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2018, ELECTROPHORESIS
This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4D) for the separation and detection of inorganic anions in post‐blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C4D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 Vpp. The separation of Cl−, NO3−, NO2−, SO42−, ClO4− and ClO3− was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 104 and 1.7 × 105 plates/m. The found limits of detection ranged between 2.5 and 9.5 μmol/L. Last, real samples of post‐blast explosive residues were analyzed on the ME‐C4D devices obtaining successfully the determination of Cl−, NO3− and SO42−. The achieved c...
ELECTROPHORESIS, 2008
Novel CE methods have been developed on portable instrumentation adapted to accommodate a capacitively coupled contactless conductivity detector for the separation and sensitive detection of inorganic anions and cations in post-blast explosive residues from homemade inorganic explosive devices. The methods presented combine sensitivity and speed of analysis for the wide range of inorganic ions used in this study. Separate methods were employed for the separation of anions and cations. The anion separation method utilised a low conductivity 70 mM Tris/70 mM CHES aqueous electrolyte (pH 8.6) with a 90 cm capillary coated with hexadimethrine bromide to reverse the EOF. Fifteen anions could be baseline separated in 7 min with detection limits in the range 27-240 mg/L. A selection of ten anions deemed most important in this application could be separated in 45 s on a shorter capillary (30.6 cm) using the same electrolyte. The cation separation method was performed on a 73 cm length of fused-silica capillary using an electrolyte system composed of 10 mM histidine and 50 mM acetic acid, at pH 4.2. The addition of the complexants, 1 mM hydroxyisobutyric acid and 0.7 mM 18-crown-6 ether, enhanced selectivity and allowed the separation of eleven inorganic cations in under 7 min with detection limits in the range 31-240 mg/L. The developed methods were successfully field tested on post-blast residues obtained from the controlled detonation of homemade explosive devices. Results were verified using ion chromatographic analyses of the same samples.
Separation & Purification Reviews, 2010
Journal of Chromatography B: Biomedical Sciences and Applications, 1998
A novel electrolyte has been developed for the effective separation by capillary electrophoresis of cations detected in low explosive residue. This electrolyte, with a pH of 4.4, employs 17.5 mM a-hydroxyisobutyric acid (HIBA) as the complexing agent, 6 mM imidazole as the ultraviolet visualization agent, 4 mM 18-crown-6 ether as a modifier to enhance the selectivity of the inorganic cations, and 5% (v / v) acetonitrile as an organic additive. Studies which assessed the value of the addition of 18-crown-6 and acetonitrile demonstrated conclusively that both were required in order to achieve unambiguous baseline separation of ammonium, potassium and monomethylammonium ions. The major advantages of the use of this electrolyte are a total run time of less than 7 min and symmetrical peak shapes. Validation on a series of preblast and postblast explosives materials determined that this procedure is reliable and robust.
TrAC. Trends in analytical chemistry, 2016
Capillary electrophoresis (CE) is a well-established analytical separation technique. Owing to its high versatility, major advancements have been made with regard to the instrumental setups during the last years. New strategies have been proposed to develop high-sensitive methods, portable CE or miniaturized devices. These techniques are of great interest in the analysis of explosives, which generally requires a highly selective approach. This review provides a recent perspective (from the beginning of 2008 to March 2015) on the use of CE for the analysis of explosives. First, a general description of explosives is made, emphasizing the role of separation techniques and specifically CE. Next, the most recent works focused on the analysis of explosives by using conventional CE, portable CE and microchip CE are compared and critically discussed. Besides, other emerging techniques for the analysis of explosives are referred and compared to CE results. Finally, future perspectives for the analysis of explosives by CE are proposed.
Jurnal Teknologi, 2007
In this study, a solid-phase microextraction (SPME) technique followed by gas chromatography (GC) was used to determine explosive residues. Several parameters including adsorption time, desorption time and temperature, SPME fiber types, stirring effect and salting out effect were optimized to obtain reproducible data with good accuracy. Addition of 10% w/v of NaCl in the aqueous medium and the use of a Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber coating led to optimal extraction efficiencies. The optimized SPME/GC-ECD method was applied to the trace analysis of explosive residues in water samples. 2,6-dinitrotoluene (2,6-DNT), trinitrotoluene (TNT) and pentaerythritol tetranitrate (PETN) were successfully detected from water samples. Direct Immersion SPME/GC-ECD was found to be an attractive technique for qualitative and quantitative analysis of explosives in post blast water samples.
