Differentiation of Cosmetic Foundation Creams Using Attenuated Total Reflection Fourier-Transform Infrared Spectroscopy: A Rapid and NonDestructive Approach in Trace Evidence Analysis

Cosmetic foundation creams are encountered as evidentiary material in criminal investigations, particularly in cases related to sexual and physical assault against women. Analyzing foundation cream exhibit is a challenging task as the exhibit is recovered in trace quantity with similar hue. In the present study, ATR FTIR spectroscopy which is a rapid, nondestructive, sensitive, reliable, and safe alternative to other analytical techniques has been used to differentiate 31 cosmetic foundation creams belonging to 23 different brands supported by chemometric methods such as principal component analysis (PCA) and linear discriminant analysis (LDA). The discriminating power of visual analysis is found to be 98.0%, while PCA and LDA further increased the discriminating power to 99.3% and 100%, respectively. The blind test is conducted with three unknown samples (pretended to be unknown to the analyst), which were correctly linked with their respective source. Further, the effect of substrate such as tissue paper (dry and wet) and white cotton cloth during sample analysis are also examined to simulate the actual forensic casework conditions. The stains on substrates could be identified and linked to its parent product as well. The reported method provides significant results for the differentiation of cosmetic foundation creams.     

Identification and Comparison of Electrical Tapes Using Instrumental and Statistical Techniques: II. Organic Composition of the Tape Backing and Adhesive*

Abstract: The microtexture and elemental composition of the backing of electrical tapes have been shown to be highly discriminating. In this study, the organic composition of electrical tape was evaluated as a complementary means of distinguishing tape brands. The backing and adhesive of 72 rolls of electrical tape were analyzed via Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) and discriminant analysis was used to classify all samples by brand. Generally, the accuracy for FTIR data (88–99%) was higher than that for elemental data (86–94%). FTIR spectra from the adhesive layer were the most discriminating. In separate studies, two fragments of blast-damaged tape were correctly assigned to their brand of origin and discriminant analysis was used to quantitatively associate or exclude tape samples from two bombing cases.     

Camouflaging Facial Emphysema: A new syndrome

Some cosmetic products manufactured in Korea for the treatment of eczema, seborrhea and psoriasis have been suspected to contain anti-inflammatory corticosteroids such as prednisolone, hydrocortisone, betamethasone, dexamethasone and triamcinolone acetonide without these ingredients being indicated on the label. Due to their severe side effects such as permenent skin atopy, these corticosteroids have to be monitored in cosmetic products from a forensic point of view. Many cosmetic product samples (N=65) have been collected from both local and online markets in Korea. The corticosteroid content of these samples was analyzed by LC-MS/MS with diagnostic ions (m/z). Linearity was studied with 0.1-10 μg/mL range in all corticosteroids. Good correlation coefficients (r(2)≥0.997) were found and the limits of quantification were 4.68-7.97 ng/mL for each of the corticosteroids. At three different concentrations spanning the linear dynamic ranges, mean recoveries were 97.2-113.5%and precisions (RSD) for intra-day and inter-day analysis were less than 8.9%. Also, accuracy (Bias %) was less than 11.8%. The results showed that between 0.76-0.94 μg/g levels of prednisolone were detected in four cosmetic products and triamcinolone acetonidewas detected with a concentration in the range of 11.5-272 μg/g in nine samples. This fact reveals that some manufacturers have arbitrarily added these corticosteroids in their cosmetic products without indicating them on the label. Thus, these cosmetic products have to be monitored and if proven illegal preparations removed from the market.     

Monitoring of clobetasol propionate and betamethasone dipropionate as undeclared steroids in cosmetic products manufactured in Korea

Some cosmetic products manufactured in Korea have been suspected to contain anti-inflammatory corticosteroids, such as clobetasol propionate and betamethasone dipropionate, for the treatment of eczema, seborrhea and psoriasis, without any indication on the label of the cosmetic products. Due to their severe side effects, such as permanent skin atopy, these two corticosteroids in cosmetic products need to be monitored from a forensic point of view. Cosmetic product samples (number of samples=47) of manufacturers charged by consumers have been collected in local and online markets of Korea, and they were validated and analyzed by a simple high performance liquid chromatography (HPLC) method with ultraviolet diode array (UV-DAD). LC-MS/MS and LC-MS were used to confirm these steroids in cosmetic samples with diagnostic ions (m/z) and isotope ratio. Linearity was studied with 0.5-10μg/mL range in both steroids. Good correlation coefficients (r(2)≥0.999) were found, and their limits of quantifications were 0.59μg/mL and 0.66μg/mL in clobetasol propionate and betamethasone dipropionate, respectively. At three different concentrations spanning the linear dynamic ranges, mean recoveries were always higher than 93%, and precisions for intra-day and inter-day analyses were both less than 3.5%. The results show 32-96.4μg/g levels of clobetasol propionate in five different cosmetic products. Also, betamethasone dipropionate in a sample was monitored at the level of 195.1μg/g. This fact reveals that some manufacturers have added these steroids in their cosmetic products to advertise the treatment effect for skin atopy. Thus, these cosmetic products need to be monitored carefully, and ultimately removed from the market.     

