The forensic deaths caused by pesticide poisoning between the years 2006 and 2009 in Izmir, Turkey

Pesticide poisoning is still a significant health problem in Turkey. We conducted a retrospective study of autopsy cases at Izmir Branch of the Council of Forensic Medicine to describe the characteristics of deaths caused by pesticide poisoning between 2006 and 2009. The distributions of the cases according to gender and age were as follows: men 74.1% (n = 40, mean [±SD] age, 44.7 ± 14.1), women 25.9% (n = 14, mean [±SD] age, 39.2 ± 18.9). The majority of pesticide-poisoning deaths were suicides (n = 43, 80%) followed by accidents (n = 4, 8%) and homicide (n = 1, 2%). The manner of death could not be determined in six cases (11%). Suicides mostly occurred at home (n = 26, 63%) (p < 0.05). Methomyl was the most frequent pesticide (n = 9, 17%) among the all cases. This study reported that most of the pesticides found in poisoning cases were highly hazardous types. Combined efforts of medical professionals and law makers are needed for enacting strict laws against highly hazardous pesticides.     

Using Cluster Analysis and ICP‐MS to Identify Groups of Ecstasy Tablets in Sao Paulo State,Brazil

The variations found in the elemental composition in ecstasy samples result in spectral profiles with useful information for data analysis, and cluster analysis of these profiles can help uncover different categories of the drug. We provide a cluster analysis of ecstasy tablets based on their elemental composition. Twenty‐five elements were determined by ICP‐MS in tablets apprehended by Sao Paulo's State Police, Brazil. We employ the K‐means clustering algorithm along with C4.5 decision tree to help us interpret the clustering results. We found a better number of two clusters within the data, which can refer to the approximated number of sources of the drug which supply the cities of seizures. The C4.5 model was capable of differentiating the ecstasy samples from the two clusters with high prediction accuracy using the leave‐one‐out cross‐validation. The model used only Nd, Ni, and Pb concentration values in the classification of the samples.     

血液中Cr、Cd、As、Tl和Pb的电感耦合等离子体质谱分析

目的 建立血液中Cr、Cd、As、Tl和Pb的电感耦合等离子体质谱(ICP-MS)分析方法. 方法血液采用微波消解仪进行处理,以115In元素作内标,使用ICP-MS方法对血液中Cr、Cd、As、Tl和Pb进行分析.结果 方法检出限为0.00001～0.00249μg/L,准确度为90.1%～110.7%,精密度为4.0%～7.9%. 结论建立的方法准确、快速、线性范围宽、灵敏度高,适用于Cr、Cd、As、Tl和Pb中毒案件的检测.     

微波消解ICP-MS法检测生物检材中汞元素

目的 建立生物检材中汞的电感耦合等离子体质谱分析方法.方法 采用微波消解法处理样品,以铟(115In)作内标,用电感耦合等离子体质谱仪对血液、尿液和头发中的汞含量进行分析.选择金与汞形成金汞齐,对金消除汞记忆效应的能力进行考察.结果 方法检出限为0.01μg/L,准确度为97.0%～107.1%.检测中添加金质量浓度在...     

Bromadiolone poisoning: LC-MS method and pharmacokinetic data

Abstract:  Poisoning with superwarfarins, like bromadiolone, is a growing public health problem, and the mortality is high. Pharmacokinetic data on bromadiolone in humans are however scarce, and there are no reports following repeated exposures to bromadiolone. We have developed a method for quantification of bromadiolone in whole blood, using liquid chromatography–mass spectrometry (LC-MS). The analytical method is reported. Limit of detection was 0.005 mg/L and limit of quantification was 0.01 mg/L. The concentrations of bromadiolone in whole blood and plasma in serial samples from a 62-year-old woman were measured. The half-life of bromadiolone in blood was estimated to be about 6 days in the initial phase of elimination and about 10–13 days in the terminal phase. The mean plasma/blood ratio of bromadiolone was 1.7 ± 0.6. Stability testing of bromadiolone in whole blood samples after two cycles of freeze and thaw revealed that bromadiolone concentrations decreased.     