Capillary electrophoresis method for simultaneous determination of inorganic anions and cations was developed using 2,6-pyridinedicarboxylic acid (PDC) as a background electrolyte (BGE) with indirect UV detection. In order to detect both anions and cations simultaneously, the electromagnetic flow was reversed by the addition of cetryltrimethylammonium hydroxide (CTAH). The parameters which influenced the separation of inorganic ions such as electrolyte pH, concentration of PDC, applied voltage and temperature were investigated. Four anions (Cl -, NO 3 -, SO 4 2-, SCN -) and three cations (Ca 2+ , Fe 2+ , Fe 3+ ) were successfully determined simultaneously in less than 7 min under the optimized conditions (25mM PDC, 0.5mM CTAH, pH 4.7). The method was applied to the analysis of post-blast explosive residues of black powder and ammonium nitrate-fuel oil (ANFO). The analytical performances of the method are discussed in terms of analysis time, repeatability, reproducibility, linearity of response and detection limits.
A capillary electrophoresis method for simultaneous determination of inorganic anions and cations was developed using 2,6-pyridinedicarboxylic acid (PDC) as a background electrolyte (BGE) with indirect UV detection. In order to detect both anions and cations simultaneously, the electromagnetic flow was reversed by the addition of cetryltrimethylammonium hydroxide (CTAH). The parameters which influenced the separation of inorganic ions such as electrolyte pH, concentration of PDC, applied voltage and temperature were investigated. Four anions (Cl-, NO3-, SO42-, SCN-) and three cations (Ca2+, Fe2+, Fe3+) were successfully determined simultaneously in less than 7 min under the optimized conditions (25mM PDC, 0.5mM CTAH, pH 4.7). The method was applied to the analysis of post-blast explosive residues of black powder and ammonium nitrate-fuel oil (ANFO). The analytical performances of the method are discussed in terms of analysis time, repeatability, reproducibility, linearity of response and detection limits.
Trends in Analytical Chemistry, 2017
Recent developments in electrochemical detection for microchip capillary electrophoresis Significant progress in the development of miniaturized microfluidic systems has occurred since their inception over a decade ago. This is primarily due to the numerous advantages of microchip analysis, including the ability to analyze minute samples, speed of analysis, reduced cost and waste, and portability. This review focuses on recent developments in integrating electrochemical (EC) detection with microchip capillary electrophoresis (CE). These detection modes include amperometry, conductimetry, and potentiometry. EC detection is ideal for use with microchip CE systems because it can be easily miniaturized with no diminution in analytical performance. Advances in microchip format, electrode material and design, decoupling of the detector from the separation field, and integration of sample preparation, separation, and detection on-chip are discussed. Microchip CEEC applications for enzyme/immunoassays, clinical and environmental assays, as well as the detection of neurotransmitters are also described.
Journal of Chromatography A, 2008
Anions and cations of interest for the post-blast identification of homemade inorganic explosives were separated and detected by ion chromatographic (IC) methods. The ionic analytes used for identification of explosives in this study comprised 18 anions (acetate, benzoate, bromate, carbonate, chlorate, chloride, chlorite, chromate, cyanate, fluoride, formate, nitrate, nitrite, perchlorate, phosphate, sulfate, thiocyanate and thiosulfate) and 12 cations (ammonium, barium(II), calcium(II), chromium(III), ethylammonium, magnesium(II), manganese(II), methylammonium, potassium(I), sodium(I), strontium(II), and zinc(II)). Two IC separations are presented, using suppressed IC on a Dionex AS20 column with potassium hydroxide as eluent for anions, and non-suppressed IC for cations using a Dionex SCS 1 column with oxalic acid/acetonitrile as eluent. Conductivity detection was used in both cases. Detection limits for anions were in the range 2-27.4 ppb, and for cations were in the range 13-115 ppb. These methods allowed the explosive residue ions to be identified and separated from background ions likely to be present in the environment. Linearity (over a calibration range of 0.05-50 ppm) was evaluated for both methods, with r 2 values ranging from 0.9889 to 1.000. Reproducibility over 10 consecutive injections of a 5 ppm standard ranged from 0.01 to 0.22% relative standard deviation (RSD) for retention time and 0.29 to 2.16%RSD for peak area. The anion and cation separations were performed simultaneously by using two Dionex ICS-2000 chromatographs served by a single autoinjector. The efficacy of the developed methods was demonstrated by analysis of residue samples taken from witness plates and soils collected following the controlled detonation of a series of different inorganic homemade explosives. The results obtained were also confirmed by parallel analysis of the same samples by capillary electrophoresis (CE) with excellent agreement being obtained. Crown
Analytical Chemistry, 2007
