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1.
Mar Environ Res ; 162: 105160, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33011584

RESUMO

Recently, sea-dumped chemical weapons (CWs) containing toxic chemical warfare agents (CWAs) have raised international attention. It is well known that CWAs are leaking from corroded munitions causing a risk to the surrounding marine environment, while the impact on marine biota is still unknown. In this study, cod (Gadus morhua) was used as a model species to study the possible bioaccumulation of phenylarsenic CWAs and their negative effects at multiple levels of biological organization on fish living in the vicinity of a major CWs dumpsite in the Bornholm Basin in the Baltic Sea. In total, 14% of the cod muscle samples collected close to the main dumpsite contained trace levels of phenylarsenic CWAs. However, most of the biomarkers measured did not show clear differences between this area compared with a lesser contaminated reference area. On the other hand, significant changes in some biomarkers were observed in individuals containing trace levels of CWA-related chemicals. The results gained in this study have significant importance for environmental risk assessment and for evaluating the risk of CWA contamination for human seafood consumers.


Assuntos
Substâncias para a Guerra Química , Gadus morhua , Poluentes Químicos da Água , Animais , Países Bálticos , Substâncias para a Guerra Química/análise , Monitoramento Ambiental , Humanos , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
2.
Mar Environ Res ; 161: 105046, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33070929

RESUMO

Within the framework of the international project DAIMON (Decision Aid for Marine Munitions), the impact of dumped chemical munitions on fish health was investigated. The Skagerrak Straight (North Sea, at 600 m depth) contains munitions with chemical warfare agents (CWA), scuttled after the end of World War II. Studies of liver histopathology in Atlantic hagfish (Myxine glutinosa) were carried out at three sampling sites: at a wreck with CWA in the Skagerrak (n = 82), a Skagerrak reference site considered to be free of CWA (n = 14) and at a reference site in the northern North Sea outside the Skagerrak (n = 17). Liver lesions were diagnosed and categorized according to standardized ICES and BEQUALM protocols and OSPAR guidelines. Non-specific liver lesions were found in 87.6% of 113 hagfish examined. The prevalence of pre-neoplastic lesions was 7.1% and of neoplastic lesions 6.2%. There was no statistically significant difference in prevalence between hagfish samples from the wreck site and from the reference site near the wrecks. However, at the reference site in the northern North Sea, the prevalence of non-specific lesions was low and neither pre-neoplastic nor neoplastic lesions were observed.


Assuntos
Substâncias para a Guerra Química , Feiticeiras (Peixe) , Animais , Substâncias para a Guerra Química/análise , Monitoramento Ambiental , Peixes , Fígado/química , Espécies Sentinelas
3.
Mar Environ Res ; 162: 105097, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32992222

RESUMO

The sea bottom of the Skagerrak Strait (North Sea) contains munitions loaded with chemical warfare agents (CWA), mostly stored in shipwrecks scuttled intentionally after the end of the World War II. The munition shells inside the wrecks are in different states of deterioration and corrosion and their environmental risk potential is unknown. The Atlantic hagfish (Myxine glutinosa), a sediment-dwelling chordate, was used as a model organism to study the potential impact of dumped CWA on the local ecosystem by using biochemical biomarkers. The hagfish were collected in 2017 and 2018 at three sampling sites: in the immediate vicinity of a wreck with CWA in the Skagerrak, a few kilometres from the wreck, and a reference site 21 km from the wreck, considered to be free of CWA. Significant differences were observed between the wreck site and the reference sites in the activities of glutathione reductase, superoxide dismutase and glutathione S-transferase, while the activity levels of catalase and acetylcholinesterase were identical at all sites. The recorded differences demonstrated negative biological effects in the hagfish sampled close to the dumped chemical munitions. Due to the limited knowledge of hagfish biology and of the extent of CWA contamination in Skagerrak, the results presented here warrant more research to further elucidate the potential environmental risks of the scuttled wrecks. The usefulness of the species as a bioindicator organism is further discussed.