The use of vapour phase ultra-violet spectroscopy for the analysis of arson accelerants in fire scene debris.

A method has been developed for the analysis of arson accelerants in fire scene debris by vapour phase ultra-violet (UV) spectroscopy. The method is rapid, inexpensive, simple to use and is sufficiently sensitive and discriminating to be of use for the analysis of crime scene samples. Application to casework samples is described. On occasion, the method offers additional information to that which can be obtained by gas chromatography-flame ionisation detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS) and represents a useful adjunct to these techniques. In addition, the method offers advantages where the use of GC-MS analysis of arson accelerants in fire scene debris is not a practical proposition.     

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.     

Gunshot residue testing in suicides: Part I: Analysis by scanning electron microscopy with energy-dispersive X-ray

Several different methods can be employed to test for gunshot residue (GSR) on a deceased person's hands, including scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM-EDX) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Each of these techniques has been extensively studied, especially on living individuals. The current studies (Part I and Part II) were designed to compare the use and utility of the different GSR testing techniques in a medical examiner setting. In Part I, the hands of deceased persons who died from undisputed suicidal handgun wounds were tested for GSR by SEM-EDX over a 4-year period. A total of 116 cases were studied and analyzed for caliber of weapon, proximity of wound, and results of GSR testing, including spatial deposition upon the hands. It was found that in only 50% of cases with a known self-inflicted gunshot wound was SEM-EDX positive for at least 1 specific particle for GSR. In 18% of the cases there was a discernible pattern (spatial distribution) of the particles on the hand such that the manner in which the weapon was held could be determined. Since only 50% of cases where the person is known to have fired a weapon immediately prior to death were positive for GSR by SEM-EDX, this test should not be relied upon to determine whether a deceased individual has discharged a firearm. Furthermore, in only 18% of cases was a discernible pattern present indicating how the firearm was held. The low sensitivity, along with the low percentage of cases with a discernible pattern, limits the usefulness of GSR test results by SEM-EDX in differentiating self-inflicted from non-self-inflicted wounds.     

Determination of gamma-hydroxybutyrate (GHB) and its precursors in blood and urine samples: a salting-out approach

Gamma-hydroxybutyrate (GHB) is an increasingly popular drug of abuse that causes stimulation, euphoria, anxiolysis or hypnosis, depending on the dose used. Low doses of the drug are used recreationally, and also implicated in drug-facilitated sexual assaults. Because of the unusually steep dose-response curves, accidental GHB overdosing, leading to coma, seizures or death can occur. Being a controlled substance, GHB is often substituted with its non-scheduled precursors gamma-butyrolactone (GBL) and 1,4-butanediol (BD), which are rapidly metabolized into GHB in the body. Here we describe an assay for GHB, GBL and BD in blood and/or urine samples. GHB and BD were extracted from diluted 200 microL aliquots of samples with t-butylmethylether (plus internal standard benzyl alcohol) in test tubes preloaded with NaCl. After acidification and centrifugation the solvent phase was transferred to a test tube preloaded with Na(2)SO(4), incubated for 30 min, centrifuged again, and evaporated in vacuum. The residue was mixed with N-methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) in acetonitrile, and injected into a GC-MS. When analyzing GBL, the salting-out step was omitted, and analysis was performed with a GC-FID apparatus. As revealed by the validation data this procedure is suitable for quantitative determination of GHB and its precursors in blood and/or urine samples.     

The forensic analysis of soil organic by FTIR

In order to elucidate the discriminating power of various soil analytical techniques, over 100 soils samples were analyzed using conventional analysis (i.e., color, percent organic and density gradient) and a novel FTIR technique. The FTIR technique involves collecting a spectrum of a soil sample that has been oxidatively pyrolysed, and therefore all organic have been degraded. This spectrum is subtracted from the spectrum of the same sample that contained the organic prior to pyrolysis. This resultant IR spectrum represents the organic portion of the sample. The use of organic components increases the discrimination in soils that are otherwise similar. We have illustrated the usefulness of this technique by selecting four soil samples, which have identical Munsel color values but can be discriminated by subtractive ETIR. We propose that the ETIR spectra of the organic portion of soil serves a useful purpose in forensic investigations.     

