Optimization of the separation of organic explosives by capillary electrophoresis with artificial neural networks

The separation of 12 explosives by capillary electrophoresis was optimized with the aid of artificial neural networks (ANNs). The selectivity of the separation was manipulated by varying the concentration of sodium dodecyl sulfate (SDS) and the pH of the electrolyte, while maintaining the buffer concentration at 10 mM borate. The concentration of SDS and the electrolyte pH were used as input variables and the mobility of the explosives were used as output variables for the ANN. In total, eight experiments were performed based on a factorial design to train a variety of artificial neural network architectures. A further three experiments were required to train ANN architectures to adequately model the experimental space. A product resolution response surface was constructed based on the predicted mobilities of the best performing ANN. This response surface pointed to two optima; pH 9.0-9.1 and 60-65 mM SDS, and pH 8.4-8.6 and 50-60 mM SDS. Separation of all 12 explosives was achieved at the second optimum. The separation was further improved by changing the capillary to an extended cell detection window and reducing the diameter of the capillary from 75 microm to 50 microm. This provided a more efficient separation without compromising detection sensitivity.     

Determination of Inorganic Ion Profiles of Illicit Drugs by Capillary Electrophoresis

A portable capillary electrophoresis instrument with dual capacitively coupled contactless conductivity detection (C⁴D) was used to determine the inorganic ionic profiles of three pharmaceutical samples and precursors of two illicit drugs (contemporary samples of methylone and para‐methoxymethamphetamine). The LODs ranged from 0.10 μmol/L to 1.25 μmol/L for the 10 selected cations, and from 0.13 μmol/L to 1.03 μmol/L for the eight selected anions. All separations were performed in less than 6 min with migration times and peak area RSD values ranging from 2 to 7%. The results demonstrate the potential of the analysis of inorganic ionic species to aid in the identification and/or differentiation of unknown tablets, and real samples found in illicit drug manufacture scenarios. From the resulting ionic fingerprint, the unknown tablets and samples can be further classified.     

Relationship between type of trauma exposure and posttraumatic stress disorder among urban children and adolescents

This study examines the association between trauma exposure and posttraumatic stress disorder (PTSD) among 157 help-seeking children (aged 8-17). Structured clinical interviews are carried out, and linear and logistic regression analyses are conducted to examine the relationship between PTSD and type of trauma exposure controlling for age, gender, and ethnicity. Confrontation with traumatic news, witnessing domestic violence, physical abuse, and sexual abuse are each significantly associated with PTSD. Witnessing a crime, being the victim of a crime, and exposure to accidents, fire, or disaster are not associated with PTSD. These findings underscore the association between interpersonal violence and childhood PTSD.     

An examination of the sequence of intersecting lines using attenuated total reflectance-Fourier transform infrared spectral imaging

In this study, the potential of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectral imaging as a technique to determine the sequence of line crossings was examined. The technique was successful in determining the sequence of heterogeneous line intersections produced using ballpoint pens and laser printers. By imaging at characteristic frequencies, it was possible to form spectral images showing the spatial distribution of the materials. By examining the spectral images from the inks, it was possible to determine whether the ink was above or below the toner. In blind testing, ATR-FTIR spectral imaging results were directly compared to those obtained by eight experienced forensic document examiners using methods regularly employed in casework. ATR-FTIR spectral imaging was shown to achieve a 100% success rate in the blind tests, whereas some incorrect sequence determinations were made by the forensic document examiners when using traditional techniques. The technique was unable to image ink-jet printing, gel pens, roller ball pens, and felt-tip pens, and was also unable to determine the sequence of intersecting ballpoint pen lines.     

Reversal sign on ante- and postmortem brain imaging in a newborn: report of one case

A 16-day-old female newborn was admitted to the emergency department after cardiopulmonary arrest. Total-body radiographs and non-enhanced CT of the brain showed fracture of the right clavicle, pericerebral hemorrhage and brain damage with reversal sign. The infant died on the day of her hospital admission. Because child abuse was suspected, a medicolegal autopsy was ordered by the legal authorities. Prior to autopsy, total-body MRI and CT were performed. Results of the ante- and postmortem investigations were compared with each other and then with the autopsy findings. Postmortem brain imaging showed persistence of the reversal sign. To the best of our knowledge, this is the first case describing hypoxic ischemic damage of the brain parenchyma on antemortem CT and persisting on postmortem imaging in a child abuse case.     

Forensic Analysis of Explosives Using Isotope Ratio Mass Spectrometry (IRMS)—Part 1: Instrument Validation of the DELTAplusXP IRMS for Bulk Nitrogen Isotope Ratio Measurements

Abstract: A significant amount of research has been conducted into the use of stable isotopes to assist in determining the origin of various materials. The research conducted in the forensic field shows the potential of isotope ratio mass spectrometry (IRMS) to provide a level of discrimination not achievable utilizing traditional forensic techniques. Despite the research there have been few, if any, publications addressing the validation and measurement uncertainty of the technique for forensic applications. This study, the first in a planned series, presents validation data for the measurement of bulk nitrogen isotope ratios in ammonium nitrate (AN) using the DELTA^plusXP (Thermo Finnigan) IRMS instrument equipped with a ConFlo III interface and FlashEA? 1112 elemental analyzer (EA). Appropriate laboratory standards, analytical methods and correction calculations were developed and evaluated. A validation protocol was developed in line with the guidelines provided by the National Association of Testing Authorities, Australia (NATA). Performance characteristics including: accuracy, precision/repeatability, reproducibility/ruggedness, robustness, linear range, and measurement uncertainty were evaluated for the measurement of nitrogen isotope ratios in AN. AN (99.5%) and ammonium thiocyanate (99.99+%) were determined to be the most suitable laboratory standards and were calibrated against international standards (certified reference materials). All performance characteristics were within an acceptable range when potential uncertainties, including the manufacturer’s uncertainty of the technique and standards, were taken into account. The experiments described in this article could be used as a model for validation of other instruments for similar purposes. Later studies in this series will address the more general issue of demonstrating that the IRMS technique is scientifically sound and fit‐for‐purpose in the forensic explosives analysis field.     

Trace Element Analysis of Rough Diamond by LA‐ICP‐MS: A Case of Source Discrimination?*,†

Abstract: Current profiling of rough diamond source is performed using different physical and/or morphological techniques that require strong knowledge and experience in the field. More recently, chemical impurities have been used to discriminate diamond source and with the advance of laser ablation–inductively coupled plasma–mass spectrometry (LA‐ICP‐MS) empirical profiling of rough diamonds is possible to some extent. In this study, we present a LA‐ICP‐MS methodology that we developed for analyzing ultra‐trace element impurities in rough diamond for origin determination (“profiling”). Diamonds from two sources were analyzed by LA‐ICP‐MS and were statistically classified by accepted methods. For the two diamond populations analyzed in this study, binomial logistic regression produced a better overall correct classification than linear discriminant analysis. The results suggest that an anticipated matrix match reference material would improve the robustness of our methodology for forensic applications.