Assuntos
Substâncias para a Guerra Química , Feiticeiras (Peixe) , Animais , Biomarcadores , Substâncias para a Guerra Química/análise , Ecossistema , Mar do Norte , Espécies Sentinelas
4.
Mar Environ Res ; 161: 105079, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32877876

RESUMO

The leakage of any substances at the sea bottom consequently leads to contamination. The polluted area will strongly depend on the type of pollution which can be dissolved, material and the physical state of the bottom layers. Although the systems that monitor the particles or pollution on the sea surface already exists, there is no similar tool for the bottom area. This work aims at developing the High Resolution Dispersion Model (HRDM) that calculates transport of the pollution in case of potential leakage from chemical ammunition dumped into the Baltic Sea. The model has been embedded into existing operational system that covers the whole region of the Baltic Sea. Thus, it consists of the three main elements: operational atmospheric model that makes calculations every day, coupled ice-ocean model covering the whole Baltic Sea area and HRDM. The horizontal resolution of the atmospheric part is about 10 km, the coupled system is driven on 2.3 km grid and HRDM is implemented on 50 m horizontal resolution. The clients are able to make integration since 2014. Access to the system is granted via REpresentational State Transfer (REST) API that separates user interface from the server site. It is possible to make simulations for instantaneous and continuous type of leakage. The results are served in binary form (as a netcdf file) and as a georeferenced tiff picture. The temporal resolution of the output data is 1 h. The HRDM consists of half-life of sulfur mustard and the results for both - with and without half-life calculations are included in the output files. The HRDM has been created as a part of Decision Support System and is not (and will not be) available for public.


Assuntos
Substâncias para a Guerra Química , Países Bálticos , Substâncias para a Guerra Química/análise
5.
Mar Environ Res ; 161: 105112, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32861968

RESUMO

About 50 000 tons of chemical weapons (CW) were dumped to the Baltic Sea after the Second World War. Munitions are located in the deep areas of the Baltic Sea, and there they act as a point source of contamination to the ecosystem. Corroded munitions release chemical warfare agents (CWAs) to nearby water and sediments. In this study we investigated known dumpsites (Bornholm, Gotland and Gdansk Deep) and dispersed chemical munitions, to evaluate the extent of contamination of nearby sediments, as well as to assess the degradation process of released CWA. It was found that CWA-related phenylarsenic chemicals (Clark I, Clark II and Adamsite) and sulfur mustard are released to the sediments and undergo environmental degradation to chemicals, of which some remain toxic. The extent of pollution of released CWAs and their corresponding degradation products reaches more than 250 m from the CW objects, and seem to follow a power curve decrease of concentration from the source. Bornholm Deep is characterised with the highest concentration of CWAs in sediments, but occasional concentration peaks are also observed in the Gdansk Deep and close to dispersed munitions. Detailed investigation of spreading pattern show that the range of pollution depends on bottom currents and topography.


Assuntos
Substâncias para a Guerra Química , Poluentes Químicos da Água , Países Bálticos , Substâncias para a Guerra Química/análise , Substâncias para a Guerra Química/toxicidade , Ecossistema , Sedimentos Geológicos , Poluentes Químicos da Água/análise
6.
Mar Environ Res ; 161: 105077, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32853855

RESUMO

Sulphur mustard (HD) was the most widely produced chemical warfare agent (CWA) in the history of chemical warfare (CW). Simultaneously, the loads of HD account as by far the largest fraction of the sea-dumped CW. Nowadays its presence in the marine ecosystems recognized as a serious threat for marine users and maritime industries. Although, during over a decade of research much has been done to assess the environmental threats linked with underwater chemical munitions. There are, however, essential gaps in scientific knowledge including scarce information about the aquatic toxicity thresholds of HD and its degradation products. Standardized biotests were performed according to the Organisation for Economic Co-operation and Development (OECD) Test No. 202: Daphnia sp. Acute Immobilisation Test guidelines. Obtained results provide a solid foundation for comparison and categorisation of threats of HD and its degradation products. With the D. magna LC50 aquatic acute toxicity threshold at as low as 224 ± 12 µg × L-1, 1,2,5-trithiepane is very toxic, being one of the most toxic CWA degradation products that have been investigated up to date. It exhibits stronger effects than 1,4,5-oxadithiepane and diluted HD that turn out to be toxic. In total, the toxicity of 7 compounds has been estimated. Whenever possible, toxicity thresholds were compared with previously existing data originating from different biotests and mathematical modelling.


