Identification of inorganic improvised explosive devices using sequential injection capillary electrophoresis and contactless conductivity detection

A simple sequential injection capillary electrophoresis (SI-CE) instrument with capacitively coupled contactless conductivity detection (C(4)D) has been developed for the rapid separation of anions relevant to the identification of inorganic improvised explosive devices (IEDs). Four of the most common explosive tracer ions, nitrate, perchlorate, chlorate, and azide, and the most common background ions, chloride, sulfate, thiocyanate, fluoride, phosphate, and carbonate, were chosen for investigation. Using a separation electrolyte comprising 50 mM tris(hydroxymethyl)aminomethane, 50 mM cyclohexyl-2-aminoethanesulfonic acid, pH 8.9 and 0.05% poly(ethyleneimine) (PEI) in a hexadimethrine bromide (HDMB)-coated capillary it was possible to partially separate all 10 ions within 90 s. The combination of two cationic polymer additives (PEI and HDMB) was necessary to achieve adequate selectivity with a sufficiently stable electroosmotic flow (EOF), which was not possible with only one polymer. Careful optimization of variables affecting the speed of separation and injection timing allowed a further reduction of separation time to 55 s while maintaining adequate efficiency and resolution. Software control makes high sample throughput possible (60 samples/h), with very high repeatability of migration times [0.63-2.07% relative standard deviation (RSD) for 240 injections]. The separation speed does not compromise sensitivity, with limits of detection ranging from 23 to 50 μg·L(-1) for all the explosive residues considered, which is 10× lower than those achieved by indirect absorbance detection and 2× lower than those achieved by C(4)D using portable benchtop instrumentation. The combination of automation, high sample throughput, high confidence of peak identification, and low limits of detection makes this methodology ideal for the rapid identification of inorganic IED residues.     

Determination of inorganic improvised explosive device signatures using laser electrospray mass spectrometry detection with offline classification

The mass spectral detection of low vapor pressure, inorganic-based explosive signatures including ammonium nitrate, chlorate, perchlorate, sugar, and the constituents contained within black powder are reported using laser electrospray mass spectrometry. The ambient pressure mass spectrometry technique combining nonresonant, femtosecond laser vaporization with electrospray postionization revealed primary and secondary signatures for trace quantities of inorganic explosives. A mixture of complexation agents in the electrospray solvent enabled the simultaneous detection of vaporized cations, anions, and neutrals in a single measurement. An offline classifier discriminated the inorganic-based explosives based on the mass spectral signatures resulting in high fidelity identification.     

Latex-coated polymeric monolithic ion-exchange stationary phases. 1. Anion-exchange capillary electrochromatography and in-line sample preconcentration in capillary electrophoresis

A sulfonated methacrylate monolithic polymer has been synthesized inside fused-silica capillaries of diameters 50-533-microm i.d. and coated with 65-nm-diameter fully functionalized quaternary ammonium latex particles (AS18, Dionex Corp.) to form an anion-exchange stationary phase. This stationary phase was used for ion-exchange capillary electrochromatography of inorganic anions in a 75-microm-i.d. capillary with Tris/perchlorate electrolyte and direct UV detection at 195 nm. Seven inorganic anions (bromide, nitrate, iodide, iodate, bromate, thiocyanate, chromate) could be separated over a period of 90 s, and the elution order indicated that both ion exchange and electrophoresis contributed to the separation mechanism. Separation efficiencies of up to 1.66 x 10(5) plates m(-1) were achieved, and the monoliths were stable under pressures of up to 62 MPa. Another latex-coated monolith in a 250-microm-i.d. capillary was used for in-line preconcentration by coupling it to a separation capillary in which the EOF had been reversed using a coating of either a cationic polymer or cationic latex particles. Several capillary volumes of sample were loaded onto the preconcentration monolith, and the analytes (inorganic anions) were then eluted from the monolith with a transient isotachophoretic gradient before being separated by electrophoresis in the separation capillary. Linear calibration curves were obtained for aqueous mixtures of bromide, nitrite, nitrate, and iodide. Recoveries of all analytes except iodide were reduced significantly when the sample matrix contained high levels of chloride. The preconcentration method was applied to the determination of iodide in open ocean water and provided a limit of detection of 75 pM (9.5 ng/L) calculated at a signal-to-noise ratio of 3. The relative standard deviation for migration time and peak area for iodide were 1.1 and 2.7%, respectively (n = 6). Iodide was eluted as an efficient peak, yielding a separation efficiency of 5.13 x 10(7) plates m(-1). This focusing was reproducible for repeated analyses of seawater.     

