Voltammetric determination of nitroaromatic and nitramine explosives contamination in soil

The contamination of soil by nitroaromatic and nitramine explosives is widespread during the manufacture, testing and disposal of explosives and ammunitions. The analysis for the presence of trace explosive contaminants in soil becomes important in the light of their effect on the growth of different varieties of plants and crops. 2,4,6-Trinitrotoluene (TNT), cyclotrimethylene trinitramine (Research Department explosive, RDX) and cyclotetramethylene tetranitramine (high melting point explosive, HMX), other related explosive compounds and their by-products must be monitored in soil and surrounding waterways since these are mutagenic, toxic and persistent pollutants that can leach from the contaminated soil to accumulate in the food chain. In this study, a voltammetric method has been developed for the determination of explosive such as RDX, HMX and TNT. The electrochemical redox behavior of RDX, HMX and TNT was studied through cyclic voltammetry and quantitative determination was carried out by using square wave voltammetry technique. Calibration curves were drawn and were linear in the range of 63-129 ppm for RDX with a detection limit of 10 ppm, 49-182 ppm for HMX with a detection limit of 1 ppm and 38-139 ppm for TNT with a detection limit of 1 ppm. This method was applied to determine the contaminations in several soil samples that yielded a relative error of 1% in the concentrations.     

Determination of nitroaromatic and nitramine explosives from a PTFE wipe using thermal desorption-gas chromatography with electron-capture detection

A method for the detection of nitroaromatic and nitramine explosives from a PTFE wipe has been developed using thermal desorption andgas chromatography with electron-capture detection (TD-GC-ECD). For method development a standard mixture containing eight nitroaromatic and two nitramine (HMX and RDX) explosive compounds was spiked onto a PTFE wipe. Explosives were desorbed from the wipe in a commercial thermal desorption system and trapped onto a cooled injection system, which was incorporated into the injection port of the GC. A dual column, dual ECD configuration was adopted to enable simultaneous confirmation analysis of the explosives desorbed. For the desorption of 50 ng of each explosive, desorption efficiencies ranged between 80.0 and 117%, for both columns. Linearity over the range 2.5-50 ng was demonstrated for each explosive on both columns with r2 values ranging from 0.979 to 0.991 and limits of detection less than 4 ng. Desorption of HMX from a PTFE wipe has also been demonstrated for the first time, albeit at relatively high loadings (100 ng).     

Liquid chromatography of sugars on silica-based stationary phases

A review is given of sugar analysis by liquid chromatography using silica columns. Aspects covered are column materials and preparation, chemically and physically modified amine columns, octadecy- and unmodified silica columns; eluent composition and elution mechanisms for the different types of columns used; detection methods, RI and UV detectors, visible lights, fluorescence, moving-wire, polarimetric and mass detection; and sample preparation and origin of samples.     

Twenty years of research on silica-based chiral stationary phases

This review provides an overview of twenty years of pioneering work (from 1985 to 2005) of our research group in the preparation and application of enantioselective packing materials for HPLC. After a brief introduction to the rational design of a new chiral stationary phase, a detailed presentation in chronological order of appearance in the literature is given of the currently developed repertoire of chiral stationary phases and their typical applications. Emphasis is placed on the different synthetic strategies exploited to obtain highly efficient, stable, and versatile chiral stationary phases.     

Retention of anions on silica-based metalloporphyrin stationary phases.

The silica-based Fe(III)-protoporphyrin and Zn-tetraphenylporphyrin stationary phases were examined for the HPLC separation of anions. The retention of nine common inorganic anions as well as benzoate anion (BA) and its hydroxy analogues (HBA) was examined using tartrate, acetate, and succinate eluents. The retention factors of inorganic anions on the FeProP stationary phase were in the order Cl- < NO3- < ClO4- < I- < SCN- and for organic anions benzoate < p-hydroxybenzoate < m-hydoxybenzoate < o-hydroxybenzoate. The retention factors of organic anions examined for a ZnTPP column were in the order p-HBA < m-HBA < BA < o-HBA.     

Rapid detection of nitroaromatic and nitramine explosives on chromatographic paper and their reflectometric sensing on PVC tablets

Rapid and inexpensive sensing of explosive traces in soil and post-blast debris for environmental and criminological purposes with optical sensors has recently gained importance. The developed sensing method for nitro-aromatic and nitramine-based explosives is based on dropping an acetone solution of the analyte to an adsorbent surface, letting the solvent to dry, spraying an analytical reagent to produce a persistent spot, and indirectly measuring its reflectance by means of a miniature spectrometer. This method proved to be useful for on-site determination of nitro-aromatics (trinitrotoluene (TNT), 2,4,6-trinitrophenylmethylnitramine (tetryl) and dinitrotoluene (DNT)) and nitramines (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)) pre-adsorbed on a poly vinyl chloride (PVC) surface, with the use of different spray reagents for each group of explosives producing different colors. The calibration equations of the tested compounds as reflectance vs. concentration showed excellent linearity (correlation coefficient: 0.998-0.999). The linear quantification interval in terms of absolute quantity of analyte was 0.1-0.5 μg. The developed method was successfully tested for the analysis of military explosives Comp B and Octol, and was validated against high performance liquid chromatography (HPLC). The reflectometric sensing method could also be used for qualitative identification of the nitrated explosives on a chromatographic paper. The reagent-impregnated paper could also serve as sensor, enabling semi-quantitative determinations of TNT and tetryl.     