Assuntos
Substâncias para a Guerra Química , Gás de Mostarda , Poluentes Químicos da Água , Animais , Substâncias para a Guerra Química/análise , Substâncias para a Guerra Química/toxicidade , Daphnia , Ecossistema , Dose Letal Mediana , Gás de Mostarda/análise , Gás de Mostarda/toxicidade , Testes de Toxicidade Aguda , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
7.
J Anal Toxicol ; 44(4): 391-401, 2020 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-32103269

RESUMO

A recently proposed model for the incorporation of xenobiotics of forensic interest into the human skeleton suggests nerve agent metabolites may incorporate into bone at relatively elevated concentrations based on their unique chemical properties. To test the hypothesis that nerve agent metabolites interact with bone, methods for the extraction, isolation and semi-quantitative detection of nerve agent metabolites (MPA, EMPA, IMPA, iBuMPA, CMPA and PMPA, corresponding to the nerve agents VX, Russian VX, sarin, cyclosarin and soman, respectively) from osseous tissue were developed using liquid chromatography-mass spectrometry with both quadrupole time-of-flight and triple quadrupole (QqQ) instruments. The optimized methods were validated on the QqQ instrument. Despite high ion suppression, the achieved limits of detection (5-20 pg/g for four analytes; 350 pg/g for the fifth analyte) were lower than many of those published for the same analytes in other biomatrices, including serum and urine. These methods were tested on the skeletal remains of minipigs exposed to the chemical weapon VX in vivo. The VX metabolite was detected in multiple minipig bone samples; to the authors' knowledge, this is the first time in vivo nerve agent exposure has been detected from bone. Further, detected concentrations and diaphyseal-to-epiphyseal area count ratios reflect animal exposure history. Although the results are limited, they are promising, indicating that nerve agent metabolites may interact with bone as a pharmacokinetic compartment and can be extracted from bone postmortem. Additional studies, assessing the effects of different agents, exposure pathways and taphonomic variables, are needed; however, these results suggest the method may be used with human bone to detect use of chemical weapons from postmortem biomatrices even well after a suspected attack. More general implications for both nerve agent toxicology and skeletal toxicology are also discussed.


Assuntos
Osso e Ossos/química , Agentes Neurotóxicos/análise , Animais , Substâncias para a Guerra Química/análise , Cromatografia Líquida , Humanos , Limite de Detecção , Compostos Organofosforados/análise , Compostos Organotiofosforados/análise , Sarina/análise , Soman/análise , Suínos
8.
Anal Bioanal Chem ; 412(5): 1097-1110, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31907592

RESUMO

A three-layered composite wipe was fabricated by laminating individual layers of non-woven polypropylene, activated carbon fabric (ACF) and aramid fabric for the sampling and investigation of chemical warfare agents (CWA)-contaminated urban porous and non-porous surfaces. The material of main ACF layer was characterized to ascertain its suitability to act as an efficient adsorbent for the surface wipe sampling. The performance of ACF-based composite wipe was determined by evaluating its extraction efficiency, wiping efficacy and adsorption capacity for the sampling of blister and nerve agent class of CWA-contaminated surfaces using gas chromatography-mass spectrometry (GC-MS). Parameters like amount of wipe required, solvent selection, amount of solvent, time of extraction etc. were optimized to achieve the maximum recovery of contaminating analytes required for the forensic investigations. Overall recoveries of contaminating analytes after sampling and extraction were found to be in the range of 45-85% for all types of surfaces. No breakthrough in wiping process was noticed up to contamination density (CD) 1.6 mg/cm2 for non-porous surface and 3.2 mg/cm2 for porous surfaces. ACF-based wipe was found capable to significantly reduce the vapour hazards from liquid sulphur mustard (HD) and sarin (GB). Contamination from surfaces could be preserved within the wipe up to 15 days for the extended forensic investigation purposes. Limit of detections (LOD) of contaminants was determined in the range of 0.8-6.8 ng/cm2 while limit of quantitation (LOQ) was achieved up to the range of 2.4-14.4 ng/cm2 for wipe sampling of different surfaces. Graphical abstract.


