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Analysis of hydrogen cyanide in air in a case of attempted cyanide poisoning
Abstract
A 32-year-old man attempted to poison his ex-girlfriend with hydrogen cyanide by hiding the pesticide Uragan D2 in her car. During the police investigation, chemical analysis of the air inside the car was performed. Hydrogen cyanide was detected through on-site air analysis using a portable Fourier transform infrared (FTIR) spectroscopy gas analyzer and colorimetric gas detection tubes. Furthermore, impinger air-sampling was performed for off-site sample preparation and analysis by gas chromatography-mass spectrometry (GC-MS). All three independent techniques demonstrated the presence of hydrogen cyanide, at concentrations of 14-20 ppm. Owing to the high volatility of hydrogen cyanide, the temperature and the time since exposure have a substantial effect on the likelihood of detecting hydrogen cyanide at a crime scene. The prevailing conditions (closed space, low temperature) must have supported the preservation of HCN in the car thus enabling the identification even though the analysis was performed several days after the hydrogen cyanide source was removed. This paper demonstrates the applicability of combining on-site FTIR measurements and off-site GC-MS analysis of a crime scene in order to ensure fast detection as well as unambiguous identification for forensic purposes of hydrogen cyanide in air.
... There are many analytical methods presented in literature for the detection of cyanides in different matrices ranging from water (Isaad et al., 2013;Kang and Shin, 2014;Rosentreter et al., 2015), air (Greenawald et al., 2015;Magnusson et al., 2012;Musshoff et al., 2011;Orloff et al., 2006), human breath (Lauridsen et al., 2015) and smoking cigarette (Pre and Vassy, 1991). Cyanide can also be detected in biological fluids such as blood (Boadas-Vaello et al., 2008;Calafat and Stanfill, 2002;Desharnais et al., 2012;Ferrari and Giannuzzi, 2015;Frison et al., 2006;Kage et al., 1996;Lindsay et al., 2004;Youso et al., 2010), urine (Liu et al., 2009;Logue et al., 2005;Minakata et al., 2009;Zhang et al., 2015) and saliva (Paul and Smith, 2006). ...
... The HCN concentrations were reported to be between 0.2 and 1.09 ppbv. Okafor and Maduagwu (2000) and Magnusson et al. (2012) reported very high HCN concentrations using colorimetric determination in their studies from 14 to 42 ppm. Comparison from different studies showed that HCN concentration in the air varied depending on nature of activities in the local environment, method of sampling as well as analytical method used. ...
Hydrogen cyanide (HCN) is commonly released into the atmosphere from vehicle emissions, biomass burning and industrial processes such as gold mining, pesticide production, and chemical manufacturing. The aim of this study was to quantify the ambient HCN concentration in a residential area close to a gold mine using solid-phase micro extraction (SPME) coupled with gas chromatography–mass spectrometry (GC–MS) and calculate it's potential health risks. Air samples were collected at a distance of 0.1, 1.0 and 2.0 km away from the gold mine. All cyanide compounds were extracted using 75 μm carbowax/polydimethylsiloxane-coated SPME fibre and analysed using GC–MS. Calibration curve was constructed using standard concentrations ranged between 5 and 500 μg L⁻¹. This method showed good linearity (r² = 0.999) and accuracy (recoveries = 84–119%), reproducibility (relative standard deviation < 11.5%) and the LOD was 0.16 ppbv. HCN was detected in 68% of samples ranging between 0.16 and 8.56 ppbv. HCN concentration was significantly higher (p < 0.05) for samples taken at 0.1 km away from the gold mine compared to concentrations at 1.0 and 2.0 km. The non-carcinogenic risk of HCN from air inhalation was negligible as the calculated hazard quotient was less than 1. The method used in this study was sensitive enough to detect ambient HCN concentrations at levels which were below the reference concentration for long term inhalation exposure by the U.S. Environmental Protection Agency (0.72 ppbv) and it used simpler and less time consuming method compared to the conventional sample preparation method, enabling rapid community exposure assessment.
... It is an intermediate in manufacturing synthetic fabrics, dyes, and others. Exposure to HCN can lead to fatal consequences and may occur through various sources including cigarette smoke, combustion byproducts, naturally occurring cyanide compounds in food, as well as industrial activities [1][2][3]. The onset of symptoms depends on the dose and duration of the exposure [4,5]. ...
