Four new illicit cocaine impurities from the oxidation of crude cocaine base: formation and characterization of the diastereomeric 2,3-dihydroxy-3-phenylpropionylecgonine methyl esters from cis- and trans-cinnamoylcocaine

Four new impurities have recently been detected in the gas chromatographic signature profiles of many illicit cocaine hydrochloride exhibits. These impurities are only seen in exhibits that have been oxidized and are most prominent in samples that have been highly oxidized. Exhibits containing these compounds were subjected to gas and liquid chromatographic-mass spectrometric analyses to determine the identity of the impurities. These impurities were subsequently synthesized to verify their structures. Four diastereomeric diols formed from the oxidation of cis- and trans-cinnamoylcocaine were characterized by nuclear magnetic resonance spectrometry, mass spectrometry, and synthesis. Oxidation of cis-cinnamoylcocaine in neutral conditions yielded (2R,3R)-dihydroxy-3-phenylpropionylecgonine methyl ester and (2S,3S)-dihydroxy-3-phenylpropionylecgonine methyl ester, while trans-cinnamoylcocaine produced (2R,3S)-dihydroxy-3-phenylpropionylecgonine methyl ester and (2S,3R)-dihydroxy-3-phenylpropionylecgonine methyl ester. The recent appearance of these new impurities suggests that some illicit cocaine processors have modified their oxidation procedures of crude cocaine base for transformation into illicit refined cocaine hydrochloride.     

Simultaneous Quantitative Determination of Amphetamines,Opiates, Ketamine,Cocaine and Metabolites in Human Hair: Application to Forensic Cases of Drug Abuse

A method using liquid chromatography–tandem mass spectrometry (LC–MS/MS) to simultaneously quantify amphetamines, opiates, ketamine, cocaine, and metabolites in human hair is described. Hair samples (50 mg) were extracted with methanol utilizing cryogenic grinding. Calibration curves for all the analytes were established in the concentration range 0.05–10 ng/mg. The recoveries were above 72%, except for AMP at the limit of quantification (LOQ), which was 48%. The accuracies were within ±20% at the LOQ (0.05 ng/mg) and between −11% and 13.3% at 0.3 and 9.5 ng/mg, respectively. The intraday and interday precisions were within 19.6% and 19.8%, respectively. A proficiency test was applied to the validated method with z-scores within ±2, demonstrating the accuracy of the method for the determination of drugs of abuse in the hair of individuals suspected of abusing drugs. The hair concentration ranges, means, and medians are summarized for abused drugs in 158 authentic cases.     

Identification of acepromazine in hair: an illustration of the difficulties encountered in investigating drug-facilitated crimes

After a drug-facilitated sexual assault (DFSA), a woman was found in a drowsy state at home. She remembered having drunk an unknown beverage by the accused. Blood samples (collected 8 hours after the DFSA), two glasses, and a teaspoon seized by the police were analyzed. Acepromazine, a phenothiazine tranquilizer used in human and veterinary medicine, was detected in the residue of one of the glasses. In spite of acepromazine absence in the victim's blood, the possible use of acepromazine in the DFSA was reported to the police. Two weeks later, a suspect admitted having orally administered acepromazine to the victim. Using a liquid chromatography-tandem mass spectrometry method, this compound was subsequently detected (31 pg/mg) in a sample of the victim's hair collected a month and a half after the DFSA. A potential short elimination half-life in humans and/or the well-known in vitro degradation of acepromazine could explain the negative blood result. DFSA toxicological investigations are challenging and can be complicated when a rather unusual substance is concerned. In particular, special care should be taken when interpreting the results, taking into account elimination and/or instability data, when available.     

Development and validation of a simple GC-MS method for the simultaneous determination of 11 anticholinesterase pesticides in blood--clinical and forensic toxicology applications

Anticholinesterase pesticides are widely used, and as a result they are involved in numerous acute and even fatal poisonings. The aim of this study was the development, optimization, and validation of a simple, rapid, specific, and sensitive gas chromatography-mass spectrometry method for the determination of 11 anticholinesterase pesticides (aldicarb, azinphos methyl, carbofuran, chlorpyrifos, dialifos, diazinon, malathion, methamidophos, methidathion, methomyl, and terbufos) in blood. Only 500 μL of blood was used, and the recoveries after liquid-liquid extraction (toluene/chloroform, 4:1, v/v) were more than 65.6%. The calibration curves were linear (R(2) ≥ 0.996). Limit of detections and limit of quantifications were found to be between 1.00-10.0 and 3.00-30.0 μg/L, respectively. Accuracy expressed as the %E(r) was found to be between -11.0 and 7.8%. Precision expressed as the percent relative standard deviation was found to be <9.4%. The developed method can be applied for the investigation of both forensic and clinical cases of accidental or suicidal poisoning with these pesticides.     

Headspace‐Gas Chromatographic‐Mass Spectrometric Analysis of South American Commercial Solvents and their Use in the Illicit Conversion of Cocaine Base to Cocaine Hydrochloride

This study presents data that establish the makeup of solvents utilized in illicit cocaine hydrochloride production, as determined via the identification of the occluded solvents in the crystal matrix of the final product. The occluded solvent ratios can differ dramatically from the ratios of the original processing solvents. Additionally, the presented data suggest the diversion of commercial solvents to illicit cocaine hydrochloride laboratories. Thirty‐five commercial solvents were obtained from five chemical manufacturing companies in South America. Each solvent was qualitatively and quantitatively analyzed using static headspace‐gas chromatography‐mass spectrometry (HS‐GC‐MS). After obtaining the chemical profile for each commercial solvent, solvents and/or solvent mixtures were prepared to be comparable in composition to several of the commercial products. Over 90 individual batches of cocaine hydrochloride were prepared from cocaine base using these solvents or solvent mixtures, which match those most commonly employed in clandestine laboratories. Additionally, a number of unique manufacturing by‐products produced from processing solvents were identified, and their significance is discussed.     

