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1.
K. A. M. Creber P. V. Samuleev W. S. Andrews 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(2):597-600
Chemical warfare agents have been stockpiled for almost a decade and their destruction has become an environmental issue that
will continue to require attention for many years. There are hundreds of thousands of tonnes yet to be destroyed, and the
current chemical or incineration techniques are not without problems. While many researchers are seeking better chemical techniques,
we decided to try ionizing radiation to destroy sulphur mustard with the goal of producing non-toxic products. We irradiated
a variety of sulphur mustard samples by both a mixed field source (β, γ and neutrons) and a pure gamma source. The mixed field
irradiation of wet sulphur mustard for long irradiation times was the most successful at destroying the chemical agent. 相似文献
2.
Adam M. Graichen Richard W. Vachet 《Journal of the American Society for Mass Spectrometry》2013,24(6):917-925
The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations. Figure
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3.
A reversed-phase high-performance liquid chromatography (HPLC) method with cold vapor atomic absorption spectrometry (CV-AAS) detection is developed for mercury speciation. In this paper, the efficiency of tetrabutylammonium bromide reagent and sodium chloride in a methanol-water mixture as mobile phase is evaluated for HPLC separation of methylmercury and inorganic mercury coupled with on-line CV-AAS determination. Both mercury species are separated on a reversed-phase C(18) column. Several parameters (e.g. composition and flow-rate of mobile phase) are investigated for the optimization of HPLC separations. CV-AAS technique parameters are also studied for their effect on sensitivity (sodium borohydride and sodium hydroxide concentrations in the reducing agent, reducing agent flow-rate, length of the reduction coil and nitrogen flow-rate). Quantitative recoveries for both inorganic mercury and methylmercury are obtained from a spiked natural water sample. 相似文献
4.
Selective Photooxidation of a Mustard‐Gas Simulant Catalyzed by a Porphyrinic Metal–Organic Framework
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Dr. Yangyang Liu Dr. Ashlee J. Howarth Prof. Joseph T. Hupp Prof. Omar K. Farha 《Angewandte Chemie (International ed. in English)》2015,54(31):9001-9005
The photooxidation of a mustard‐gas simulant, 2‐chloroethyl ethyl sulfide (CEES), is studied using a porphyrin‐based metal–organic framework (MOF) catalyst. At room temperature and neutral pH value, singlet oxygen is generated by PCN‐222/MOF‐545 using an inexpensive and commercially available light‐emitting diode. The singlet oxygen produced by PCN‐222/MOF‐545 selectively oxidizes CEES to the comparatively nontoxic product 2‐chloroethyl ethyl sulfoxide (CEESO) without formation of the highly toxic sulfone product. In comparison to current methods, which utilize hydrogen peroxide as an oxidizing agent, this is a more realistic, convenient, and effective method for mustard‐gas detoxification. 相似文献
5.
Polysulfone-graft-poly(tert-butyl acrylate) (PSf-g-PtBA) membranes with PtBA weight fraction ranging from 19.7% to 34% were prepared from the mixing at different ratios of two PSf-g-PtBA samples, which have approximately one PtBA branch per PSf chain but different PtBA chain lengths. PSf-g-PAA membranes, where PAA denotes poly(acrylic acid), were prepared either from the in situ hydrolysis of PtBA in pre-formed PSf-g-PtBA membranes or from casting solutions of PSf-g-PAA. Neutralization of PAA with tetraalkylammonium hydroxide yields PSf-g-P(AA-TAA), where P(AA-TAA) denotes poly(tetraalkylammonium acrylate). Casting solutions of PSf-g-P(AA-TAA) yielded PSf-g-P(AA-TAA) membranes. This paper investigates the variation in the permeability of water and 2-chloroethyl ethyl sulfide (CEES) vapor across the membranes as a function the weight fraction of PtBA, PAA, or P(AA-TAA), where CEES is used as a simulant for the chemical warfare agent sulfur mustard bis(2-chloroethyl) sulfide. Also presented are the TEM images of thin sections of the different membranes revealing the morphology of the PtBA, PAA, and P(AA-TAA) domains. 相似文献
6.