Hydrogen cyanide (HCN) gas, a major industrial pollution, is generated as a result of burning fossil fuels and indirectly contributes to the greenhouse effect. Therefore, deep eutectic solvents (DES) can provide a low-cost and effective method for its detection and removal. Density function theory (DFT) computations have been used to conduct a theoretical investigation of a DES, composed of choline chloride (ChCl) and 1,3-propanediol (PD). The potential of DES for HCN adsorption or binding has been examined using computational calculations. Herein, the viability of adsorption of HCN by the DES composed of ChCl and PD in 1:1 and 1:2 ratio, that is, 2a and 3a have been studied and further, the number of HCN molecules have been varied. The study was conducted by analysing the interactions and electronic properties obtained from DFT computations. Density of states (DOS) spectra were determined and used to examine the stability of the complex formed between DES and HCN. Significant interactions between DES systems and HCN molecules have been observed. Natural bond orbital (NBO) analysis indicated an increase in the strength of interactions upon an increase in PD molecules. Molecular dynamics (MD) simulations of the DESs with and without HCN were performed and investigated. Root mean square deviation (RMSD) and root mean square fluctuation (RMSF) trajectories were extracted and used to analyse the interactions in DES and HCN at different ratios. The RMSD plots showed increased values with lower fluctuations with an increase in the number of HCN molecules, demonstrating that the structures remained in equilibrium despite the rise in the number of HCN molecules. RMSD patterns revealed the stability of the complex formed between DES and HCN molecules. RMSF plot indicated the stable geometries obtained upon interacting DES with HCN molecules. The number of hydrogen bonds increased with an increase in the number of DES molecules.
... For example, some of the already reported reaction based cyanide sensors include aldehyde, ketones [14], coumarins [15], hydrazones [16], acridinium salts [17], unsaturated compound based sensors [18], cationic boranes [19], oxazines [20]. However, slow response time, requirement of high temperature, need of basic medium, high detection limit, less selectivity, inefficiency in aqueous medium, and risk of releasing HCN hamper the sensing ability of these chemodosimeters [21,22]. Unfortunately, non-reversible nature of previously reported all reaction based cyanide sensors makes these chemosensors unpractical in real field applications. ...
Rising detrimental effects of cyanide due to its frequent large-scale utilization demand rapid and sensitive detection of cyanide ions. Herein, two new fluorene based chemosensors 1 and 2 have been developed through the Suzuki–Miyaura coupling reaction for fluorescence enhancement based selective detection of cyanide with sensitivity levels down to 0.2 ppb and 0.4 ppb, respectively. The plausible sensing mechanism is based on Michael type adduct formation due to the reaction of cyanide with chemosensors and was confirmed by ¹H NMR titration, Job’s plot, dynamic light scattering (DLS), and density functional theory (DFT). Chemosensors 1 and 2 showed excellent linear response towards CN¯ ions (0−100 nM) in the Benesi–Hildebrand plot with association constants (Ka) 1.61 × 10⁶ and 7.1 × 10⁵ M¯¹, respectively that corresponds to their favorable chemical reaction. Excellent selectivity of chemosensors for cyanide in the presence of other interferences was investigated through fluorescence emission, UV-Visible, and DFT analysis. Surprisingly, an immediate reversible colorimetric change upon alternate shaking and steadiness of chemosensor−CN¯ solution was noticed indicating that chemosensors can act as promising recyclable sensors for colorimetric on-site detection of CN¯. Meanwhile, chemosensors 1 and 2 displayed highly selective colorimetric detection of CN¯ under daylight and UV radiations (365 nm). Further, cyanide responsive test kits were fabricated that provided a low-cost and portable method for on-site detection of CN¯ ions in an aqueous medium. Finally, chemosensors were successfully applied for designing logic gates, and detection of cyanide in industrial waste and food samples.
... Numerous industrial modernisations and high demand in the market for many chemical processes in sectors such as petrochemicals, gold and silver extraction, plastic and steel manufacturing, copper photography, etc., have led to an enormous growth of these industries, which generates and excretes high quantities of cyanides that are increasingly contaminating the surrounding environment. [11] In sum, there is demand for fast, inexpensive detection of HCN gas and cyanide salts that can be registered with the naked eye. ...