激光剥蚀电感耦合等离子体质谱技术检测车辆油漆金属元素

目的建立车辆油漆的激光剥蚀电感耦合等离子体质谱（laser ablation inductively coupled plasma mass spectrometry,LA—ICP—MS）分析方法。方法对38种车辆油漆样品采用激光剥蚀,电感耦合等离子体质谱进行测定,通过各油漆样品本含有金属元素种类和金属元素响应相对比值的差异对油漆样品进行区分。结果38种样品中有30种可直接依据所含金属元素种类的差异进行对其进行区分,其余8种依据元素间响应值比值的差异进行区分,方法重现性良好,精密度（RSD）小于10％。结论所建立的LA—ICP—MS方法简便快速、精密度良好、对样品微损,适用于法庭科学对车辆油漆的检测。     

A case of fatal aconitine poisoning by Monkshood ingestion

Accidental aconitine poisoning is extremely rare in North America. This report describes the confirmation of a case of accidental aconitine poisoning using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method. The case involved a 25-year-old man who died suddenly following a recreational outing with friends where he consumed a number of wild berries and plants including one that was later identified as Monkshood (Aconitum napellus). Postmortem blood and urine samples were available for analysis. All routine urine and blood toxicology screens were negative. The LC-MS/MS method allowed sensitive quantification of aconitine, the main toxin in A. napellus, and showed 3.6 and 149 microg/L in blood and urine, respectively. These concentrations were similar to that reported in other aconitine-related deaths. This case illustrates the dangers of consuming unidentified plants, and documents concentrations of aconitine in blood and urine in a fatal case of A. napallus-related poisoning.     

Detection of Pb,Ba, and Sb in Cadaveric Maggots and Pupae by ICP-MS*

The concentrations of lead (Pb), barium (Ba), and antimony (Sb), characteristic of GSR, were determined in soil sediments and immature (larvae) of cadaveric flies of the family Calliphoridae, by inductively coupled plasma mass spectrometry (ICP-MS). This research refers to a case study from two real crime scenes in which the corpses were in an advanced state of decomposition. In case 1, the victim had holes similar to gunshot wounds, and in case 2, there was no evidence of perforations in the corpse. Soil sediment collection was performed at three different points of the terrain, at a minimum distance of 10 m from the corpse, for cases 1 and 2. In relation to the collection of immatures, larvae were collected in regions of the mouth, nose, and orifices similar to the entry of firearms projectile into the body, for case 1, and collection of larvae and pupae, located on the body and underneath it, for case 2. It was possible to detect and quantify the three elements of interest (Pb, Ba, and Sb) by ICP-MS in both sediment and cadaveric larvae. Concentrations of 4.44, 8.74, and 0.08 μg/g were obtained for Pb, Ba, and Sb, respectively, in the soil for case 1. For the case 2, the concentrations in Pb, Ba, and Sb were from 16.34 to 26.02 μg/g; from 32.64 to 57.97 μg/g and from 0.042 to 0.30 μg/g, respectively. In the larvae, Pb, Ba, and Sb were quantified in cases 1 and 2 with a concentration of 6.28 and 1.78 μg/g for Pb, 1.49 and 2.94 μg/g for Ba, 0.50 μg/g and <LD for Sb, respectively. These new results present the detection of characteristic elements of GSR in cadaveric larvae in humans in a real crime scene, besides highlighting the importance of the study of immature flies, using the ICP-MS technique in forensic analysis.     

Poisoning deaths in Central China (Hubei): A 10-year retrospective study of forensic autopsy cases

A retrospective study of autopsy cases was conducted at the Department of Forensic Medicine, Tongji Medical College (DFM-TMC), in Hubei, China to describe the characteristics of poisoning deaths from 1999 to 2008. A total of 212 poisoning deaths were investigated by DFM-TMC during the 10-year period. The poisoning deaths ranged from 17 cases in 1999 to 27 cases in 2008. Of the 212 cases, 82 deaths (38.7%) were from pesticides, 36 deaths (17.0%) from carbon monoxide, 34 deaths (16.0%) from drugs, 22 deaths (10.4%) from alcohol, 17 deaths (8.0%) from other chemicals, 15 deaths (7.1%) from poisonous plants and animals, and six deaths (2.8%) from heavy metals. Of the 82 pesticide poisoning deaths, 43 (52.4%) cases were caused by rodenticides, mainly tetramine (N = 39). The majority of poisoning deaths were accidents (63.7%), followed by suicides (25.9%) and homicides (3.8%). The manner of death could not be determined in 14 cases (6.6%).     

