Destruction of diphenylarsine chloride (CLARK I) with activated ozone

The new technology of Plasmazon® uses the extremely strong oxidation of radicals to break up the compocunds of organic connections, e.g. chemical warfare agents like Clark I. In making a comparison of oxidation to normal ozone, the factor of the Plasmazon® -technology is available up to 10³. The investigation in an experimental test shows that it is possible to destroy the warfare agent character of Clark I. As the possibility of a large-lot application this technology is the method of choice for other chemical or biological warfare agents.     

活性炭吸附化学战剂--沙林染毒水的试验研究

研究了 5种国产活性炭吸附水中沙林的性能及影响因素。果壳质活性炭的吸附性能优于煤质活性炭。果壳活性炭WP 2 0 2的吸附等温线方程为 qe=11 45C0 39e ,其粉状炭在 10min时能达到吸附容量的 98%。活性炭颗粒小则吸附速度快 ,温度升高不利于吸附。活性炭与水中的氯反应后 ,吸附性能下降 3 0 % ,在含盐量 2 0 0 0mg/L的苦咸水中吸附量降低 5 %。处理化学战剂 -沙林染毒水宜多种水处理技术相结合 ,并采用活性炭吸附作为最后一级处理单元     

Investigation of long-term hazards of chemical weapon agents in the environment of Sardasht area,Iran

Environmental Science and Pollution Research - The present study aimed to investigate the persistence and existence of chemical warfare agents (CWAs) and related dissipation products in the...     

臭氧洗消化学战剂模拟剂DPCP试验研究

用臭氧对神经性化学战剂的模拟剂氯磷酸二苯酯（DPCP）进行洗消，试验考察了初始酸度、O₂流量、放电功率、放电室压力、反应温度、初始浓度和O₃流量等因素对DPCP降解率的影响。碱性条件下DPCP降解率高于酸性条件下的降解率；反应温度、O₃流量、放电功率的增加，DPCP降解率上升；初始浓度增加，DPCP降解率下降；氧气流量和放电室压力增加，DPCP降解率先上升，后下降。在最佳反应条件下，50 mg/L的DPCP处理16 min降解率达到98%，矿化率40.1%。     

Impregnation on activated carbon for removal of chemical warfare agents (CWAs) and radioactive content

Environmental Science and Pollution Research - Nuclear, biological, and chemical warfare (NBC) agents cause an inevitable threat to defense forces and civilians. Exposure to these toxic agents...     

Possible treatment with medicinal herbs and their ingredients of lung disorders induced by sulfur mustard exposures: a review

Environmental Science and Pollution Research - Chemical warfare (CW) agents are toxic synthetic chemicals that affect human’s health, and sulfur mustard (SM) is a well-known chemical weapon...     

Soil phytoremediation from the breakdown products of the chemical warfare agent, yperite

A plant-based bioremediation (phytoremediation) strategy has been developed and shown to be effective for the clean-up of soil contaminated by the breakdown products of the chemical warfare agent (CWA), yperite. The method involves exploiting the plant growth hormone, indole-3-acetic acid (IAA), to intensify the phytoremediation. For determination of the yperite breakdown products, gas chromatography is used. Soil and plant samples were analysed with a gas chromatograph fitted with an atomic emission detector. The method of standard-free determination was employed to identify sulphur-containing substances (SCSs). A series of soil tests was conducted, which showed that the level of SCSs decreased 4, 8, and more than 20-fold compared with that found in contaminated soil. This decrease was dependent upon the IAA concentrations used for plant treatment. The treated plants accumulated 2.7 to 2.9-fold larger amounts of the SCSs than did the untreated plants. Owing to its simplicity, environmental safety and inexpensiveness, the method can be recommended for the restoration of soil fertility in areas of storage and destruction of blister CWAs.     