Near-infrared spectroscopy combined with chemometrics to classify cosmetic foundations from a crime scene

Cosmetic smears are a form of trace evidence that can link the crime scene, suspects, and victims. Foundation and lipstick are the most common sources of cosmetics that can easily smear, with most current research focused on the evidential analysis of lipsticks. This research aims to create a database of cosmetic foundations on different materials and to access the robustness of using Near-infrared with chemometrics as a non-destructive technique to identify unknown samples collected from a crime scene. Small amounts of six shades of three brands of foundations were smeared on clothing materials, which were then analysed with a combination of Near-infrared with chemometric analysis. Principle component analysis (PCA) was used to reduce data dimensionality and explore potential patterns in sample separation and Linear Discriminant Analysis (LDA) was utilised to assign unknown samples to one of the established classes. The selected techniques proved to be promising for database construction and as a preliminary method of analysis, with 93% of the spectra being correctly classified. Notably, darker foundation shades were less likely to be correctly classified (90% classified correctly) compared to lighter ones (96.7% classified correctly). This could not be improved with Standard Normal Variate (SNV) data pre-treatment or selecting specific NIR regions. This finding is of particular importance; according to the Crime Survey for England and Wales (year ending March 2020) police recorded sexual offences demonstrated that those in Mixed and Black or Black British ethnic groups were significantly more likely to be a victim of sexual assault compared to White, Asian or Other ethnic groups. It is, therefore, crucial to add a wide range of foundation shades, particularly of darker tones, to the future database.     

Forensic Investigation of Formaldehyde in Illicit Products for Hair Treatment by DAD‐HPLC: A Case Study

The illegal use of formalin (commercial formaldehyde) in cosmetic products harms the health of individuals exposed to this substance. Over the last years, the commercial availability of these products, especially those containing irregular dosage of formaldehyde, has increased in Brazil. This work analyzes some products for hair treatment available in the Brazilian market and verifies their safety. The adopted analytical methodology involved sample derivatization with 2,4‐dinitrophenylhydrazine, followed by high‐performance liquid chromatography with ultraviolet detection (UV–VIS) at λ = 365 nm. The limit of quantification is 2.5 × 10^?3% w/w, and the recovery tests were around 93%. Some of the samples contained high and illegal formaldehyde levels ranging from 9% to 19% (w/w) and others presented suitable concentrations of the analyte. On the basis of the results, this work discusses the efficiency and practicality of this analytical method for forensic purposes.     

A survey of the potency of Japanese illicit cannabis in fiscal year 2010

In recent years, increased 'cannabis potency', or Δ(9)-tetrahydrocannabinol (THC) content in cannabis products, has been reported in many countries. A survey of Japanese illicit cannabis was conducted from April 2010 to March 2011. In Japan, all cannabis evidence is transferred to the Minister of Health, Labour and Welfare after criminal trials. The evidence was observed at Narcotics Control Department offices in major 11 cities. The total number of cannabis samples observed was 9072, of which 6376 were marijuana. The marijuana seizures were further classified, and it was found that in terms of the number of samples, 65.2% of them were seedless buds, and by weight 73.0% of them were seedless buds. Seedless buds were supposed to be 'sinsemilla', a potent class of marijuana. THC, cannabinol (CBN) and cannabidiol (CBD) in marijuana seizures exceeding 1g were quantified. The number of samples analyzed was 1115. Many of them were shown to contain CBN, an oxidative product from THC. This was a sign of long-term storage of the cannabis and of the degradation of THC. Relatively fresh cannabis, defined by a CBN/THC ratio of less than or equal to 0.1, was chosen for analysis. Fresh seedless buds (335 samples) contained an average of 11.2% and a maximum of 22.6% THC. These values are comparable to those of 'high potency cannabis' as defined in previous studies. Thus, this study shows that highly potent cannabis products are distributed in Japan as in other countries.     

Grouping of ammunition types by means of frequencies of occurrence of GSR

An attempt was made to build a classification scheme for gunshot residues (GSR) samples originating from four types of ammunition, collected from shooters' hands immediately after shooting. The secured material was examined with the use of SEM-EDX method in the automatic manner. The obtained results were expressed as frequencies of occurrence of particles assigned to various chemical classes. In order to establish the most discriminative of these features the Mann-Whitney test was performed. Cluster analysis was performed for grouping the analysed samples according to their origin, i.e. the type of ammunition. It has been found that samples of GSR originating from Browning 7.65 mm and Luger 9 mm ammunition can be fairly easy differentiated from the remaining samples, whereas samples of GSR originating from of Makarov 9 mm and these of Tokarev 7.62 mm could not be differentiated using frequencies of occurrence of particles in the selected chemical classes.     