A multicomponent mobile phase for ion chromatography applied to the separation of anions from the residue of low explosives

A multicomponent mobile phase utilizing ion-exchange, ion-exclusion, and ion-pairing principles for the rapid isocratic separation of anions in low explosives residue by ion chromatography (IC) has been developed. The notable feature of this system is that an ion-pairing reagent and an ion-exclusion reagent are combined in the same mobile phase. Contrary to expectation, these reagents act independently of each other in solution. The stock mobile-phase composition consisted of boric acid, D-gluconic acid, lithium hydroxide, and glycerol. Tetrapropylammonium hydroxide, an ion-interaction reagent was used to achieve pH 8.5. Acetonitrile (ACN) was added to enhance resolution and octanesulfonic acid, an ion-exclusion reagent, was added to adjust the retention time of perchlorate. Separation of a mixture of anions common to low explosives residue was achieved in less than 16 min using a Waters IC-Pak Anion HR column. Optimization studies were performed by changing the concentration of the ACN and by altering the pH or the type of ion-interaction or -exclusion agents. Simulated case studies were performed using postblast residues from pipe bombs. The results show this method to be a valid and reproducible procedure for forensic casework analysis. The practical significance of this system is that a reduction in the analysis time and an improvement in efficiency of late-eluting peaks can be achieved without resorting to gradient elution techniques. For the analysis of anions detected in explosives residue, the Waters IC-Pak Anion HR column has proven to be a suitable replacement for the Vydac 300IC405 column, which has been discontinued by the manufacturer.     

Attenuated total reflectance FTIR detection and quantification of low concentrations of aqueous polyatomic anions

Development of a new quantitative method for determining low concentrations of aqueous polyatomic anions using attenuated total reflectance (ATR) FTIR spectroscopy is described. Evaporated thin-film coatings of anion-selective tetraalkylated ferrocenium salts were applied to the surface of ATR crystals, which enabled anion detection limits to be lowered up to 23 000-fold below those achieved using the commercially available spectrometer with identical uncoated ATR crystals. Linear calibration curves based on d(absorbance)/dt, which is related to the rate of anion exchange in the thin film, were established in the 0.04-30 microM range. Limits of detection (10-min analyses) for perchlorate, chlorate, trifluoromethanesulfonate, perfluoro-n-butanesulfonate, perfluoro-n-octanesulfonate, tetrafluoroborate, hexafluorophosphate, and pinacolylmethylphosphonate in aqueous solution were 0.03, 0.2, 0.05, 0.07, 0.06, 0.06, 0.6, and 0.7 microM, respectively, using the thin-film coatings. This simple detection/quantification method afforded good reproducibility with relatively fast detection times.     

反相高效液相色谱法分离分析水中一些阴离子

本文试验反相高效液相色谱法分离分析水中氯离子、硝酸根和硫酸根的条件,研究可能干扰、提高选择性和提高灵敏度的方法,建立应用于自来水和海水等实际样品的分离分析方法。     

Analysis of inorganic species by capillary electrophoresis-mass spectrometry and ion exchange chromatography-mass spectrometry using an ion spray source

Mixtures of inorganic ions separated by capillary electrophoresis (CE) and ion exchange chromatography (IC) are detected by mass spectrometry (MS) using an ion spray atmospheric pressure ionization source. The selectable degree of ion-adduct declustering and molecular fragmentation in the MS interface region allows the system to be operated as an elemental analyzer or as a molecular detector suitable for oxidation state determinations. Both inorganic anions and cations (including alkalis, alkaline earths, transition metals, and lanthanides) are analyzed by CE-MS. A variety of CE separation buffers are evaluated for the cation analyses (e.g., creatinine, ammonium acetate, and tris[hydroxymethyl]aminomethane). Only one of the buffers (i.e., creatinine) can be used for CE-indirect UV detection. A CE capillary permanently coated with strong anion exchange sites and a pyromellitic acid buffer (suitable for indirect UV detection) is used for the inorganic anion separations. The coated column eliminates the need for buffer modifiers to reverse the flow in the capillary, which then reduces background noise and mass spectral complexity. The separation and detection of 13 inorganic anions are also accomplished by IC using an anion exchange column with a carbonate-bicarbonate mobile phase, on-line suppressed conductivity detection, and mass spectrometric detection.     