Bacterial release of arsenic ions and organoarsenic compounds from soil contaminated by chemical warfare agents

The objective of this paper was to investigate possible participation of microorganisms in the release of soluble arsenical compounds from organoarsenic warfare agents in contaminated soil. A number of bacterial strains were isolated with high resistance against As3+ and As5+ ions which are able to degrade the water insoluble compounds triphenylarsine (TP) and triphenylarsineoxide (TPO). These strains belong to different genera of bacteria. Release of arsenic ions and soluble organoarsenic compounds from soil by the activity of autochthonic soil bacteria and a mixture of the isolated pure cultures was demonstrated by percolation experiments with undisturbed soil samples (core drills) from the contaminated site. This release increased after addition of nutrients (mineral nitrogen and phosphorus, sodium acetate and ethanol) and is nearly independent of the percolation temperature (5 degrees C and 22 degrees C). These results show that bacteria play an important role in the release of arsenical compounds from organoarsenic warfare agent contaminated soil. This release is limited by shortage of water and, above all, of nutrients for the microorganisms in the sandy forest soil. These results are important both for the management and security and possibly for bioremediation of military waste sites containing similar contaminations. Furthermore, this is the first report on bacterial degradation of organoarsenic warfare compounds.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.     

Oxidation of triphenylarsine to triphenylarsineoxide by Trichoderma harzianum and other fungi

Arsenic resistant strains of bacteria and fungi were isolated from soil contaminated by chemical warfare agents. Until now, no metabolic products of microbial attack against the phenyl residues of the model substrate triphenylarsine (TP) were found if it was incubated together with these strains in liquid culture assays. However, one of the isolated fungi, Trichoderma harzianum As 11, was found to oxidize TP to triphenylarsineoxide (TPO). The yeast Trichosporon mucoides SBUG 801 and the white-rot fungus Phanerochaete chrysosporium were also able to oxidize the As(III) in TP. In addition, P. chrysosporium transformed phenylarsineoxide (PAO) to phenylarsonic acid (PAA) under O2-atmosphere. By means of a respirometer system, the oxidation of TP by T. harzianum As 11 was confirmed by a significantly higher consumption of oxygen in the presence of these compounds. HPLC analysis of the oxidation products TPO and PAA in the medium of the assays provided evidence for the transfer reaction of As(III) to As(V) in organic bonds. The oxidation products TPO and PAA are more hydrophilic than TP and PAO. Therefore, it was concluded that particular fungi contribute to the mobilization of arsenic in soil contaminated by chemical warfare agents.     

Determination of chemical warfare agents in soil and material samples

A gas Chromatographic method for the determination of phenylarsenic compounds (sternutators) and their metabolites in soil and material samples is described. The chemical warfare agents (CWA), but not their hydrolysis and oxidation products, can be detected with GC/ECD. After derivatization with thiols or dithiols, the sum of diphenylarsenic and phenylarsenic compounds can be determined with GC/ECD. The comparison of the analytical results with and without derivatization shows that the sternutators in the investigated samples are metabolized in part.     

Determination of chemical warfare agents

Chlorovinylannes (Lewisites) were produced and handled during WW I and WW II as chemical warfare agents. Residues of these cwa and their metabolites are still present today and continue to contaminate soil and water. A gas Chromatographic method for the detection and determination of chlorovinylarsines (Lewisites) and their metabolites is shown. Lewisite II and Lewisite III, but not Lewisite I and the metabolites of Lewisite I and Lewisite II can be detected and determined using GC/ECD. After derivatization with thiols, the sum of Lewisite I or Lewisite II and their metabolites are detected. With the proper selection of the thiol, matrix interferences can be eliminated because of the different retention times of the derivatives.     

Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

Herbicide effects on typha latifolia (Linneaus) germination and root and shoot development

Aqueous 7-d germination and growth experiments were performed to compare responses of T. latifolia to exposures of atrazine (2-chloro-4-ethylamino-6-isopropylamine-s-atrazine) and paraquat dichloride (1,1′-dimethyl-4,4′-bipyridinium dichloride). T. latifolia seed germination was < 50 % in concentrations ≥ 1.0 mg/L of paraquat dichloride. No observed effect concentration (NOEC) and lowest observed effect concentration (LOEC) for paraquat and root growth were 0.001 and 0.01 mg/L, respectively, while NOEC and LOEC for paraquat and shoot growth were 0.01 and 0.1 mg/L, respectively following 7-d exposures. Greater than 72 % of seeds germinated in each concentration up to 30 mg/L atrazine. After 7-d exposure, NOEC and LOEC for atrazine and root growth were 0.1 and 1.0 mg/L, while atrazine and shoot growth NOEC and LOEC values were 15 and 30 mg/L, respectively. This research provides data concerning relative sensitivity of T. latifolia seedlings to the herbicides atrazine and paraquat, as well as the potential use of T. latifolia as a representative plant test species.     