A series of intramolecularly hydrogen bonded zwitterionic compartmental ligands HL1‐HL4 containing a pendent diamine arm which is monoprotonated and an aldehyde functionality at two different ortho positions of a 4‐halophenoxide is reported herein. Single crystal X‐ray diffraction (SXRD) provides persuasive evidence for the identification of this class of proton‐transferred zwitterions at room temperature. Solid‐state photoluminescent nature of these zwitterions remain intact in aqueous and organic solutions. Grinding of HL1 and HL2 with Cu2+/Ni2+ salts develop turn‐on probes 1‐4. Compounds 1 and 4 are dinuclear Cu(II) and Ni(II) species, respectively. While, 2 is a tetranuclear Cu(II) complex. Interestingly, compound 3 is a mononuclear Ni(II) species in which both nitrogens in the hanging diamine arm are protonated and therefore, not coordinated to the Ni(II) center. All these probes (1‐4) display an instant response to the poison gas hydrogen cyanide (HCN) and cyanide salts present in solid matrices and aqueous (100 % water) solution as well. Selective and rapid sensing of HCN gas and cyanide salts in solid/soil/water phases, without any interference, by the mechanosynthesized complexes 1‐4 can be perceived easily by the naked eye under a hand‐held UV lamp.
... The duration of hydrogen cyanide in the atmosphere is estimated to be approximately 5 months (Karlsson and Botz 2004;Scheneider et al. 1997). Zhao et al. (2000) 195 ± 16 pptv (winter) Lower stratosphere 233.5 ± 160.6 ppt Singh et al. (2003) 280 ± 4 pptv Viggiano et al. (2003) Stratosphere 164 pptv Scheneider et al. (1997) Gold field 0.76 ppb Orloff et al. (2006) Vehicular emissions 654 t/year Moussa et al. (2016) Vehicular emission 0.45 mg/km Karlsson and Botz (2004) Indoor air Vehicular exposure in garage 0.32 μg/m 3 Karlsson and Botz (2004) Air in car 14-20 ppm Mangnusson et al. (2012) Fire ...
Cyanide toxicity and their environmental impact are well known. Nevertheless, they are still used in the mining, galvanic and chemical industries. As a result of industrial activities, cyanides are released in various forms to all elements of the environment. In a natural environment, cyanide exists as cyanogenic glycosides in plants seeds. Too much consumption can cause unpleasant side effects. However, environmental tobacco smoke (ETS) is the most common source of cyanide. Live organisms have the ability to convert cyanide into less toxic compounds excreted with physiological fluids. The aim of this paper is to review the current state of knowledge on the behaviour of cyanide in the environment and its impact on the health and human life.
... Furthermore, hydrogen cyanide gas is highly poisonous by all routes of administration. [28] Therefore, it is recommended that samples with free cyanide residues must be stabilized with sodium hydroxide to a pH > 9 for analytical requirements and health reasons. ...
Goiter is an important health problem all over the world and iodine deficiency is its most common cause. Perchlorate, thiocyanate and nitrate (called as major NIS inhibitors) are known to competitively inhibit iodide uptake by the thyroid gland and thus, human exposure to major NIS inhibitors is a public health concern. In this study, an ion chromatographic method for the determination of most common NIS inhibitor ions in drinking waters was developed and validated. This is the first study where an analytical method is used for the determination of major NIS inhibitors in drinking water by an ion chromatography system in a single run. Chromatographic separations were achieved with an anion-exchange column and separated ions were identified by a conductivity detector. The method was found to be selective, linear, precise accurate and true for all of interested ions. The limits of the detections (LOD) were estimated at 0.003, 0.004 and 0.025mgL(-1) for perchlorate, thiocyanate and nitrate, respectively. Possible interference ions in drinking waters were examined for the best separation of NIS inhibitors. The excellent method validation data and proficiency test result (Z-score for nitrate: -0.1) of the FAPAS(®) suggested that the developed method could be applied for determination of NIS inhibitor residues in drinking waters. To evaluate the usefulness of the method, 75 drinking water samples from Antalya/Turkey were analyzed for NIS inhibitors. Perchlorate concentrations in the samples ranged from not detected (less than LOD) to 0.07±0.02mgL(-1) and the range of nitrate concentrations were found to be 3.60±0.01mgL(-1) and 47.42±0.40mgL(-1). No thiocyanate residues were detected in tested drinking water samples.
... Furthermore, hydrogen cyanide gas is highly poisonous by all routes of administration. [28] Therefore, it is recommended that samples with free cyanide residues must be stabilized with sodium hydroxide to a pH > 9 for analytical requirements and health reasons. ...