Latex-coated polymeric monolithic ion-exchange stationary phases. 2. Micro-ion chromatography

Latex-coated monolithic polymeric stationary phases are used for micro-ion chromatography (mu-IC) of inorganic anions. Monolithic columns were prepared by the in situ polymerization of butyl methacrylate, ethylene dimethacrylate, and 2-acrylamido-2-methyl-1-propanesulfonic acid within fused-silica capillaries of varying internal diameters. Introduction of ion-exchange sites was achieved by coating the anionic polymeric monolith with either Dionex AS10 or Dionex AS18 quaternary ammonium functionalized latex particles to give total ion-exchange capacities in the range 9-24 nequiv for a 30-cm column. The resultant mu-IC columns were used for the separation of anionic analytes using chloride or acetate as the eluent-competing ion and direct UV spectrophotometric detection at 195 nm or using hydroxide as the eluent-competing ion and suppressed or nonsuppressed contactless conductivity detection. Separation efficiencies of 13,000 plates/m were observed (for iodate), and separation efficiency was maintained for large increases in flow rate (up to 42 microL/min, corresponding to a linear flow velocity of 18.5 mm/s), enabling highly reproducible, rapid separations to be achieved (seven analyte anions in less than 2 min). Use of a hollow fiber micromembrane suppressor enabled effective suppression of hydroxide eluents over the range 0.5-5.0 mM, thereby permitting suppressed conductivity detection to be performed. However, the relatively large size of the suppressor resulted in reduced separation efficiencies (e.g., 5400 plates/m for iodate). Detection limits obtained with suppressed conductivity detection were in the range 0.4-1.2 microM.     

Determination of trace perchlorate concentrations by anion-selective membranes and total reflection X-ray fluorescence analysis

In the present work a method for the determination of perchlorate trace levels by total reflection X-ray fluorescence (TXRF) is introduced. Perchlorate anions were concentrated on anion-selective membranes that had been prepared on the surface of TXRF quartz reflectors. Various complexation substances were used in the membranes. The reflectors were immersed in water solutions containing nanogram per milliliter (ppb) concentrations of perchlorate. After this step, the reflectors were taken out of the solution and they were analyzed by TXRF, using a copper X-ray tube and helium flow on the target (to lower the argon peak which is present in the air). The effects of various experimental parameters were examined, and the possibility of discrimination between chloride and perchlorate anions was shown. Minimum detection limits lower than 1 ng/mL and good linearity at the concentration range of 1-50 ng/mL were achieved. The method is applicable for the analysis of perchlorate in drinking water samples.     

Synthesis and evaluation of polymer-based zwitterionic stationary phases for separation of ionic species

Three different zwitterionic functional stationary phases for chromatography were synthesized on the basis of 2-hydroxyethyl methacrylate (HEMA) polymeric particles. Two synthesis routes, producing materials designated S300-ECH-DMA-PS or S300-TC-DMA-PS, involved activation of the hydroxyl groups of the HEMA material with epichlorohydrin or thionyl chloride, respectively, followed by dimethylamination and quaternizing 3-sulfopropylation with 1,3-propane sultone. The third route was accomplished by attaching methacrylate moieties to the HEMA through a reaction with methacrylic anhydride, followed by graft photopolymerization of the zwitterionic monomer 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium] propanesulfonate, initiated by benzoin methyl ether under 365-nm light. According to elemental analyses, both the S300-ECH-DMA-PS and S300-TC-DMA-PS materials appeared to have overall charge stoichometries close to unity, whereas the grafted material, S300-MAA-SPE, seemed to carry an excess of anion exchange sites in addition to the zwitterionic groups. Yet all three zwitterionic stationary phases were capable of separating inorganic anions and cations simultaneously and independently using aqueous solutions of perchloric acid or perchlorate salts as eluent, albeit with markedly different selectivities. On the S300-TC-DMA-PS and S300-MAA-SPE materials, the retention times increased for cations and decreased for anions with increasing eluent concentration, whereas with the S300-ECH-DMA-PS material, the retention times of both anions and cations decreased with increasing eluent concentration. These results demonstrate the importance of choosing appropriate synthesis conditions in order to prepare covalently bonded zwitterionic separation materials with an acceptable charge balance.     

Methods for the stable isotopic analysis of chlorine in chlorate and perchlorate compounds.

Chlorate and perchlorate compounds, used as herbicides, solid fuel propellants, and explosives, are increasingly recognized as pollutants in groundwater. Stable isotope characterization would permit both environmental monitoring of extent of remediation and forensic characterization. Stoichiometric reduction to chloride (greater than 98% yield), by Fe(II) for chlorate and alkaline fusion-decomposition for perchlorate, allows analysis by standard methods to give highly reproducible and accurate delta37Cl results (0.05/1000, 2 x standard error). Analysis of various compounds from different suppliers yielded delta37Cl values for chlorate samples near to +0.2/1000 (SMOC), but one has within-sample heterogeneity of 0.5/1000, possibly due to crystallization processes during manufacture. Results for perchlorate samples also are generally near +0.2/1000, but one is +2.3/1000 (SMOC). The initial results suggest that both forensic and environmental applications might be feasible.     