Analysis of halogenated polycyclic aromatic hydrocarbons in urban air, snow and automobile exhaust

Urban air, snow and automobile exhaust samples were extensively cleaned up by open column liquid chromatography. The appropriate fractions were analysed for halogenated polycyclic aromatic hydrocarbons (XPAH) by gas chromatography/negative chemical ionization mass spectrometry (GC/NCIMS). XPAH were found in all three sample types. A urban air sample was found to contain chlorinated pyrenes, fluoranthenes and benzopyrene and brominated pyrenes and fluoranthenes. Furthermore, the concentration of 1-chloropyrene in that air sample was estimated to be 10 pg/m³. XPAH were also found in snow samples taken in the vicinity of a motor-way. Ethylene dibromide and ethylene dichloride, are probably the source of the halogen atoms in the XPAH detected in car exhaust.     

Evaluation of the efficacy of a portable LIBS system for detection of CWA on surfaces

Laser-induced breakdown spectroscopy (LIBS) is a laser-based optical technique particularly suited for in situ surface analysis. A portable LIBS instrument was tested to detect surface chemical contamination by chemical warfare agents (CWAs). Test of detection of surface contamination was carried out in a toxlab facility with four CWAs, sarin (GB), lewisite (L1), mustard gas (HD), and VX, which were deposited on different substrates, wood, concrete, military green paint, gloves, and ceramic. The CWAs were detected by means of the detection of atomic markers (As, P, F, Cl, and S). The LIBS instrument can give a direct response in terms of detection thanks to an integrated interface for non-expert users or so called end-users. We have evaluated the capability of automatic detection of the selected CWAs. The sensitivity of our portable LIBS instrument was confirmed for the detection of a CWA at surface concentrations above 15 μg/cm². The simultaneous detection of two markers may lead to a decrease of the number of false positive.     

Current and emerging strategies for organophosphate decontamination: special focus on hyperstable enzymes

Organophosphorus chemicals are highly toxic molecules mainly used as pesticides. Some of them are banned warfare nerve agents. These compounds are covalent inhibitors of acetylcholinesterase, a key enzyme in central and peripheral nervous systems. Numerous approaches, including chemical, physical, and biological decontamination, have been considered for developing decontamination methods against organophosphates (OPs). This work is an overview of both validated and emerging strategies for the protection against OP pollution with special attention to the use of decontaminating enzymes. Considerable efforts have been dedicated during the past decades to the development of efficient OP degrading biocatalysts. Among these, the promising biocatalyst SsoPox isolated from the archaeon Sulfolobus solfataricus is emphasized in the light of recently published results. This hyperthermostable enzyme appears to be particularly attractive for external decontamination purposes with regard to both its catalytic and stability properties.     

CS-Fe和CS-Fe/Ni的制备及其用于去除钴离子

以氯化铁为铁源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原法制备壳聚糖稳定纳米铁（CS-Fe）；并以氯化铁为铁源，硫酸镍为镍源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原共沉淀法制备壳聚糖稳定纳米铁镍（CS-Fe/Ni）。通过SEM、EDS、XRD、FT-IR等表征手段，对所制备的CS-Fe和CS-Fe/Ni的形貌及微观结构进行表征，并以Co²⁺为目标去除物评价CS-Fe和CS-Fe/Ni的反应活性。初步研究表明，制成的CS-Fe含有单质纳米铁，颗粒多数以30~90 nm球形颗粒为主；而CS-Fe/Ni材料中含有纳米铁镍，颗粒多数以30~60 nm球形颗粒为主；在相同的实验条件下，反应60 min，CS-Fe/Ni对Co²⁺的去除率高达100%，但是CS-Fe仅为88%，即CS-Fe/Ni对Co²⁺的去除率比CS-Fe高。     

Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.