Assuntos
Substâncias para a Guerra Química/análise , Gás de Mostarda/análise , Sarina/análise , Manejo de Espécimes/instrumentação , Têxteis , Adsorção , Monitoramento Ambiental/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Limite de Detecção , Microscopia Eletrônica de Varredura , Padrões de Referência , Solventes/química , Propriedades de Superfície
9.
Artigo em Inglês | MEDLINE | ID: mdl-31670058

RESUMO

Human studies investigating the efficacy of emergency decontamination protocols for chemical incidents require the use of non-hazardous chemical simulants. Methyl salicylate (MeS) has almost exclusively been used for this purpose. Whilst MeS is a simulant of the chemical warfare agent (CWA) sulphur mustard, it is not an ideal simulant for many other chemical threats with greater persistence and lower volatility. Benzyl salicylate (BeS) has been investigated here as a low toxicity simulant for lower volatility, persistent chemical threat agents and toxic industrial chemicals (TICs). To evaluate the suitability of BeS as a simulant for human decontamination studies a gas chromatography-triple quadrupole mass spectrometry method was designed, optimised and validated, for the analysis of human skin and hair. Quantification was achieved using isotope-dilution, EI and collision-induced dissociation and multiple reaction monitoring for both qualifier and quantifier ion transitions. The mass transitions were m/z 285 → 91 and m/z 210 → 181, respectively for the quantifier and qualifier ions of BeS, and m/z 289 → 91 and m/z 214 → 185 for the quantifier and qualifier ions for the BeS-d4 internal standard, respectively. The method exhibited excellent coefficients of determination (R2 = 0.9992-0.9999) with LOD and LOQ values at 0.023 ng/ml and 0.23 ng/ml. Across three Quality Controls (QCs), 11.5 ng/ml, 115 ng/ml and 1150 ng/ml) average accuracy (intra-day 95.6-100.3%, inter-day 98.5-104.91%) and precision (intra-day RSD (%) 2-13.7%, inter-day RSD (%) 3.3-8.8%) were determined. The validated method was applied in a proof of principle volunteer study for the determination of total BeS recovered from skin and hair. The average total BeS recovery after 70 min was 37.9% from skin and there was a significant increase between baseline and post-intervention levels for hair. These data demonstrate that BeS is an appropriate simulant for persistent chemicals and that the analytical method employed here is suitable for BeS analysis in human studies.


Assuntos
Substâncias para a Guerra Química/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Salicilatos/análise , Espectrometria de Massas em Tandem/métodos , Adulto , Descontaminação/métodos , Feminino , Cabelo , Humanos , Marcação por Isótopo/métodos , Masculino , Pessoa de Meia-Idade , Reprodutibilidade dos Testes , Pele
10.
Chemistry ; 25(51): 11892-11902, 2019 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-31309626

RESUMO

Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response-recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co3 O4 functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co3 O4 micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co3 O4 -HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co3 O4 and Co3 O4 sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co3 O4 -HFIP. The rGO/Co3 O4 -HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic-organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials.