Biosorption of chromate anions from aqueous solution by a cationic surfactant-modified lichen (Cladonia rangiformis (L.))

Biosorption has been appearing as a useful alternative to conventional treatment systems for the removal of toxic metals from aqueous stream. The batch removal of chromate anions (CrO(4)(2-)) from wastewater under different experimental conditions using a cationic surfactant-modified lichen (Cladonia rangiformis (L.)) was investigated in this study. Cetyl trimethyl ammonium bromide (CTAB) was used for biomass modification. The results of the experiments showed that biomass modification substantially improved the biosorption efficiency. Effects of pH, biosorption time, initial CrO(4)(2-) concentration, biosorbent dosage, and the existence of the surfactant on the biosorption of CrO(4)(2-) anions were studied. Studies up to date have shown that the biosorption efficiency of chromium increased as the pH of the solution decreased. In the present study, the removal of chromate anions from aqueous solutions at high pH values with surfactant-modified lichen was investigated. From the results of the experiments it was seen that the removal of chromate anions by modified lichen was 61% at the solution natural pH (pH 5.11) but at the same pH value the removal of chromate anions by unmodified lichen was 6%. Also concentrations ranging from 30 to 150 mg/L Cr(IV) were tested and the biosorptive removal efficiency of the metal ions from aqueous solution at high pH was achieved more than 98%.     

Use of electrolytes containing multiple co-anions in the analysis of anions by capillary electrophoresis using indirect absorbance detection

Background electrolytes (BGEs) containing more than one UV-absorbing probe co-anion were investigated as possible means to control peak symmetries and improve the sensitivity of indirect detection in the separation of a mixture of inorganic and organic anions having a range of electrophoretic mobilities. In initial experiments, chloride and propanoate, which do not absorb at the detection wavelength, were added individually to a BGE containing phthalate as the UV-absorbing probe co-anion. The response ratios (i.e., the detector response for an analyte obtained with the BGE containing the probe and added co-anion divided by the response of the BGE containing the probe alone) were found to be dependent on the relative mobilities of the analyte, probe, and co-anion. In general, it was found that the analyte mainly displaced the BGE component to which its mobility was closest and exclusively displaced any BGE component having the same mobility. This behavior was utilized to design BGEs containing multiple probes to improve peak shapes by matching the mobilities of the BGE components with those of the analytes. A BGE comprising chromate and phthalate as probes was used to demonstrate the improvement in peak shapes when such an approach was used. This was further extended to a BGE containing three probes, namely, chromate, phthalate, and benzoate. System peaks were observed for each multiple-component BGE and for n BGE co-anions; n - 1 system peaks were induced. A simple linear function relating the mobility of the system peak for a two-co-anion BGE to the mobilities and relative concentrations of each of the co-anions was derived empirically. Finally, a series of probes was investigated to determine the optimum multiple BGE composition giving the best peak shapes and sensitivity in the separation of a mixture of 15 analytes. The best combination was a two-probe BGE consisting of chromate and 4-hydroxybenzenesulfonic acid.     

Tentacle-type zwitterionic stationary phase prepared by surface-initiated graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)-ammonium] propanesulfonate through peroxide groups tethered on porous silica

A novel stationary phase with tentacle-type zwitterionic interaction layer was synthesized by free radical graft polymerization of 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium]propanesulfonate (SPE) from the surface of Kromasil porous silica particles. The polymerization was initiated by thermal cleavage of tert-butylperoxy groups covalently attached to the particle surface, and the material therefore carries a tentacle-type polymeric interaction layer with 3-sulfopropylbetaine functional moieties. The composition of the surface graft was determined by elemental analysis, and the surface charge was measured using photon correlation spectroscopy. The measured zeta-potentials were close to 0 and nearly independent of pH, and the tentacle character of the interactive layers were evident from the lack of colloidal stability in the absence of salt (antipolyelectrolytic behavior) and a marked increase in column back-pressure when the concentration of perchloric acid or perchlorate salt was increased. The chromatographic properties were evaluated on columns packed with the functionalized material, and it was shown that this zwitterionic stationary phase could simultaneously and independently separate inorganic anions and cations using aqueous solutions of perchloric acid or perchlorate salts as eluents. The material was also capable of separating two acidic and three basic proteins in a single run, using gradient salt elution at constant pH.     