An ion chromatographic method for the quantitative determination of free cyanide in bottled natural mineral waters were measured in terms of selectivity, linearity, the limit of detection, limit of quantification, repeatability, precision, and accuracy. Chromatographic separation of free cyanide ions was accomplished with an anion-exchange column and detected by pulsed amperometric detection with a silver working electrode. The method was found to be selective, linear (r2 = 0.999) at a concentration range of 0.5 to 134 μg L−1, precise, and accurate. Recovery values of free cyanide in all classes of natural mineral water varied from 65.9 ± 1.6 to 95.2 ± 0.7 at different spiking levels (5–70 μg L−1). Parameters (total dissolved solids, mineral interferences, and added sodium hydroxide) affecting the recovery values were studied in this project. The limit of detection and limit of quantification were found to be 0.295 and 0.983 μg L−1, respectively. The proposed method was applied to 27 different brands of commercially available bottled natural mineral water products sold in Turkish markets. These natural mineral waters were classified as: (i) very low mineral concentration, (ii) low mineral concentration, (iii) intermediate mineral concentration, and (iv) high mineral concentration based on their total dissolved solids contents according to European Union Directive (Directive 80/777/EEC). Levels of free cyanide residues in the samples ranged from > limit of detection to 6.12 μg L−1. The highest average concentration of free cyanide residues was found in the class of “high mineral concentration waters.” However, the determined free cyanide values in all of the tested natural mineral water samples were found to be within the limits of European Union legislation.
Cyanide poisoning may result from a variety of exposures including structural fires, industrial exposures, medical exposures and certain plant products. Cyanide poisoning cases may be accidental and intentional motivated by suicidal or homicidal purposes. Cyanogenic plant toxicity is one of the most common plant poisonings among the grazing livestock. Such cases are occasionally reported and investigated for medico legal, police and forensic settings. Forensic evidences, such as stomach contents and whole blood of the victims, are usually collected and analysed in order to confirm the cause of death. Various analytical techniques have been suggested for the toxicological detection and measurement of hydrocyanic acid (syn. hydrogen cyanide, prussic acid, HCN) and its metabolites from biological and environmental samples. However. the volatility and reactivity of cyanide leaves direct measurements highly susceptible to errors introduced during the sample collection and separation step. An alternative approach, that can help to minimize false positive and false negative results, is to detect stable biomarkers of cyanide metabolism, rather than cyanide itself. Some studies proved 2-aminothiazoline-4-carboxylicacid (ATCA) to be a stable cyanide metabolite and thus ATCA has been considered a promising biomarker for cyanide poisoning. Some important aspects of cyanide poisoning and its detection, mainly by mass spectrometric methods, are discussed in this article.
Esse artigo pesquisou em bases de dados viáveis a literatura que abranja o tema estudado. E logo com os dados encontrados analisou a relevância preservação do local de crime para a investigação pericial. Por fins sobre o que é o local de crime dentro da ciência forense, a fim de compreender a importância de sua preservação e mostrar sua utilidade dentro da investigação de suspeitos de crimes e trazer sobre o tema escolhido através de uma revisão. A busca de dados, foi realizada uma busca de artigos científicos nas seguintes bases de dados: PubMed e Periódico CAPES, utilizando os descritores, sendo estudos publicados de 2000 até fevereiro de 2023 foram revisados. A preservação do local do crime propícia aos investigadores um melhor resultado dos seus achados no local, promovendo uma melhor resposta quando forem ser analisados para a solução do crime. Além de ser uma das partes mais importantes dentro da perícia criminal, está muito unida a outras áreas que quando se encaixam formam o meio perfeito para solução de catástrofes ou tentativas.
Owing to the extraordinary characteristics Carbon Nanotubes exhibit, these have been employed for wide range of applications. The recognition of chemical contaminants is one such area of research which always involve advancement in concern to the environmental protection and public health. In this regard, Carbon nanotubes decorated with nickel nanoparticles (CNT@Ni) nano‐hybrid has been fabricated and characterized with scanning electron microscopy, Transmission electron microscopy, energy dispersive X‐Ray analysis, X‐Ray Diffraction and Fourier transform infrared spectroscopy. Anion recognition studies were performed for CNT@Ni nano‐hybrid, a significant response was observed for Cyanide ion (CN⁻) detection and exhibited a detection limit of 7.2 nM. Further, detected CN⁻ was electrochemically reduced to non‐toxic OCN⁻ in order to prevent the environment from its toxic effects while disposing off.