Emergence of fentanyl-related deaths in Travis County,Texas and surrounding areas: A retrospective review of postmortem fentanyl-related drug toxicities from 2020 to 2022

The opioid epidemic has affected the United States (US) for decades with fentanyl and its analogs accounting for a recent surge in morbidity and mortality. Currently, there is a relative lack of information characterizing fentanyl-related fatalities specifically in the Southern US. A retrospective study was conducted to examine all postmortem fentanyl-related drug toxicities in Travis County, Texas, encompassing Austin (one of the fastest-growing cities in the US), from 2020 to 2022. Fentanyl contributed to 2.6% and 12.2% of deaths submitted for toxicology between 2020 and 2022, respectively, representing a 375% increase in fentanyl-related deaths over this 3-year period (n = 517). Fentanyl-related fatalities primarily occurred in males in their mid-30s. Fentanyl and norfentanyl concentrations ranged from 0.58 to 320 ng/mL and 0.53 to 140 ng/mL with mean (median) concentrations of 17.2 ± 25.0 (11.0) and 5.6 ± 10.9 (2.9) ng/mL, respectively. Polydrug use was present in 88% of cases, with methamphetamine (or other amphetamines) (25%), benzodiazepines (21%), and cocaine (17%) representing the most frequently identified concurrent substances. Co-positivity rates of various drugs and drug classes widely varied over time. Scene investigations reported illicit powder(s) (n = 141) and/or illicit pill(s) (n = 154) in 48% (n = 247) of fentanyl-related deaths. Illicit oxycodone (44%, n = 67) and illicit “Xanax” (38%, n = 59) pills were frequently reported on scene; however, toxicology only identified oxycodone and alprazolam in 2 and 24 of these cases, respectively. The results of this study provide a better understanding of the fentanyl epidemic in this region creating an opportunity to promote increased awareness, shift focus to harm reduction, and aid in minimizing public health risks.     

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.     

Detection and Classification of Ignitable Liquid Residues in the Presence of Matrix Interferences by Using Direct Analysis in Real Time Mass Spectrometry,

Conventional Gas Chromatography‐Mass Spectrometry (GC‐MS) methods for the analysis of ignitable liquids (ILs) are usually time‐consuming, and the data produced are difficult to interpret. A fast IL screening method using direct analysis in real time mass spectrometry (DART‐MS) is proposed in this study. GC‐MS, QuickStrip DART‐MS, and thermal desorption DART‐MS methods were used to analyze neat ILs and thermal desorption DART‐MS without extraction was used to analyze ILs on five substrates (e.g., carpet, wood, cloth, sand, and paper). Compared to GC‐MS, DART‐MS methods generated different spectral profiles for neat ILs with more peaks in the higher mass range and also provided better detection of less volatile compounds. ILs on substrates were successfully classified (98 ± 1%) using partial least squares discriminant analysis (PLS‐DA) models based on thermal desorption DART‐MS data. This study shows that DART‐MS has great potential for the high‐throughput screening of ILs on substrates.     

Forensic Identification of Blood in the Presence of Contaminations Using Raman Microspectroscopy Coupled with Advanced Statistics: Effect of Sand,Dust, and Soil

Body fluid traces recovered at crime scenes are among the most common and important types of forensic evidence. However, the ability to characterize a biological stain at a crime scene nondestructively has not yet been demonstrated. Here, we expand the Raman spectroscopic approach for the identification of dry traces of pure body fluids to address the problem of heterogeneous contamination, which can impair the performance of conventional methods. The concept of multidimensional Raman signatures was utilized for the identification of blood in dry traces contaminated with sand, dust, and soil. Multiple Raman spectra were acquired from the samples via automatic scanning, and the contribution of blood was evaluated through the fitting quality using spectroscopic signature components. The spatial mapping technique allowed for detection of “hot spots” dominated by blood contribution. The proposed method has great potential for blood identification in highly contaminated samples.     

Detection of Acute Diazepam Exposure in Bone and Marrow: Influence of Tissue Type and the Dose‐Death Interval on Sensitivity of Detection by ELISA with Liquid Chromatography Tandem Mass Spectrometry Confirmation*

Abstract: Enzyme‐linked immunosorbent assay (ELISA) and liquid chromatography tandem mass spectrometry (LC/MS/MS) were used to detect diazepam exposure in skeletal tissues of rats (n = 15) given diazepam acutely (20 mg/kg, i.p.), and killed at various times postdose. Marrow, epiphyseal, and diaphyseal bone were isolated from extracted femora. Bone was cleaned, ground, and incubated in methanol. Marrow underwent ultrasonic homogenization. Extracts and homogenates were diluted in phosphate buffer, and then underwent solid‐phase extraction and ELISA. Relative sensitivity of detection was examined in terms of relative decrease in absorbance (ELISA) and binary classification sensitivity (ELISA and LC/MS/MS). Overall, the data showed differences in relative sensitivity of detection of diazepam exposure in different tissue types (marrow > epiphyseal bone > diaphyseal bone), which is suggestive of heterogenous distribution in these tissues, and a decreasing sensitivity with increasing dose‐death interval. Thus, the tissue type sampled and dose‐death interval may contribute to the probability of detection of diazepam exposure in skeletal tissues.