The Survival of Gunshot Residues in Cremated Bone: An Inductively Coupled Plasma Optical Emission Spectrometry Study

Gunshot residue (GSR) has been sought and demonstrated on many types of material and with many techniques. Inductively coupled plasma optical emission spectrometry (ICP‐OES) could be a useful method on difficult substrates, but a systematic study on burnt material has never been performed. Hence, this study aims at evaluating the usefulness and reliability of this method on burnt samples. Sixteen adult bovine ribs (eight with soft tissues, eight totally skeletonized) were shot using two kinds of projectile (both 9 mm full metal‐jacketed or unjacketed). Then, every sample was led to complete calcination in an electric oven. The area of the gunshot entrance wound was swabbed and analyzed by ICP‐OES; the results were also correlated with a previously published parallel study by scanning electron microscopy (SEM) equipped with an SEM–energy dispersive X‐ray analyzer. ICP‐OES proved to be very sensitive and reliable even on degraded material and can be an appropriate nondestructive method for detecting residues on difficult and delicate substrates such as burnt bone.     

Diesel fumes do kill: a case of fatal carbon monoxide poisoning directly attributed to diesel fuel exhaust with a 10-year retrospective case and literature review*

While it is known that diesel fuel combustion engines produce much lower concentrations of carbon monoxide (CO) than gasoline engines, these emissions could certainly generate lethal ambient concentrations given a sufficient amount of time in an enclosed space and under suitable environmental conditions. The authors report a case of CO poisoning which was initially referred for autopsy as a presumed natural death of a truck driver found in the secure cab of a running diesel tractor trailer truck. Completion of the preliminary investigation ascribed death to complications of ischemic heart disease (IHD), pending toxicological analysis that included quantification of CO. When the toxicology results showed lethal blood COHbg, the cause of death was re-certified as CO intoxication secondary to inhalation of (diesel) vehicular exhaust fumes. Because of the unique source of fatal CO intoxication in this case, the contributory IHD and the possible contaminants in the putrefied blood, a 10-year retrospective review was conducted on all nonfire related CO deaths autopsied (n = 94) at the Office of the Chief Medical Examiner in Louisville, KY from 1994 to 2003. For validation of the COHbg detection method used by the Kentucky Office of Forensic Toxicology (KYOFT), blood samples from these cases along with controls were submitted to three laboratories using various analytical methods yielding no statistically significant differences. Lastly, an extensive literature review produced no scientifically reported cases of fatal CO poisoning attributed to diesel fuel exhaust.     

Differentiation of bullet type based on the analysis of gunshot residue using inductively coupled plasma mass spectrometry

Porcine tissue samples shot with two different types of bullets, jacketed and nonjacketed, were collected in the fresh state and throughout moderate decomposition. Wound samples were microwave-digested and analyzed using inductively coupled plasma mass spectrometry (ICP-MS) to detect all elements present at measurable levels in gunshot residue (GSR). Elements detected included antimony (Sb), barium (Ba), and lead (Pb), which are considered characteristic of GSR, as well as iron (Fe) and copper (Cu). These five elements were used to differentiate shot tissue and unshot tissue, as well as tissue shot by the two different bullet types, both in the fresh state and throughout moderate decomposition. The concentrations of Cu, Sb, and Pb were able to distinguish the two bullet types in fresh tissue samples at the 95% confidence level. Cu and Pb were able to differentiate the bullet types throughout moderate decomposition at the 99% confidence level.     

Characterization of Undigested Particulate Material Following Microwave Digestion of Recycled Document Papers

Abstract:  Recycled document paper was microwave digested in a solution of HNO₃ and H₂O₂ prior to analysis by inductively coupled plasma mass spectrometry (ICP-MS) to determine the trace elemental concentrations within the paper. Undigested particulate material was observed and subsequently characterized as a mixture of kaolin (clay) and TiO₂ by Fourier transform infrared spectroscopy and X-ray diffraction spectroscopy. The effect of the particulate material on the elemental concentrations was then investigated. Paper samples were completely digested in hydrofluoric acid (HF) and element concentrations determined in the HF and HNO₃/H₂O digests were statistically compared using Student's t -test (95% confidence limit). Statistical differences in element concentrations between the two digests were observed for only four elements and there was no evidence of element adsorption by the particulate material. Hence, the HNO₃/H₂O₂ digestion proved sufficient to digest paper for ICP-MS analysis, eliminating the need to use the hazardous and corrosive HF matrix.     