A commercial portable capillary electrophoresis (CE) instrument has been used to separate inorganic anions and cations found in postblast residues from improvised explosive devices (IEDs) of the type used frequently in terrorism attacks. The purpose of this analysis was to identify the type of explosive used. The CE instrument was modified for use with an in-house miniaturized lightemitting diode (LED) detector to enable sensitive indirect photometric detection to be employed for the detection of 15 anions (acetate, benzoate, carbonate, chlorate, chloride, chlorite, cyanate, fluoride, nitrate, nitrite, perchlorate, phosphate, sulfate, thiocyanate, thiosulfate) and 12 cations (ammonium, monomethylammonium, ethylammonium, potassium, sodium, barium, strontium, magnesium, manganese, calcium, zinc, lead) as the target analytes. These ions are known to be present in postblast residues from inorganic IEDs constructed from ammonium nitrate/fuel oil mixtures, black powder, and chlorate/perchlorate/sugar mixtures. For the analysis of cations, a blue LED (470 nm) was used in conjunction with the highly absorbing cationic dye, chrysoidine (absorption maximum at 453 nm). A nonaqueous background electrolyte comprising 10 mM chrysoidine in methanol was found to give greatly improved baseline stability in comparison to aqueous electrolytes due to the increased solubility of chrysoidine and its decreased adsorption onto the capillary wall. Glacial acetic acid (0.7% v/v) was added to ensure chrysoidine was protonated and to enhance separation selectivity by means of complexation with transition metal ions. The 12 target cations were separated in less than 9.5 min with detection limits of 0.11-2.30 mg/L (calculated at a signal-to-noise ratio of 3). The anions separation system utilized a UV LED (370 nm) in conjunction with an aqueous chromate
The forensic identification of bulk explosives plays a significant role in bombing investigation. The type and composition of explosives can be used to link suspects to the bombing crimes. In this study solid-phase microextraction (SPME) was employed for the recovery of seven selected nitro explosives from the aqueous samples using gas chromatography-electron capture detector (GC-ECD). Several SPME parameters including extraction time, desorption time, desorption temperature, as well as the concentration of sodium chloride (NaCl) for salting-out effect were optimized using Carboxen/polydimethylsiloxane (CAR/PDMS)-coated fiber. Addition of 10% w/v of NaCl in the aqueous compounds under study for the optimized SPME method was found to be within 2 to 10 ppb except for PETN (1.4 ppm). Solid-phase extraction (SPE) utilizing LiChrolut® EN sorbent was employed for an analyte preconcentration technique prior to SPME in post-blast water samples collected from sampling trays. Three water samples collected at two sampling points nearest to the explosion point were found to contain traces of PETN (0.020 – 0.039 ppm). SPE-SPME with direct immersion mode followed by GC-ECD analysis was found to be a viable method for qualitative and quantitative analysis of explosive residues in post-blast water samples.
Talanta, 2013
In order to train scientist field investigators after terrorist attacks, the laboratory of the Prefecture de Police of Paris simulated a suicide bombing attack in a bus. After collection of the residues, analyses were carried out to determine the composition of the original explosive charge. This article focuses on the combined use, for the first time, of three new capillary electrophoresis methods for the determination of inorganic anions and cations, and carbohydrates in two representative extracts. Capillary electrophoresis appears as an effective tool to identify and quantify the compounds in real extracts and is fully complementary to chromatographic methods.
Malaysian Journal of Analytical Sciences, 2008
Nitroaromatic, nitramine and nitrate ester compounds are a major group of high order explosive or better known as military explosives. Octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX), 2,4,6trinitro-toluene (TNT), pentaerythritol tetranitrate (PETN) and 2,4-dinitrotoluene (2,4-DNT) are secondary high explosives classified as most commonly used explosives components. There is an increasing demand for pre-concentration of these compounds in water samples as the sensitivity achieved by instrumental analytical methods for these high explosives residues are the main drawback in the application at trace levels for forensic analysis. Hence, a simple cartridge solid phase extraction (SPE) procedure was optimized as the off-line extraction and pre-concentration method to enhance the detection limit of high explosive residues using micellar electrokinetic chromatography (MEKC) and gas chromatography with electron-capture detection (GC-ECD) methods. The SPE cartridges utilized LiChrolut EN as the SPE adsorbent. By employing pre-concentration using SPE, the detection limits of the target analytes in water sample were lowered by more than 1000 times with good percentage recovery (> 87%) for MEKC method and lowered by 120 times with more than 2 % percentage recovery for GC-ECD methods. In order to test the feasibility of the developed method to real cases, post-blast water samples were analyzed. The post-blast water samples which were collected from Baling Bom training range, Ulu Kinta, Perak contained RDX and PETN in the range of 0.05-0.17 ppm and 0.0124-0.0390 ppm respectively.