氯酸钾炸药爆炸性能研究

实验配制了7种典型氯酸钾炸药,进行了猛度测试,获得了相关实验数据.实验表明,氯酸钾与凡士林、铝粉配制的炸药具有较强的猛度,其猛度值与2#岩石炸药猛度值相当,相当于梯恩梯炸药的67%;75%氯酸钾、20%硫磺和5%铝粉配制成的炸药其猛度值相当于梯恩梯的47%.     

Counterionic Detection by ICP-AES for Determination of Inorganic Anions in Water Elution Ion Chromatography Using a Zwitterionic Stationary Phase

The analytical methods for the determination of inorganic anions by water elution ion chromatography using a zwitterionic column (C14SB-coated column) have been explored, where pure water was used as the mobile phase. In the present ion chromatography, the complicated peaks derived from various "ion pairs" appeared on the chromatogram when the sample solution contained several kinds of cations and anions. The chromatograms with the complicated peaks were simplified by using a preconditioning cation-exchange column. In the preconditioning column, various kinds of countercations of the analyte anions were converted to a particular kind of common cation, and thus all the analyte anions were separated as the common cation form. The more effective separation was achieved by converting to a divalent cation (Mg(2+)) form than a monovalent cation (Na(+)) form, because the anions paired with the divalent cation provided longer elution times than those paired with the monovalent cation. All the analyte anions separated as the common cation form were simply determined from their calibration curves drawn from conductivity detection. In addition, the counterionic determination of the anions was also attempted by using ICP-AES. The analyte anions were determined by measuring their countercations with ICP-AES, where the calibration curve of the countercation measured by ICP-AES could be used.     

Indirect laser-induced fluorescence detection for capillary electrophoresis using a violet diode laser

The violet (415 nm) diode laser is used for indirect laser-induced fluorescence detection in capillary electrophoretic separations of inorganic anions and chemical warfare agent degradation products. Inorganic anions were detected using 8-hydroxypyrene-1,3,6-trisulfonic acid as the indirect probe and achieved submicromolar (40-80 ppb) detection limits in a 2-min separation. The chemical warfare agent degradation products methylphosphonic acid, ethyl methylphosphonate, isopropyl methylphosphonate, and pinacolyl methylphosphonate were detected using the porphyrin tetrakis(4-sulfophenyl)porphine as the indirect probe and achieved detection limits of 0.1 microM (9 ppb), which are 1 order of magnitude better than that achieved using indirect UV detection. Baseline stability achieved with the violet diode laser was excellent, with dynamic reserve (DR) values of > 1000, which are 15 times better than that achieved using an unstabilized HeCd laser.     

A general, positive ion mode ESI-MS approach for the analysis of singly charged inorganic and organic anions using a dicationic reagent

Anion analysis continues to be of great importance to many scientific and technical fields. We propose here a general and sensitive method of detecting singly charged anions by ESI-MS and LC-ESI-MS as positive ions. This method utilizes a dicationic reagent to form a complex with the anion that retains an overall positive charge for analysis by MS. Nitrate, thiocyanate, perchlorate, perfluorooctanoic acid (PFOA), halogenated acetic acids, and various other inorganic and organic anions and are investigated. The use of tandem mass spectrometry to enhance the detection limits of some of the anions is demonstrated. Chaotropic anions provided the lowest detection limits, with PFOA detected at the hundreds of femtograms level. Indeed, this single approach provides the lowest reported detection limits for a variety of anions, especially PFOA, nitrate, monochloroacetic acid, dichloroacetic acid, and bromochloroacetic acid, among others. The integrated areas and signal-to-noise ratios for five ions during a chromatographic run in both the positive and negative ion modes are compared. The ability of this method to detect differences in related ions is shown for four arsenic species. Finally, a tap water sample is analyzed for the anions in this study using the dicationic reagent method.     

Efficient removal of chromate and arsenate from individual and mixed system by malachite nanoparticles

Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ～4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface.     

Perchlorate-selective polymeric membrane electrode based on bis(dibenzoylmethanato)cobalt(II) complex as a neutral carrier

A synthesized bis(dibenzoylmethanato)Co(II) complex (Co(DBM)(2)), has been used as a ionophore for the preparation of a new perchlorate ion-selective electrode. The electrode exhibits a Nernstian response over the perchlorate concentration range of 8.0x10(-7)-1.0x10(-1)M with a slope of 60.3+/-0.5 mV per decade of concentration. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot is 5.6x10(-7)M. The electrode shows good selectivity towards perchlorate with respect to many common anions. The response time of the sensor is very fast (< or = 5s), and can be used for at least 2 months in the pH range of 2.0-9.0. The electrode was used to determine perchlorate in water and human urine. The interaction of the ionophore with perchlorate ions was demonstrated by UV-vis spectroscopy.