one day on wallpaper and paint.     

Pressure sensitive adhesives and paper spray-mass spectrometry for the collection and analysis of fentanyl-related compounds from shipping materials

The rise of fentanyl and fentanyl analogs in the drug supply pose serious threats to public health. Much of these compounds enter the United States through shipping routes. Here we provide a method for fentanyl screening and analysis that utilizes pressure-sensitive adhesive (PSA) lined paper to recover drug residues from parcel-related surfaces. The paper used is commercially available repositionable notes (also called post-it or sticky notes). From this paper, mass spectra were obtained by paper spray-mass spectrometry (PS-MS), where PSA paper served as both a sampling and analysis substrate. Seven fentanyl-related compounds were analyzed: fentanyl, 4-anilino-N-phenethylpiperidine (4-ANPP), N,1-diphenethyl-N-phenylpiperidin-4-amine (phenethyl-4-ANPP), valerylfentanyl, 4-fluoroisobutyrylfentanyl (4-FIBF), carfentanil, and p-fluorofentanyl. These compounds were recovered by PSA paper and identified by PS-MS from packaging tape and plastic at 50 ng and from cardboard and shipping labels at 100 ng. The impact of cutting agents on PS-MS analysis of fentanyl analogs was explored. No trends of analyte suppression were found at high concentrations of the cutting agents caffeine, diphenhydramine, and lidocaine when recovered from surfaces. A cartridge that required no precise cutting of PSA paper prior to sampling or analysis was evaluated for use in PS-MS for fentanyl screening. Recovery and detection of fentanyl from plastic sheeting was demonstrated with this cut-free cartridge. The cut-free cartridge showed somewhat less consistency and lower analyte signal than the standard cartridge, but performance was suitable for potential screening applications. In combining PSA surface sampling with PS-MS for drug screening, both sampling and detection of fentanyl-related compounds is simple, rapid, and low-cost.     

Thermal development of latent fingermarks on porous surfaces—Further observations and refinements

In a further study of the thermal development of fingermarks on paper and similar surfaces, it is demonstrated that direct contact heating of the substrate using coated or ceramic surfaces at temperatures in excess of 230 °C produces results superior to those obtained using hot air. Fingermarks can also be developed in this way on other cellulose-based substrates such as wood and cotton fabric, though ridge detail is difficult to obtain in the latter case. Fluorescence spectroscopy indicates that the phenomena observed during the thermal development of fingermarks can be reproduced simply by heating untreated white copy paper or filter paper, or these papers treated with solutions of sodium chloride or alanine. There is no evidence to suggest that the observed fluorescence of fingermarks heated on paper is due to a reaction of fingermark constituents on or with the paper. Instead, we maintain that the ridge contrast observed first as fluorescence, and later as brown charring, is simply an acceleration of the thermal degradation of the paper. Thermal degradation of cellulose, a major constituent of paper and wood, is known to give rise to a fluorescent product if sufficient oxygen is available [1], [2], [3], [4], [5]. However, the absence of atmospheric oxygen has only a slight effect on the thermal development of fingermarks, indicating that there is sufficient oxygen already present in paper to allow the formation of the fluorescent and charred products. In a depletion study comparing thermal development of fingermarks on paper with development using ninhydrin, the thermal technique was found to be as sensitive as ninhydrin for six out of seven donors. When thermal development was used in sequence with ninhydrin and DFO, it was found that only fingermarks that had been developed to the fluorescent stage (a few seconds of heating) could subsequently be developed with the other reagents. In the reverse sequence, no useful further development was noted for fingermarks that were treated thermally after having been developed with ninhydrin or DFO. Aged fingermarks, including marks from 1-year-old university examination papers were successfully developed using the thermal technique.     

Validation of Walkway Tribometers: Establishing a Reference Standard*

Abstract: Tribometers are mechanical devices used to measure walkway coefficient of friction (COF) for the purpose of assessing slip risk. The purpose of this study was to define a tribometer reference standard and use it to assess the performance of various tribometers. Eighty subjects were randomly assigned to walk across one of four wet walkway surfaces (polished black granite, porcelain, vinyl composition tile, and ceramic tile) to establish the relative slipperiness of each surface. Eleven tribometers were subsequently used to measure and rank the COF of all four surfaces. Our results revealed that only four of the 11 tribometers (Wessex pendulum, Sigler pendulum, Mark II, and Mark III) met our compliance criteria by both correctly ranking all four surfaces and differentiating between surfaces of varying degrees of slipperiness. Our protocol demonstrates that human gait‐based measures of slipperiness can be used to create reference standards against which tribometer measurements can be validated.