… of Chromatography A, 2008
A new method has been developed to allow the determination of the chlorate, chloride and perchlorate anions in inorganic explosive residues to be made using isotachophoresis (ITP). To enable a good separation of these species to be achieved the method involves the use of two complexing agents. Indium(III) is used to allow the determination of chloride whilst using nitrate as the leading ion and ␣-cyclodextrin is used to allow the separation of chlorate and perchlorate. Separations were carried out using a miniaturised poly(methyl methacrylate) (PMMA) separation device. The method was applied to analysing both model samples and actual inorganic explosive containing residue samples. Successful determinations of these samples were achieved with no interference from other anions typically found in inorganic explosive residues. Limits of detection (LOD) for the species of interest were calculated to be 0.80 mg l −1 for chloride, 1.75 mg l −1 for chlorate and 1.40 mg l −1 for perchlorate.
Journal of Forensic Sciences, 1999
Improvised explosive devices are an increasing concern among law enforcement agencies within the United States because of their destructive capability. Capillary electrophoresis has been used previously for the forensic analysis of inorganic constituents in explosives. Micellar electrokinetic capillary electrophoresis (MECE), also known as micellar electrokinetic chromatography (MEKC), is well suited for the forensic analysis of organic constituents of these materials because of its high sensitivity and small sample requirements. In the present study, pipe bombs filled with known types of smokeless gun powder were detonated under controlled conditions. Samples of explosive residue were collected from the post-blast fragments and analyzed using MECE. The results were compared to the known types and analyzed to investigate the feasibility of matching post-blast residue to a specific powder used as explosive charge.
1997
A fast sample preparation method for the trace determination of some exploxives, by-products and degradation compounds in water by capillary gas chromatography is described. It is based on multiple extractions of the water sample with sub-milliliter amounts of solvent and subsequent concentration of the unified extracts by reducing its volume to a few microliters according to Dünges. The most suitable solvent was methyl-tert.-butylether. With electron caption detection and an aqueous sample volume of 25 to 100 ml, the determination level is in the pg/ml range.
Journal of Chromatography A, 2004
When explosives are present in natural aqueous media, their concentration is usually limited to trace levels. A preconcentration step able to remove matrix interferences and to enhance sensitivity is therefore necessary. In the present study, we evaluated solid-phase microextraction (SPME) technique for the recovery of nine explosives from aqueous samples using high-performance liquid chromatography with ultraviolet detection (HPLC-UV). Several parameters, including adsorption and desorption time, coating type, rate of stirring, salt addition, and pH, were optimized to obtain reproducible data with good accuracy. Carbowax coating was the only adsorbent found capable of adsorbing all explosives including nitramines. Method detection limits (MDL) were found to range from 1 to 10 g/L, depending on the analyte. SPME/HPLC-UV coupling was then applied to the analysis of natural ocean and groundwater samples and compared to conventional solidphase extraction (SPE/HPLC-UV). Excellent agreement was observed between both techniques, but with an analysis time around five times shorter, SPME/HPLC-UV was considered to be applicable for quantitative analysis of explosives.
Acta Chromatographica
A fast LC-APCI-MS/MS screening/confirmation method was developed and validated for trace analyses of 18 analytes which are explosives and organic gun shot residues including the challenging ones with diverse ionization conditions, in soil and on hands. (+) and (−) ionization modes were used after a single-step, low-volume solvent extraction procedure developed using methanol. Tape-lifting, stub, alcohol wipes, cotton bud were compared for collecting the residues from hands of a shooter. Tape-lifting and stub gave the highest recoveries and tape-lifting was chosen. Gradient elution system using ammonium chloride:methanol was developed. Whole procedure lasted approximately 30 min, was validated in both matrices, applied to real samples as post-blast residues, smokeless powder and the hands of a shooter, after shooting. Most of the recoveries were >80% and since all the precisions were <15%, quantitation was possible for all. Limit of Detection (LOD) and Limit of Quantification (...
Journal of Chromatography A, 1993
Micellar electrokinetic capillary chromatography (MECC) is investigated for application as a complementary technique to reversed-phase high-performance liquid chromatography (HPLC) in the analysis of explosives residues. Separation efficiency, specificity, sensitivity, reproducibility, analysis time and calibration linearity are examined by comparing the suitability of HPLC and MECC in parallel analyses. Authentic soil samples from a former trinitrotoluene plant are examined, and the results show MECC to be a useful new technique in explosive analysis, yielding good sensitivity, high resolution and short analysis times.
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