2-Chloroethylethyl sulfide (CEES) is used as a simulant for mustard (HD) in a study to develop secondary ion mass spectrometry (SIMS) for rapid, semi-quantitative detection of mustard on soil. Selectivity and sensitivity are markedly improved employing multiple-stage mass spectrometry (MS(n)) using an ion trap SIMS. C(2)H(5)SC(2)H(4)(+) from CEES eliminates C(2)H(4) and H(2)S, which are highly diagnostic. CEES was detectable at 0.0012 monolayer on soil. This corresponds to approximately 15 ppm (mass/mass) for a soil having a surface area of 12 m(2) g(-1). A single analysis could be conducted using only 2 mg of soil in under 5 min. 相似文献
7.
Spectrophotometric determination of inorganic mercury (II) after preconcentration of its diphenylthiocarbazone complex on a cellulose column 总被引:1,自引:0,他引:1
Rajesh N Hari MS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(5):1104-1108
A simple and a relatively green methodology have been developed for the preconcentration of mercury based on the adsorption of its diphenylthiocarbazone complex on a cellulose column. The effects of various parameters such as effect of acidity, eluting agents, stability of the column, sample volume, interfering ions, etc. have been studied in detail. The adsorbed complex could be easily desorbed using environmentally benign polyethylene glycol-400 and the concentration of mercury was determined using visible spectrophotometry. The calibration graph was linear in the range 0-2mugmL(-1) of mercury with a detection limit of 2mugL(-1) and the validity of the proposed method was checked by studying the recovery of mercury in spiked tap water, well water and sea water samples. The highest preconcentration factor achieved for quantitative recovery (>95%) of mercury (II) was 33 for a 500mL sample volume. The method was also applied to the analysis of mercury content in city waste incineration ash (CRM176). The relative standard deviation of the method was found to be 3.5%. 相似文献
8.
H Shimada M Kiyozumi M Kawagoe S Fukudome S Kojima 《Chemical & pharmaceutical bulletin》1990,38(3):757-760
The effects of various chelating agents, sodium N-benzyl-D-glucamine dithiocarbamate (BGD), sodium N-p-methylbenzyl-D-glucamine dithiocarbamate (MBGD), sodium N-p-hydroxymethylbenzyl-D-glucamine dithiocarbamate (HBGD), and N-p-carboxybenzyl-D-glucamine dithiocarbamate (CBGD), which were newly synthesized, and sodium N-methyl-D-glucamine dithiocarbamate (MGD), on the distribution and excretion of inorganic mercury were compared in rats exposed to HgCl2. Rats were injected i.p. with 203HgCl2 (300 micrograms of Hg and 74 kBq of 203Hg/kg) and 30 min or 24 h later, they were injected with a dithiocarbamate (1200 mumol/kg). At 30 min after mercury administration, BGD and MBGD significantly enhanced the biliary excretion of mercury, while CBGD, MGD, and HBGD enhanced the urinary excretion of mercury to a small extent. At 24 h after mercury injection, BGD was the most effective on the biliary excretion of the metal, while MGD and HBGD significantly enhanced the urinary excretion of the metal. All of these dithiocarbamates were effective in mobilizing mercury from the kidney at 30 min after mercury treatment. At 24 h after mercury treatment, HBGD and BGD effectively depressed mercury content in the kidney. These results show that the injection of BGD and HBGD at both 30 min and 24 h after mercury treatment can much more effectively mobilize mercury from the kidney without redistribution of mercury to other tissues, such as brain, heart, and lung, when compared with injection of other chelating agents. The pattern of mobilization and excretion of mercury following treatment with each chelating agent was related to the organic/aqueous partition coefficient of each dithiocarbamate-mercury complex. 相似文献
9.
Determination of mercury species in natural waters at picogram level with on-line RP C18 preconcentration and HPLC-UV-PCO-CVAAS 总被引:1,自引:0,他引:1
A new technique has been developed for the determination of methyl-, ethyl-, methoxyethyl-, ethoxyethyl-, phenyl- and inorganic mercury in natural water samples. The mercury compounds have been complexed for the preconcentration on RP C18 columns by sodium pyrrolidinedithiocarbamate (SPDC), sodium diethyldithiocarbamate (SDDC) and hexamethyleneammonium (HMA) — hexamethylenedithiocarbamate (HMDC), separated by HPLC and determined by UV-PCO-CVAAS (ultra violet, post column oxidation, cold vapour atomic absorption spectrometry). The standard deviations are in the range of 6.9 to 11.8%. The recoveries amount to 86%, 78%, 88%, 83%, 79% and 84% for methyl-, ethyl-, methoxyethyl-, ethoxyethyl-, phenyl- and inorganic mercury for the enrichment from 300 ml water samples. The detection limit for methyl mercury is 0.5 ppt. This new on-line preconcentration procedure has been tested with rain, drinking, surface and process water samples. 相似文献
10.