Assuntos
Substâncias para a Guerra Química/análise , Óxidos/química , Propanóis/química , Substâncias para a Guerra Química/química , Gases , Grafite , Compostos Orgânicos
11.
Anal Chim Acta ; 1077: 1-13, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31307698

RESUMO

UV photoionization (UV-PI) is a promising non-radioactive ionization method for ion mobility spectrometry (IMS). It could work at either direct photoionization mode or chemical ionization mode by adding photoionizable dopants, and thus its applications extend to a wide range of compound classes. This work is to present a comprehensive review on the development of UV-PI-IMS. It focuses on UV-PI's capabilities and how to use them fully. A summary discussion of the ionization processes in UV-PI would be presented first for understanding the fundamentals of UV-PI-IMS. Followed by descriptions of the technical configurations of UV-PI source in IMS. Improvements in the design of UV-PI source for achieving optimum results will be presented with references to examples. Further, a broad range of applications, including environmental contaminants analysis, trace explosives and chemical warfare agents detection, food safety and quality analysis, and clinical diagnosis, would be presented to demonstrated the analytical performance of UV-PI-IMS. In the conclusion, perspectives on areas of UV-PI technique which have the potential to be improved would be reasonably presented.


Assuntos
Espectrometria de Mobilidade Iônica/métodos , Animais , Substâncias para a Guerra Química/análise , Poluentes Ambientais/análise , Substâncias Explosivas/análise , Contaminação de Alimentos/análise , Humanos , Raios Ultravioleta , Compostos Orgânicos Voláteis/análise
12.
Yakugaku Zasshi ; 139(5): 685-691, 2019.
Artigo em Japonês | MEDLINE | ID: mdl-31061336

RESUMO

The precise proof of a crime using objective evidence is becoming increasingly important as Japan's crime rate climbs. This need arises not only from the current high rate of anonymous crime, but also the introduction of a Saiban-in (citizen judge) system, and the increased silence of suspects following investigation visualization. Forensic science is an academic field that investigates legal (and illegal) matters using science, and subsequently applies research results to resolving real crime cases. Materials examined during forensic practice include both common specimens, such as fingerprints, footprints, blood stains, and hairs, and less common specimens, such as soils, plants, dust, and pollens. In the event of biological, chemical, or explosive terrorism, air and surface wipe specimens-possibly containing chemical warfare agents, microbes, and explosives-can become critical target materials. Alternatively, on discovering powders and/or liquids that are suspected to be illegal drugs, preliminary tests are performed at the crime scene itself. Subsequently, confirmatory examinations are performed at a forensic science laboratory. Current research efforts are underway to develop simpler and more reliable tools for on-site drug testing, and to develop analytical methods capable of differentiating regioisomers of drugs, performing drug metabolism studies as a way to identify drugs of abuse, and studying the organic synthesis of authentic standard compounds. In this review, we outline current state-of-the-art technologies in forensic chemistry.


Assuntos
Ciências Forenses , Substâncias para a Guerra Química/análise , Crime/legislação & jurisprudência , Crime/estatística & dados numéricos , Ciências Forenses/métodos , Humanos , Drogas Ilícitas/análise , Japão/epidemiologia , Espectrometria de Massas , Metanfetamina/análise
13.
Yakugaku Zasshi ; 139(5): 715-724, 2019.
Artigo em Japonês | MEDLINE | ID: mdl-31061340

RESUMO

As a countermeasure against terrorism involving highly toxic chemical warfare agents, the rapid identification of the causative toxic substances is extremely important. This symposium review describes analytical methods the author's group has developed for detecting nerve gases after either high level or low level exposure. As a method for assessing human exposure to high levels of nerve gases, a technology that detects nerve gas hydrolysis products, i.e., strong anion exchange extraction-tert-butyldimethylsilyl derivatization-selectable one-dimensional or two-dimensional GC-MS, is explained. As a method for assessing human exposure to low levels of nerve gases, two technologies that detect adducts of nerve gas with blood cholinesterase, i.e., adduct purification-enzymatic digestion-LC/MS and fluoride-mediated regeneration-solid phase extraction-large volume introduction GC-MS, are explained.