In this study, Co, Cu, Pd, and Pd/Cu composite metal ions were used to synthesize metal nanoparticles with high efficiency in purifying hydrogen cyanide gas. The pure liquid phase catalytic purification of hydrogen cyanide gas was studied. According to the removal rate, the Pd/Cu composite metal ions had the best purification efficiency among the nanoparticles of different metal types. The removal rate order was Pd/Cu>Pd>Cu>Co. The gas after reaction were analyzed by gas chromatography, and it was found that HCN was converted into CO2, N2 and NH3 by nanoparticles. Then, Pd/Cu composite metal ions with the highest purification efficiency were used to study the electrochemical synergistic liquid-phase catalytic purification of HCN gas. The effects of electrochemical conditions and current on the electro-hydraulic synergistic purification were studied. The removal efficiency of HCN by electrochemical synergistic liquid phase catalysis was better than that by pure liquid phase catalysis. The different nanoparticles before and after HCN absorption were characterized and analyzed to explore the purification process of HCN. The purification mechanism of hydrogen cyanide by Pd-Cu catalyst under applied voltage was studied under certain conditions. During the catalytic reaction, the nano-catalyst was partially dissolved in liquid phase and partially HCN reacts with metal ions on the free or nanoparticles to form complex [Mc(CN)n]2-n. Homogeneous and quasi-homogeneous reactions in liquid phase interweave together to form a more complex reaction system.
Chemical warfare agents (CWAs) have lately been used in the Syrian Arab Republic, the Republic of Iraq, Malaysia, and the United Kingdom. In the two latter cases, normal investigation by authorities, such as evidence collection and identification of unknown materials found at the crime scenes, was possible. However, in Syria and Iraq the inspectors from the Organization for the Prohibition of Chemical Weapons (OPCW) collected evidence in a hostile environment and under tight time constraints. The collected samples were analyzed at the OPCW’s designated laboratories under a strict scope of analysis. The verification protocol for determining the presence or absence of Chemical Weapons Convention (CWC) related chemicals includes sample preparation followed by analysis by different chromatographic, spectrometric, and spectroscopic techniques. According to the rules of the OPCW for the sample analyses, the identification is considered unambiguous if two different analytical techniques giving consistent results confirm the presence of the same chemical.
Cyanogen (C2N2) is a new soil fumigant being tested worldwide for soil fumigation or sterilization before planting. This study established a multi-fumigant detection method for C2N2 and its degradation product hydrogen cyanide (HCN) by gas chromatography–mass spectrometry (GC–MS). The GC–MS method was then applied to investigate the degradation of C2N2 and HCN in eight different agricultural soils. The optimal headspace sampling conditions using a Box–Behnken experimental design were an extraction temperature of 60 °C, an extraction time of 0.7 h, and a solvent volume of 35 mL (30% H2SO4). Under these conditions, the extraction rates of C2N2 and HCN were 89.22% ± 0.65% and 92.50% ± 0.63%, respectively. The limits of quantification for both target compounds were 0.001 mg·kg⁻¹. The recoveries of C2N2 and HCN ranged from 84.7% to 102.9% and from 80.18% to 95.34%, respectively, at spiked levels of 0.05, 0.2, and 1.0 mg·kg⁻¹ with relative standard deviation ≤2.2%. A residual dynamics experiment showed that C2N2 and HCN disappeared rapidly in the soils. The first-order double-exponential decay model best described the decline of C2N2 and HCN concentrations in soil. The half-lives of C2N2 and HCN in soil were 8.553–27.964 h and 11.823–35.674 h, respectively. The GC–MS method provides a simple, fast, and organic solvent-free procedure to analyze multiple fumigants in the soil matrix. The proposed method is therefore recommended as a screening tool for the field investigation of C2N2- and HCN-fumigated sites.
Supramolecular assemblies of cyclopentadienone derivative 3 exhibit cyanide induced emission enhancement and undergo modulation of self-assembled structure to generate ‘metal free’ supramolecular porous anionic assemblies. The as prepared anionic assemblies show high sensitivity and selectivity for the detection of picric acid among various nitro-derivatives tested in aqueous media and in vapour phase. Further, due to the porous nature, the anionic ensemble selectively detects cationic dyes such as methylene blue among various dyes tested in aqueous media.
In recent years, developing countries have increased their cassava (Manihot esculenta) production for food security. Cassava contains cyanogen glycosides, mainly as linamarin, which through biocatalysis, i.e. enzyme hydrolysis, results in hydrogen cyanide (HCN). HCN is released into the environment through numerous ways with subsequent volatilisation. Thus, the HCN released during the period 2002–2013 was estimated between 0.025 × 10 −3 to 6.71 ppq (African), 0.012 × 10 −3 to 1.01 ppq (Asian) and 0.007 × 10 −3 to 0.920 × 10 −3 ppq (South American). Furthermore, a decade’s (2014–2024) projection of HCN volatilisation displays increases of 60.5% (Africa), 57.7% (Asia) and 50.5% (South America) when compared with the current production. Furthermore, gas released during cassava plants’ growth, i.e. HCN, NH3, and NO2, was quantified in healthy plants. Varying concentrations of HCN were released. These further indicated the presence of a pseudohalogenic gas in the environment – a contributor to climate change.