Rajesh N Gurulakshmanan G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,69(2):391-395
A simple method has been developed for the preconcentration of mercury based on the adsorption of its diphenylthiocarbazone complex on a neutral alumina column. The influence of acidity, eluting agents, stability of the column, sample volume and interfering ions has been investigated in detail. The adsorbed complex could be eluted using environmentally benign polyethylene glycol (PEG 400) and the concentration of mercury was determined by visible spectrophotometry at a wavelength maximum of 520nm. A detection limit of 4microgL(-1) could be achieved and the developed procedure was successfully applied for the determination of mercury in spiked water samples and city waste incineration ash (CRM176). The preconcentration factor attainable for quantitative recovery (>95%) of mercury(II) was 100 for a 1000mL sample volume. 相似文献
11.
The determination of mercury by the title method with sodium tetrahydroborate as reducing agent can be interfered with by volatile nitrogen oxides which inhibit the reduction of mercury by scavenging the reducing agent. The nitrogen oxides are formed as reduction products of nitric acid during sample decomposition. The interference effect was encountered in the determination of mercury in sewage sludge digests, and the main symptom was poor reproducibility of the shape of the mercury peak. The area of the mercury peak is more resistant to the interference than the peak height. The nitrogen oxide interference did not cause any systematic error in the mercury determination when calibration was done by standard addition. The interference can be easily remedied by purging the sample with argon. 相似文献
12.
Tracer ( approximately 10(-8)M) mercury(II) can be quantitatively extracted with 5-(4-pyridyl)nonane in benzene from aqueous thiocyanate solutions that are up to 6M in HCl, 1M in H(2)SO(4) or 0.25M in HNO(3), in a single extraction. Optimal conditions for the extraction are given, based on a critical study of the relevant factors such as the effects of the acids, thiocyanate, salting-out and complexing agents and the reagent concentration. The mechanism underlying these extractions is discussed on the basis of the results obtained from partition and slope-analysis data. The extraction of the metal as Hg(PyN)(2)(SCN)(2) is indicated. The extracted mercury can be stripped from the non-aqueous layer with various aqueous solutions, including nitric acid (2M), sodium citrate ( 1M) and sodium thiosulphate (0.1 M). Common salts do not depress the extraction. Distribution coefficients and separation factors of several elements relative to mercury(II) are reported for media that contain the optimal concentrations of the mineral acids and are in 0.2M in potassium thiocyanate. The data have been applied for the determination of mercury in soil and water samples by atomic-absorption spectrometry. 相似文献
13.
Jyh-Myng Zen Fu-Shien Hsu Nai-Yuen Chi Sen-Yuan Huang Mu-Jye Chung 《Analytica chimica acta》1995,310(3):407-417
The effect of various organic compounds on the Nafion/chelating agent mercury film electrodes (NCAMFEs) in square-wave anodic-stripping voltammetry (SWASV) is explored. Two chelating agents used to prepare the NCAMFEs are dimethylglyoxime and 2,2'-bipyridyl. Triton X-100, sodium dodecyl sulfate, albumin, gelatin, starch, camphor, and humic acid are used as model organic compounds, while cadmium, lead, and copper are used as test metal ions. The NCAMFEs are considerably more resistant to organic interferences than the Nafion-coated mercury film electrode. The implications of these interferences for the reliability and feasibility of stripping measurements using the NCAMFEs in real samples are discussed. Results presented for untreated urine and natural water samples demonstrate the analytical utility of the NCAMFEs in SWASV. 相似文献
14.