Assuntos
Terrorismo Químico/prevenção & controle , Substâncias para a Guerra Química/análise , Substâncias para a Guerra Química/isolamento & purificação , Exposição Ambiental/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Agentes Neurotóxicos/análise , Agentes Neurotóxicos/isolamento & purificação , Extração em Fase Sólida/métodos , Substâncias para a Guerra Química/metabolismo , Substâncias para a Guerra Química/toxicidade , Exposição Ambiental/efeitos adversos , Humanos , Hidrólise , Agentes Neurotóxicos/efeitos adversos , Agentes Neurotóxicos/metabolismo
14.
Spectrochim Acta A Mol Biomol Spectrosc ; 219: 129-134, 2019 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-31030040

RESUMO

Since the introduction of a benchtop vacuum ultraviolet (VUV) absorption spectroscope with an increased wavelength range towards to the high energetic ultraviolet radiation, gas chromatography coupled to VUV has been proven a powerful tool in several fields of application such as petroleomics, permanent gas analytic, pesticide analytic and many more. In this study, the potential of GC-VUV for investigations was examined, focusing on drug- and explosive precursors as well as chemical warfare simulants. The ability of VUV absorption spectra to differentiate isomers is presented, among others for nitroaromatics. In addition, the limit of detection for target compounds was determined to 0.7 ng absolute on column. Furthermore, non-negative matrix factorization (NMF) was successfully implemented as alternative deconvolution approach and evaluated for the deconvolution of unknown substances. In comparison, the spectral library-based deconvolution was applied to a standard mixture and a simulated case study. The results reveal that the NMF is a useful additional tool for deconvolution because, unlike library-based deconvolution, it allows to investigate unknown substances as well.


Assuntos
Substâncias para a Guerra Química/análise , Cromatografia Gasosa/métodos , Substâncias Explosivas/análise , Preparações Farmacêuticas/análise , Espectrofotometria Ultravioleta/métodos , Isomerismo , Vácuo
15.
Anal Bioanal Chem ; 411(15): 3405-3415, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-31011788

RESUMO

Sulfur mustard (HD) reacts with human serum albumin (HSA) at Cys34 and produces a long-term biomarker of HD exposure. Here, we present a novel, sensitive, and convenient method for quantification of HD exposure by detection of HD-HSA adducts using pronase digestion, benzyl chloroformate (Cbz-Cl) derivatization, and ultra-high-pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). The HSA in HD-exposed plasma in vitro was precipitated with acetone and digested (2 h, 50 °C) with pronase to form the alkylated dipeptide, S-hydroxyethylthioethyl-CysPro (HETE-CP). The HETE-CP adduct was derivatized with Cbz-Cl to generate N-carbobenzoxy HETE-CP (HETE-C(Cbz)P). The derivatized product was analyzed by UHPLC-MS/MS. HD surrogate, 2-chloroethyl ethyl sulfide (2-CEES), was introduced as a non-isotope internal standard (ISTD) instead of traditional d8-HD for quantification. The method was found to be linear between 1.00 and 200 ng/mL HD exposure (R2 > 0.998) with precision of ≤ 9.0% relative standard deviation (RSD) and accuracy ranged between 97.1 and 111%. The limit of detection (LOD) is 0.500 ng/mL (S/N~5), over 15 times lower than that of the previous method (7.95 ng/mL). Time-consuming affinity purification or solid phase extraction (SPE) is not needed in the experiment and the operation takes less than 5 h. This study provides a new strategy and useful tool for retrospective analysis of HD exposure by HETE-CP biomarker detection. Graphical abstract Flow diagram for quantification of sulfur mustard exposure by detection of HETE-CP dipeptide adduct after benzyl chloroformate derivatization using ultra-high-pressure liquid chromatography tandem mass spectrometry.