A preliminary investigation into the use of FTIR microscopy as a probe for the identification of bullet entrance holes and the distance of firing

FTIR spectroscopy has been found to be a valuable probe for the analysis of the distribution of organic components such as nitroglycerine in gunshot residues deposited on and around the bullet entrance hole of the clothing of the victim in short range firearm discharges. The method can be utilised for the detection and estimation of organic gunshot residues (OGSR) on the hands and clothing of the shooter. The method is specific and sensitive and is likely to be free from interference from, for example, environmental pollution. The method shows potential to be utilised as a suitable alternative to the widely used SEM-EDX analysis of the total contents of lead, barium and antimony present in the gunshot deposits around the bullet entrance hole. The method was tested in the laboratory and the results were validated by Gas Chromatography-Mass Spectrometry (GC-MS).     

Systematical method for polyacrylamide and residual acrylamide detection in cosmetic surgery products and example application

IntroductionIn this paper, the authors presented a case of acrylamide poisoning in a middle-aged woman who had underwent unsuccessful cosmetic surgery six years earlier. The victim was told that the product that had been injected into her face was Restylane®, which mainly contained sodium hyaluronate and was the first and only Food and Drug Administration (FDA)-approved dermal filler for lip enhancement in the USA for more than 20 years. Widespread facial infections occurred several years post-injection; finally, the victim had to undergo removal surgery. Acrylamide poisoning was strongly suspected based on the victim's clinical manifestation. The product that had been injected into the victim's face was probably polyacrylamide hydrogel-based product, which had been prohibited by the State Food and Drug Administration (SFDA) in China in 2006. To confirm this suspicion, a systematical method was established to differentiate varieties of cosmetic surgery products and identify residential acrylamide.MethodsThe removed objects, original products and a certified reference sample of Restylane® were collected for examination. A direct microscopic examination was applied as a rapid screening method. Fourier transform infrared (FTIR) microspectroscopy analysis was subsequently performed to distinguish the main components from each sample. Automated solid phase extraction, ultra high performance liquid chromatography (SPE UHPLC) analysis was ultimately utilised and optimised to detect the residual acrylamide. Chromatographic separation was achieved on an ACQUITY UHPLC HSS T3 column. The mobile phase consisted of 0.01% aqueous formic acid solution and acetonitrile. The tunable UV (TUV) detection wavelength was at 202 nm.ResultsThe microscopic examination indicated that different samples had different morphological characteristics, depending on their main components. The FTIR spectrum showed that different polymers could be distinguished according to the CO stretching vibration (1655 cm^? 1), NH bending vibration (1540 cm^? 1) and CO stretching vibration (1078 and 1045 cm^? 1). The UHPLC results demonstrated that the calibration curve was linear in the range of 0.5–20.0 μg/mL, with a correlation coefficient of 0.999. The average recoveries of the method were 99–107% with an RSD of 1.6–6.3%. The detection limit was 0.1 μg/mL (S/N = 3). The analytical time was 6 min per sample. Acrylamide was detected in the allegedly Restylane® injection.ConclusionsThis systematical method provides a rapid, accurate and sensitive determination of polyacrylamide and residual acrylamide. The microscopic and FTIR spectroscopic examinations help to verify the existence of polyacrylamide quickly and easily. The optimised SPE UHPLC-TUV method offers a simpler and more sensitive approach to confirm the amount of acrylamide, comparing to the methods in the literature.     

Analysis and discrimination of architectural paint samples via a population study

This study involved the comparative analysis and discrimination of 964 architectural paint samples collected in the United States and Canada. The samples were evaluated to determine the extent to which randomly collected architectural finishes can be discriminated following standard operating protocols for paint analysis. The study also provides a basis for assessing the significance of a result in which a pair or group are undifferentiated. The techniques utilized were stereomicroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) with both backscatter electron imaging (BSI) and energy dispersive spectroscopy (EDS), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). To assess the layer characteristics (e.g., number, color, sequence, thickness), stereomicroscopy was used with FTIR and/or SEM as needed. The use of visual and microscopic evaluations in concert with FTIR resulted in 42 undifferentiated pairs, a discrimination of 99.99%. Adding SEM and Py-GC/MS analysis resulted in further discrimination of 31 pairs, resulting in eleven undiscriminated pairs of samples. At the conclusion of the study, samples that remained undifferentiated proved to originate from the same source. Therefore, no random pairs were indistinguishable at the conclusion of all examinations.     