Cyanide has been used as a poison for thousands of years. Symptoms of cyanide poisoning begin quickly and death occurs within minutes. In this study, we review 52 cyanide poisoning cases in Tehran, Iran, over a four-year interval, from 30 December 2009 to 1 January 2014. Toxicological analysis and post-mortem findings are discussed. Colour test (Prussian Blue) was used for screening for cyanide with confirmation using the voltammetry method. The youngest decedent was a 2-month old girl. Men constituted 76.9% (40) of the total 52 victims. Peak age prevalence of cases was seen in age groups 21-40 years (32 cases, i.e. 61.5%). Methadone and opioid alkaloids were the most common drugs detected in biological samples in this study. A suicide attempt was the main cause of poisoning in 33 cases. The results showed that cyanide-poisoning-related deaths are among the most public health problems in Iran. Restricted access to cyanide and stricter buying and selling controls may reduce intentional self-poisoning with this dangerous substance.
Asphyxiants deprive the body of oxygen. Simple asphyxiants displace oxygen from the lungs, whereas systemic asphyxiants interfere with transport of oxygen by hemoglobin or with mitochondrial oxidative phosphorylation. Asphyxiants may be gases, liquids, or solids, or their metabolites. The typical clinical picture of asphyxiant poisoning is one of progressive mental status changes, alteration of breathing, progressively abnormal vital signs, coma, seizures, and eventually cardiovascular collapse and death. Treatment of asphyxiant poisoning is aggressive supportive care, with control of the airway and ventilation and maintenance of cardiac output. Supportive care is often enhanced by the administration of specific antidotes.
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A hexaphenylbenzene based receptor 3 has been synthesized which forms fluorescent spherical aggregate in mixed aqueous media due to its aggregation induced emission enhancement (AIEE) attributes. These fluorescent spherical aggregates show ratiometric response towards cyanide ions via nucleophilic addition and undergo deaggregation to form smaller nanoaggregates. In addition, the solution coated paper strips of 3 can detect cyanide ions in the range of ∼2.6 ng/cm2; thus, providing a simple, portable and low cost method for detection of cyanide ions in aqueous media. Receptor 3 also behaves as a set-reset memorized sequential logic circuit with chemical inputs of CN- ions and trifluoroacetic acid (TFA) or H+ (pH ≤ 3).
Fluorescent nanorods formed by self-assembly of hexaphenylbenzene derivative in the presence of cyanide ions serve as a sensitive colorimetric and fluorogenic sensor for the detection of trinitrotoluene (TNT) at the attogram (10(-18) g) level with a detection limit of 10.21 ppq (parts per quadrillion).
Hydrogen sulphide poisoning can occur in industrial/occupational (oil refining, viscose rayon manufacturing, vulcanization of rubber, hydrochloric acid in farm wells, leather industry, sewage cleaning, roofing asphalt tanks, etc), recreational (cleaning of hot spring reservoirs, caves, sulfur springs, etc), or hospital (plaster of Paris, etc) settings. The first reports date from the 17th century where city sewage cleaners were found dead in the vicinity of the sewers. At a concentration of 0–25 ppm H2S has a specific odour of rotten eggs. This odour is an unreliable marker since at higher concentrations (> 100 ppm) the gas rapidly causes paralysis of (the olfactory system resulting in anosmia. At concentrations > 50 ppm symptoms are characterized by mucositis (conjunctivitis, upper airway irritation), nausea and dizziness, at > 200 ppm pulmonary edema can occur, at > 500 ppm neurologic problems arise (agitation, seizures followed by coma), at > 1000 ppm sudden death can occur. Main target organs are the central nervous system (CNS) and the respiratory system. Acute high dose intoxication mainly results in CNS problems whereas chronic lower dose intoxication results in acute lung injury (ALI) or acute pulmonary edema, the latter carrying a worse prognosis. There is still a great controversy in the literature about the best treatment and little is known about long time CNS and pulmonary complications in survivors.