Assuntos
Substâncias para a Guerra Química/análise , Cromatografia Líquida de Alta Pressão/métodos , Gás de Mostarda/análise , Espectrometria de Massas em Tandem/métodos , Alquilação , Biomarcadores/análise , Biomarcadores/sangue , Precipitação Química , Dipeptídeos/análise , Formiatos/química , Humanos , Limite de Detecção , Pronase/química , Proteólise , Albumina Sérica Humana/análise , Extração em Fase Sólida/métodos
16.
Appl Spectrosc ; 73(8): 841-858, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31008649

RESUMO

The use of portable gas chromatography-mass spectrometry (GC-MS) is an important capability that has been available commercially for almost 25 years. These systems have been used within a variety of different industries, including their extensive use by environmental scientists for the analysis of hazardous air pollutants. Recently, these systems were deployed to conventional military forces for use in theater to detect and identify toxic chemicals including chemical warfare agents (CWAs). The challenges of deploying such complex analytical instruments to these military users are unique. Among other things, these organizations have considerable and variable mission strains, complex and difficult logistics and coordination needs, and variability in user backgrounds. This review outlines the value portable GC-MS systems offer to these warfighters in theater, discusses some important aspects of the design of portable systems that makes their deployment to this type of end user possible, and proposes methods that can be used to overcome challenges to successful deployment of portable GC-MS to non-scientists working within hostile environments.


Assuntos
Atmosfera/química , Substâncias para a Guerra Química/análise , Cromatografia Gasosa-Espectrometria de Massas/instrumentação , Gases/análise , Substâncias Perigosas/análise , Militares/educação , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Monitoramento Ambiental , Gases/toxicidade , Humanos
17.
Molecules ; 24(5)2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30813539

RESUMO

Here, we introduced a novel thiourea-based rhodamine compound as a chromo-fluorogenic indicator of nerve agent Soman and its simulant diethyl chlorophosphate (DCP). The synthesized probe N-(rhodamine B)-lactam-2-(4-cyanophenyl) thiourea (RB-CT), which has a rhodamine core linked by a cyanophenyl thiosemicarbazide group, enabled a rapidly and highly sensitive response to DCP with clear fluorescence and color changes. The detection limit was as low as 2 × 10-6 M. The sensing mechanism showed that opening of the spirolactam ring following the phosphorylation of thiosemicarbazides group formed a seven-membered heterocycle adduct, according to MS analysis and TD-DFT calculations. RB-CT exhibited high detecting selectivity for DCP, among other organophosphorus compounds. Moreover, two test kits were employed and successfully used to detect real nerve agent Soman in liquid and gas phase.


Assuntos
Corantes Fluorescentes/síntese química , Compostos Organofosforados/análise , Rodaminas/química , Soman/análise , Tioureia/química , Substâncias para a Guerra Química/análise , Substâncias para a Guerra Química/química , Corantes Fluorescentes/química , Limite de Detecção , Estrutura Molecular , Agentes Neurotóxicos/análise , Agentes Neurotóxicos/química , Compostos Organofosforados/química , Soman/química
18.
Biosens Bioelectron ; 129: 15-23, 2019 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-30682684

RESUMO

The synthesis and employment of volatile toxic compounds as chemical weapons with a large-scale destructive power has introduced a new insidious threat over the last century. In this framework, the development of wearable sensing tools represents a critical point within the security field, in order to provide early alarm systems. Herein, a novel wearable electrochemical biosensor was developed for the rapid and on-site detection of mustard agents. Since a chemical attack is typically carried out by spraying these volatile agents into air, the sensor was designed in order to be able to measure mustard agents directly in the aerosol phase, further than in the liquid phase. The electrodes were screen-printed onto a filter paper support, which allowed to harness the porosity of paper to pre-load all the needed reagents into the cellulose network, and hence to realise an origami-like and reagent-free device. Mustard agent detection was carried out by monitoring their inhibitory effects toward the choline oxidase enzyme, through the amperometric measurement of the enzymatic by-product hydrogen peroxide. A carbon black/Prussian blue nanocomposite was used as a bulk-modifier of the conductive graphite ink constituting the working electrode, allowing for the electrocatalysis of the hydrogen peroxide reduction. After having verified the detecting capability toward a mustard agent simulant, the applicability of the resulting origami-like biosensor was demonstrated for the rapid and real-time detection of real sulfur mustard, obtaining limits of detection equal to 1 mM and 0.019 g·min/m3 for liquid and aerosol phase, respectively.