The development of analytical and interpretational protocols to facilitate the provenance establishment of polycarbonate headlamp lens material

Despite the forensic significance of polycarbonate headlamp lenses, robust analytical protocols to facilitate their discrimination are scarce. In this study, laser ablation inductively coupled plasma mass spectrometry has been applied to the analysis of polycarbonate headlamp lenses with multivariate chemometrics techniques utilized to facilitate interpretation of the data. The analytical protocol involves the analysis of 46 analytes on material comprising the exterior surface of the lens. Using this data, it was found that although minor variation exists within a single headlamp lens, discrimination between lenses produced from a single manufacturing plant was still possible using iterative forward stepwise linear discriminant analysis processes. Discrimination between all headlamp lenses, with the exception of some lenses produced on the same day in a single plant, could be achieved using the analytical protocol. Furthermore, an interpretational protocol has been developed that has successfully classified all tested headlamp lens samples, within the discrimination limits of the analytical method.     

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.     

Black Esophagus: Acute Esophageal Necrosis in Fatal Haloperidol Intoxication

Herein, we present a case of 53‐year‐old psychotic woman with acute esophageal necrosis (black esophagus), who was found lying on the floor in the living room of her flat. Pillboxes of antipsychotic drugs were located in the bin. External examination of the body was unremarkable. On internal examination, we found acute esophageal necrosis. Histologically, there was complete epithelial necrosis with focal involvement of muscularis mucosae, dense infiltrate of leukocytes, and ulcerations without any viable cells. There was no evidence of underlying organic diseases or trauma. Toxicological analysis revealed a fatal blood level of antipsychotics (haloperidol, zotepine, and chlorprothixene). Death of the deceased was attributed to fatal intoxication with three various types of antipsychotics. As far we know, this is the first described association between so‐called black esophagus and fatal blood level of neuroleptics.     

电热板消解电感耦合等离子体质谱法测定人发中33种无机元素的含量

目的建立头发中33种无机元素的电热板消解电感耦合等离子体质谱（inductivelycoupledplas—ma—IllasssDectrometry,ICP—MS）测定方法。方法以锂（6Li）、锗（^72Ge）、钇（^89Y）、铟（^115In）、铽（^159yb）作内标,硝酸和过氧化氢作为消解酸体系．采用电热板消解对头发进行前处理,ICP—MS法分析人发中33种无机元素的含量。结果电热板消解ICP—MS法的检出限为0．0001μg／g（Th）-10．9μg／g（Ca）,定量限为O．0005μg／g（Th）～25μg／g（Ca）,加标回收率为86％～113％,日内及日间精密度≤9.2％,与微波消解法检测结果相比,差异无统计学意义。结论电热板消解ICP—MS法高效、准确度高,适用于对头发中33种无机元素的分析。     

Determination of Trace Elemental Concentrations in Document Papers for Forensic Comparison Using Inductively Coupled Plasma–Mass Spectrometry

Abstract:  With improvements in manufacturing procedures, comparing physical characteristics of paper samples may not offer sufficient discrimination among different vendors. In this work, the potential to differentiate paper samples based on trace element concentrations was investigated. Paper samples from two different vendors were microwave-digested and trace element concentrations (Mg, Al, Mn, Fe, Sr, Y, Ba, Ce, and Nd) were determined using inductively coupled plasma–mass spectrometry. Differences in concentration were assessed statistically using two-way ANOVA and Tukey's honestly significant differences test. Elemental concentrations were shown to be consistent across a single sheet as well as within a single ream of paper for each vendor. Reams from vendor A were differentiated based on Al and Ba concentration while reams from vendor B were differentiated based on Mg, Mn, and Sr concentrations. Paper was differentiated according to vendor based on significant differences in Ba, Sr, Ce, and Nd concentrations.