We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental and occupational health. These parent CW agents include several vesicants: sulfur mustards [undistilled sulfur mustard (H), sulfur mustard (HD), and an HD/agent T mixture (HT)]; nitrogen mustards [ethylbis(2-chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)], and Lewisite; four nerve agents (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX), tabun (GA), sarin (GB), and soman (GD)); and the blood agent cyanogen chloride. The degradation processes considered here include hydrolysis, microbial degradation, oxidation, and photolysis. We also briefly address decontamination but not combustion processes. Because CW agents are generally not considered very persistent, certain degradation products of significant persistence, even those that are not particularly toxic, may indicate previous CW agent presence or that degradation has occurred. Of those products for which there are data on both environmental fate and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation products estimated to be of significant persistence (weeks to years) include thiodiglycol for HD; Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly S-(2-diisopropylaminoethyl) methylphosphonothioic acid (EA 2192) for VX. Methyl phosphonic acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl methylphosphonic acid, and a closely related contaminant of GB, diisopropyl methylphosphonate, are also persistent. Of all of these compounds, only Lewisite oxide and EA 2192 possess high mammalian toxicity. Unlike other CW agents, sulfur mustard agents (e.g., HD) are somewhat persistent; therefore, sites or conditions involving potential HD contamination should include an evaluation of both the agent and thiodiglycol.
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A convenient analytical procedure based on one-step, phase-transfer- catalyzed derivatization has been established for the simultaneous determination of azide, cyanide and thiocyanate in aqueous samples by gas chromatography - mass spectrometry (GC-MS). In order to obtain cleaner extracts, a polymer-bound phosphonium salt was employed as the catalyst, and pentafluorobenzyl bromide (PFB-Br) as a derivatization reagent. The extraction and derivatization of these analytes, as well as the concentration of the resultant derivatives into the organic phase were simultaneously achieved during a 30-min phase-transfer-catalyzed process at 38°C. Rapid and reliable GC-MS determination could be readily performed for these analytes, not only in various beverages but also in diluted, large-volume aqueous samples such as food washings. In addition to electron impact ionization MS (EI-MS), negative-ion chemical ionization MS (NICI-MS) was also employed to detect trace-level analytes, as well as to accomplish incontrovertible identification. The detection limits in various beverages were typically 0.1- 0.5 μg/ml by EI-MS and 25-100 ng/ml by NICI-MS, both in the full-scan mode.
A summary is presented of recently published, critically evaluated experimental vibrational and electronic energy level data for neutral and ionic transient molecules and high temperature species possessing from three to sixteen atoms. Although the emphasis is on species with lifetimes too short for study using conventional sampling techniques, there has been selective extension of the compilation to include data for isolated molecules of inorganic species such as the heavy-metal oxides, which are important in a wide variety of industrial chemical systems. Radiative lifetimes and the principal rotational constants are included. Observations in the gas phase, in molecular beams, and in rare-gas and diatomic molecule matrices are evaluated. The types of measurement surveyed include conventional and laser-based absorption and emission techniques, laser absorption with mass analysis, and photoelectron spectroscopy. Not counting isotopic species, 904 molecules are surveyed, and 2696 distinct references are given. © 1998 American Institute of Physics and American Chemical Society.
New information on the experimentally determined vibrational and electronic energy levels of approximately 500 neutral and ionic transient molecules possessing from 3 to 16 atoms has been evaluated and added to the previously established database for these species. There has been selective extension of the compilation to somewhat less reactive species such as HNCO, HCNO, H2O2, and cis- and trans-HONO, as well as to many transient molecules which include atoms beyond the third row of the Periodic Table. Electronic spectral data are also given for a number of transient molecules which possess more than six atoms. Radiative life-times and the principal rotational constants are included. Observations in the gas phase, in molecular beams, and in rare-gas and nitrogen matrices are evaluated. The types of measurement surveyed include conventional and laser-based absorption and emission techniques, laser absorption with mass analysis, and photoelectron spectroscopy.
The rate of cyanogen hydrolysis in base is first order in OH- and first order in (CN)2, but the reaction proceeds by two paths. Only 25% at 5°C to 33% at 40°C of the cyanogen reacts directly by C-C bond cleavage to give CN- and OCN- (k1 = 8.9 × 102 M-1 s-1 at 25.0°C, Ea = 15.8 kcal mol-1). The rest of the cyanogen forms 1-cyanoformamide via a second path (k2 = 2.17 × 103 M-1 s-1 at 25.0°C, Ea = 13.8 kcal mol-1). A common reactive intermediate, N≡CC(OH)=N-, is postulated for the k1 and k2 paths. The 1-cyanoformamide that forms also decomposes by C-C bond cleavage, but at a much slower rate than cyanogen. The reaction proceeds by deprotonation of 1-cyanoformamide (pKa = 10.8) to give N≡CC(=O)NH-, which reacts to give CN- and OCN- (k3 = 0.556 s-1 at 25.0°C, Ea = 22.5 kcal mol-1).