Assuntos
Técnicas Biossensoriais/instrumentação , Substâncias para a Guerra Química/análise , Gás de Mostarda/análise , Dispositivos Eletrônicos Vestíveis , Aerossóis/análise , Alcaligenes/enzimologia , Oxirredutases do Álcool/química , Técnicas Eletroquímicas/instrumentação , Enzimas Imobilizadas/química , Desenho de Equipamento , Humanos , Limite de Detecção , Papel
19.
Chemosphere ; 221: 672-682, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30677728

RESUMO

Novichok use has become symbol for the chemical substances use to carry out political assassinations. In the last century, poisonous warfare agents were used for the first time on the battlefields, almost all over the world. After the World War II, new types of organophosphorus chemical warfare agents were developed. Novichoks are only ones, but the most important part of them - the 4th generation of chemical warfare agents. Despite the Chemical Weapons Convention, entered into force in 1997, there is still real threat of use of chemical weapons. This weapon can be used by both states, and transnational terrorist organisations. Novichoks, A code-named substances, should be permanently introduced into a number of chemical substances contained in organophosphorus chemical warfare poisonous agents. This article presents a short fourth-generation nerve agents' description. Group A compounds together with G and V groups compounds are organophosphorus chemical warfare agents which are very dangerous ones. Our article is an attempt to provide answer for the question - what are Novichoks? And why they should be introduced into Chemical Weapons Convention.


Assuntos
Substâncias para a Guerra Química/análise , Intoxicação por Organofosfatos , Organofosfatos/análise , Humanos , Agentes Neurotóxicos/análise
20.
J Anal Toxicol ; 43(3): 179-187, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30364974

RESUMO

The development of one comprehensive gas chromatographic-triple quadrupole mass spectrometric (GC-MS-MS) method for the analysis of nerve agents and their breakdown products can pose a challenge due to significant differences in analyte volatility. Nerve agent breakdown products typically have a low volatility, requiring a derivatization step prior to analysis by gas chromatography (GC). However, nerve agent parent compounds are generally more volatile, which eliminates the need for derivatization and allows for direct analysis. Therefore, the analysis of these analytes is typically performed using separate analytical methods. This may require the use of multiple columns composed of different stationary phases to ensure the most efficient separation. With the wide selection of GC columns and derivatizing agents, it is potentially possible to develop a single-column/analytical method that is suitable for the detection of nerve agents and their breakdown products. We evaluated six nerve agents (tabun, sarin, soman, cyclosarin, VX and Russian VX) and the six corresponding breakdown products (EDPA, IMPA, PMPA, CMPA EMPA and MMPA). Chromatographic separation and multiple-reaction mode electron ionization detection of the nerve agents and silylated breakdown product derivatives were performed using an Agilent 7890 A gas chromatography (GC) equipped with a mid-polarity column, coupled to a 7000 triple quadrupole mass spectrometry system. A fast (12.5 min), highly sensitive (picogram) and selective method was achieved. The feasibility of this method for nerve agent and breakdown product detection in real samples was demonstrated using nerve agent-spiked human plasma at various exposure times (3 min, 1 h and 24 h). Five of the six nerve agents and all six breakdown products were successfully detected. This robust method has utility as a rapid screening tool to identify a specific nerve agent in a potential exposure event by simultaneous detection of the parent and or its corresponding breakdown product in plasma.


Assuntos
Substâncias para a Guerra Química/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Agentes Neurotóxicos/análise , Espectrometria de Massas em Tandem/métodos , Substâncias para a Guerra Química/química , Limite de Detecção , Agentes Neurotóxicos/química , Reprodutibilidade dos Testes , Fatores de Tempo
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