Impurity profiling of methamphetamine hydrochloride drugs seized in the Philippines

Methamphetamine hydrochloride is one of the most widely used illicit drugs in the Philippines. In this study, we describe the application of cluster analysis of trace impurities in the profiling of the seized methamphetamine drug samples. Thirty milligrams of a homogenized drug sample were dissolved in 1 mL of pH 10.5 buffer solution and extracted with ethyl acetate containing three internal standards. The trace impurities were identified using gas chromatography-mass spectrometry (GC-MS) and quantified by gas chromatography with a flame ionization detector (GC-FID). Following previously reported methodologies, 30 impurity peaks were selected from the GC-FID chromatograms. The peak areas and retention times were referenced to the internal standards. The peak areas of the selected peaks were then grouped for cluster analysis. In order to check for consistency of clustering, two further cluster analyses were performed using 40 and 50 impurity peaks. Changes in clustering were observed in going from 30 to 40 impurity peaks, while analyses using 40 and 50 impurity peaks gave similar results. Thus, for the seized drug samples used in this study, cluster analysis using at least 40 impurity peaks showed better consistency of clustering as compared to analysis using 30 peaks only. Ten of the impurity peaks were identified, of which four were identified for the first time in methamphetamine drug samples. These are p-bromotoluene, N-benzyl amphetamine, N-ethyl amphetamine, and N-ethyl methamphetamine. The presence of phenyl-2-propanone (P2P), N,N-dimethyl amphetamine, and N-formyl amphetamine is indicative that these casework samples were synthesized using the Leuckart method.     

Prediction of Police Officer Performance Among New Mexico State Police as Assessed by the Personality Assessment Inventory

Little research has been conducted regarding the use of the Personality Assessment Inventory (PAI) in law enforcement screening and selection. The limited body of research that does exist appears to support its utility in the selection process. The purpose of the present study was to investigate the validity and reliability of the Psychological Rating Risk Factor Statement (PRRFS) developed by Roberts, Thompson, and Johnson (2004) in predicting and discriminating problem from non-problem New Mexico State Police (NMSP) applicants. PAI profiles for each officer were obtained and transferred into the PAI Law Enforcement, Corrections, and Public Safety Selection software program, which generated probability estimates (PRRFS) to predict the likelihood that participants were not well-suited for a career in law enforcement. Subsequent logistic regression and receiver operating characteristic (ROC) statistical analyses revealed that the PRRFS was ineffective in predicting and discriminating between problem and non-problem officers. Potential explanations for this finding are discussed.     

Adhesive tape analysis: establishing the evidential value of specific techniques

This study investigated the evidential value of specific methods of analysis for packaging tapes and clear adhesive tapes available in Australia. Fifty-eight adhesive tapes were analyzed using a wide range of optical, physical, and chemical techniques. The results were collated for the purpose of creating an Australian database of adhesive tapes, which would be of assistance in criminal investigation. Each technique was evaluated for its discriminating power, both for comparative purposes and for the identification of adhesive tapes by comparing unknown samples with the database. The combined discriminating power of the techniques applied is very high. It is possible to individually identify the source of an unknown adhesive tape sample in many instances by searching the database. It is also possible to form an opinion on the significance of a failure-to-discriminate result in comparative casework. Further work is still needed to expand and update the database, as well as compiling data on the relative market share of various products.     

外伤性癫痫灶组织的基因表达谱分析

目的比较外伤性和非外伤性癫痫灶组织的基因表达谱,探索外伤性癫痫的发病机制,为相关鉴定提供依据。方法收集外伤性和非外伤性癫痫灶组织样本各15例。分别提取总RNA,经逆转录标记不同的探针与人类cDNA表达谱芯片杂交,获得扫描图像,分析信号的强度和比值,对实验数据按照RNA微阵列分析法标准化,对差异表达基因进行聚类分析。结果两组样本中共有超过2 990条基因明显表达（表达超过背景2～5倍以上）。以30%样本中的表达调节水平大于1.5倍作为差异基因筛选标准,与非外伤性癫痫组比较,外伤性癫痫组样本中存在显著性表达差异的基因有192个,其中表达上调的有115个,表达下调的有77个。结论采用基因表达谱芯片技术可以有效地识别外伤性癫痫和非外伤性癫痫的差异表达基因,并可用于外伤性癫痫发病机制和分子分型的研究。