The extreme toxicity of cyanide and environmental concerns from its continued industrial use continue to generate interest in facile and sensitive methods for cyanide detection. In recent years, there is also additional recognition of HCN toxicity from smoke inhalation and potential use of cyanide as a weapon of terrorism. This review summarizes the literature since 2005 on cyanide measurement in different matrices ranging from drinking water and wastewater, to cigarette smoke and exhaled breath to biological fluids like blood, urine and saliva. The dramatic increase in the number of publications on cyanide measurement is indicative of the great interest in this field not only from analytical chemists, but also researchers from diverse environmental, medical, forensic and clinical arena. The recent methods cover both established and emerging analytical disciplines and include naked eye visual detection, spectrophotometry/colorimetry, capillary electrophoresis with optical absorbance detection, fluorometry, chemiluminescence, near-infrared cavity ring down spectroscopy, atomic absorption spectrometry, electrochemical methods (potentiometry/amperometry/ion chromatography-pulsed amperometry), mass spectrometry (selected ion flow tube mass spectrometry, electrospray ionization mass spectrometry, gas chromatography-mass spectrometry), gas chromatography (nitrogen phosphorus detector, electron capture detector) and quartz crystal mass monitors.
An uncommon suicide by oral ingestion of potassium cyanide salts and contemporaneous inhalation of hydrogen cyanide is presented. A 48-year-old tradesman was found dead sitting in his car. A penetrating odor of bitter almonds was noticed when opening the doors. A camping stove and a cooking pot containing large amounts of dark blue crystals were found in the footwell of the car. White powder adhered to his fingers and to the area around the mouth. Furthermore bottles containing potassium ferrocyanide and different kinds of acid and leach were found in the car together with internet information about, e.g. potassium ferrocyanide and potassium cyanide. At autopsy hemorrhages and erosions of the mucosa of the respiratory tract, esophagus and stomach were found. Concentrations of cyanide were 0.2mg/l in stomach contents, 0.96mg/kg in brain tissue, 2.79mg/kg in lungs, and 5.3mg/l in blood. The white and toxic powder potassium cyanide was formed by heating of the yellow crystals of potassium ferrocyanide on the camping stove. This powder was probably ingested orally. Addition of acid converted the salt into the highly toxic gas hydrogen cyanide. Oxidation with atmospheric oxygen built the dark blue ferrous compound Prussian blue. This case report of a person who was not familiar with chemicals demonstrates the acquisition of professional information via the internet, enabling a suicide with a complex procedure.
The hydrolysis of cyanogen chloride (ClCN) was studied as a function of temperature and pH. Results were used to resolve discrepancies among previously reported kinetic constants. The pH dependence was studied over a range of 9.54-10.93 at a temperature of 21.0 degrees C. The effect of temperature was investigated over the range of 10-30 degrees C at a pH of approximately 10. Changes in the concentrations of ClCN and the reaction products cyanic acid and chloride ion were monitored with time. For the conditions corresponding to these experiments, the hydroxide-assisted hydrolysis pathway predominated. Collision frequency factor and activation energies recommended to represent the hydrolysis of ClCN in aqueous solution are A = 2.06 x 10(11) M-1 s-1 and Ea = 60,980 J mol-1 for the hydroxide-ion-assisted reaction, and A = 9.97 x 10(8) s-1 and Ea = 87,180 J mol-1 for the water-assisted reaction.
Cyanide is a likely weapon for terrorists due to its notoriety, lethality, and availability. Poisoning results in central nervous system and cardiovascular dysfunction due to inhibition of oxidative phosphorylation. Laboratory findings of anion gap metabolic acidosis and hyperlactemia aid in confirming the diagnosis. Treatment for significant poisonings includes aggressive supportive care and administration of antidotes such as sodium nitrite, sodium thiosulfate, and hydroxocobalamin. Survivors of significant poisonings can have long-term neurologic dysfunction.
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Occupational Safety and Health Administration web site
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Textbook of Military Medicine: Medical Aspects of Chemical Warfare, Office of The Surgeon General at TMM Publications
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Chemical Warfare, Office of The Surgeon General at TMM Publications, Borden
Institute, Washington, DC, 2008, pp. 371-410.
Concise International Chemical Assessment Document 61: Hydrogen Cyanide and Cyanides: Human Health Aspects
WHO, Concise International Chemical Assessment Document 61: Hydrogen Cyanide and Cyanides: Human Health Aspects, International Programme on Chemical Safety, World Health Organization, Geneva, 2004.