Chemical neutron activation analysis was developed for determining trace amounts of arsenic and mercury in a variety of environmental matrices, including water, sediment, rock, plants, animal organs, etc: The adsorption procedure via magnesium oxide as the agent was applied to preconcentrate arsenic from the digested environmental matrices where arsenic in the form of As(V) ion could be highly efficiently adsorbed by hydrous magnesium oxide. On the other hand, the extraction procedure via lead diethyldithiocarbamate as the agent was applied to preconcentrate mercury from the digested environmental matrices where mercury in the form of Hg(II) ion could be highly efficiently extracted into the solution of lead diethyldithiocarbamte in dichloromethane. Both of the preconcentrated materials prepared ultimately in the solid states, i.e., arsenic in magnesium oxide and mercury in lead diethyldithiocarbamte were taken to be neutron irradiated. The γ spectra of the preconcentrated samples irradiated generally showed clear peaks of the product radionuclides from arsenic or from mercury by the different separation procedures. The possible interfering elements such as Na, Br, etc., were prominently minimized in respect of most of the preconcentrated samples. The reliability and accuracy of the proposed analytical methods for detecting arsenic and mercury can be confirmed by the assay of commercial standard reference materials including sediment, rock, plants, and animal organs. 相似文献
15.
Comparison of magnesium sulfate and sodium sulfate for removal of water from pesticide extracts of foods 总被引:5,自引:0,他引:5
Schenck FJ Callery P Gannett PM Daft JR Lehotay SJ 《Journal of AOAC International》2002,85(5):1177-1180
Water-miscible solvents, such as acetone and acetonitrile, effectively extract both polar and nonpolar pesticide residues from nonfatty foods. The addition of sodium chloride to the resulting acetonitrile-water or acetone-water extract (salting out) results in the separation of the water from the organic solvent. However, the organic solvent layer (pesticide extract) still contains some residual water, which can adversely affect separation procedures that follow, such as solid-phase extraction and/or gas chromatography. Drying agents, such as sodium sulfate or magnesium sulfate, are used to remove the water from the organic extracts. In the present study, we used nuclear magnetic resonance spectroscopy to study the composition of the phases resulting from salting out and to compare the effectiveness of sodium sulfate and magnesium sulfate as drying agents. The study showed that considerable amounts of water remained in the organic phase after phase separation. Sodium sulfate was a relatively ineffective drying agent, removing little or no residual water from the organic solvent. Magnesium sulfate proved to be a much more effective drying agent. 相似文献
16.
Km Meenu Neeraj Kumar Kautily Rao Tiwari Tara Yadav Radha Tomar Arvind Kumar Gupta 《Phosphorus, sulfur, and silicon and the related elements》2020,195(10):881-888
AbstractIn this study, we have evaluated the performance of novel adsorbent zeolite Linde Type W and modified LTW with AgO metal oxide composite for the decontamination of chemical warfare agent simulant 2-chloroethylphenylsulphide (CEPS). Zeolites are nanoporous aluminosilicate minerals composed of silicon, aluminum and oxygen framework with cations and water molecules within the pores. The synthesized zeolite LTW and its composites Ag-O-LTW was characterized by XRD, FTIR, SEM-EDS and BET analytical techniques. The decontamination study of CWA simulant, CEPS was monitored by using GC-FID technique. The nanocrystalline zeolite LTW and Ag-O-LTW composites were found powerful adsorbents and showed great decontamination potential toward CWA simulant CEPS. The Ag-O-LTW showed better results (~98 % decontamination in 7?hours) than LTW zeolite. 相似文献
17.
The selectivity of the determination of traces of cadmium, lead, thallium and indium is improved by direct coupling of liquid/liquid extraction and anodic stripping voltammetry. Metals are extracted from aqueous solution to benzene or chloroform after the addition of sodium or zinc diethyldithiocarbamate. Stripping voltammetry of Cd, Tl and Pb at a hanging mercury drop electrode or mercury film electrode is done in benzene/methanol medium (1:1) with 0.1 M NaClO4 as supporting electrolyte. For indium, the medium is chloroform/ethanol/water (1:4:1) with 0.005 M sodium acetate/0.06 M KBr/0.06 M HCl as supporting electrolyte. The complexes in acidic solution can be decomposed by mercury (II) ions, which provides useful shifts of deposition potentials. Calibration graphs are linear at concentrations of about 10?7 M with a detection limit of 1×10?8 M. The method is applied to determine a single metal in the presence of a large amount (1000-fold) of interfering metal. 相似文献
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Gas chromatography-mass spectrometry under both electron impact and methane chemical ionization conditions has been used to detect impurities and degradation products present in the mustard simulant 2-chloroethyl ethyl sulfide, with a detection limit of 0.05 area percent. After one and two years of storage at ambient temperatures, the primary degradation product was 1,4-dithiane formed from the degradation of dimeric sulfonium ions. Oxidation and hydrolysis products were not detected. 相似文献