Development of silica-based stationary phases for high-performance liquid chromatography

Stationary phases are the basis of the development and application of high-performance liquid chromatography (HPLC). In this review we focused on the development of silica-based stationary phases, including the synthesis of silica gel and the application of silica in hydrophilic interaction chromatography (HILIC), reversed-phase liquid chromatography (RPLC), chiral separation chromatography, and ion chromatography. New stationary phases, advances in ionic liquid-modified silica, silica-based core-shell materials, and silica-based monolithic columns for HPLC are introduced separately.     

Synthesis and characterization of silica-based hyper-crosslinked sulfonate-modified reversed stationary phases

A novel type of silica-based sulfonate-modified reversed phase ((-)SO3-HC-C8) has been synthesized; it is based on a newly developed acid stable "hyper-crosslinked" C8 derivatized reversed phase, denoted HC-C8. The (-)SO3-HC-C8 phases containing controlled amounts of sulfonyl groups were made by sulfonating the aromatic hyper-crosslinked network of the HC-C(8) phase at different temperatures. The (-)SO3-HC-C8 phases are only slightly less hydrophobic than the parent HC-C8 phase. The added sulfonyl groups provide a unique strong cation-exchange selectivity to the hydrophobic hyper-crosslinked substrate as indicated by the very large C coefficient as shown through Snyder's hydrophobic subtraction reversed-phase characterization method. This cation-exchange activity clearly distinguishes the sulfonated phase from all other reversed phases as confirmed by the very high values of Snyder's column comparison function F(s). In addition, as was found in previous studies of silica-based and zirconia-based reversed phases, a strong correlation between the cation-exchange interaction and hydrophobic interaction was observed for these sulfonated phases in studies of the retention of cationic solutes. The overall chromatographic selectivity of these (-)SO3-HC-C8 phases is greatly enhanced by its high hydrophobicity through a "hydrophobically assisted" ion-exchange retention process.     

Preparation of stationary phases for open-tubular capillary electrochromatography using the sol-gel method

Capillary electrochromatography requires the deposition of a stationary phase inside the capillary. In this paper the sol-gel method is proposed for this purpose. The gels were prepared externally and injected into a fused-silica capillary, where anchorage to the capillary wall was possible through condensation reactions between the silanol groups of the capillary wall and the residual silanol groups the gel. Contrary to a commonly used practice, alkaline pretreatment of the inner capillary wall prior to the introduction and anchoring of the gel was found to be only marginally effective in improving the mechanical stability of the column. The influence of various parameters, such as the pH, the water content, the presence of alcohol (ethanol) on the formation of tetraethoxysilane (TEOS)-n-octyltriethoxysilane (C8-TEOS) hybrid gels of varied composition is discussed. The pH and the amount of water present were found to be the determining factors in the preparation of a stable gel with the desired mechanical and chromatographic properties. By carrying out the gel formation at 80 degrees C, capillary columns could be produced in 2.5 h. While an acidic pH was required during (external) gel formation, subsequent treatment of the gel inside the capillary with an alkaline solution ('aging') was found to improve separation and stationary phase capacity significantly. The capillary columns were subsequently used to separate a mixture of polycyclic aromatic hydrocarbons in less than 3 min.     

Comparison of zirconia- and silica-based reversed stationary phases for separation of enkephalins

In this study, the separation of biologically active peptides on two zirconia-based phases, polybutadiene (PBD)-ZrO2 and polystyrene (PS)-ZrO2, and a silica-based phase C18 was compared. Basic differences in interactions on both types of phases led to quite different selectivity. The retention characteristics were investigated in detail using a variety of organic modifiers, buffers, and temperatures. These parameters affected retention, separation efficiency, resolution and symmetry of peaks. Separation systems consisting of Discovery PBD-Zr column and mobile phase composed of a mixture of acetonitrile and phosphate buffer, pH 2.0 (45:55, v/v) at 70 degrees C and Discovery PS-Zr with acetonitrile and phosphate buffer, pH 3.5 in the same (v/v) ratio at 40 degrees C were suitable for a good resolution of enkephalin related peptides. Mobile phase composed of acetonitrile and phosphate buffer, pH 5.0 (22:78, v/v) was appropriate for separation of enkephalins on Supelcosil C18 stationary phase.     

Synthesis and characterization of hypercrosslinked, surface-confined, ultra-stable silica-based stationary phases

The synthesis and chromatographic characterization of a highly crosslinked self-assembled monolayer (SAM) stationary phase whose acid and thermal stability were significantly improved relative to a sterically protected octadecylsilane (ODS) stationary phase were recently described [B.C. Trammell, L. Ma, H. Luo, D. Jin, M.A. Hillmyer, P.W. Carr, Anal. Chem. 74 (2002) 4634]. Unfortunately, this highly crosslinked SAM phase is much more silanophilic than a conventional sterically protected octadecyl silane phase. 29Si CP-MAS NMR analysis shows that the high concentration of silanol groups in the self-assembled monolayer causes the increased retention and poor peak shape of basic solutes. In this work dimethyl-chloromethyl-phenylethylchlorosilane (DM-CMPES), a silane with only a single reactive silyl chloride group was tested as an alternative to chloromethyl-phenyethyltrichlorosilane (CMPES) as the basis for forming the starting phase. Most importantly this "conventional" silanization step (i.e., a non-SAM silanization) was followed by a Friedel-Crafts reaction using aluminum chloride as the catalyst and styrene heptamer as the multi-valent crosslinker to form the surface DM-CMPES groups into a network polymer which is fully confined and attached to the surface. An octyl (C8) derivative of the hypercrosslinked (HC) dimethyl-chloromethyl-phenylethyl (DM-CMPES) surface-confined stationary phase was synthesized to demonstrate the potential of a Friedel-Crafts based approach to making high efficiency, acid and thermally stable polymerized phases on silica with selectivity closer to conventional aliphatic phases. The stability of the retention factors of these phases under very aggressive conditions (5%, (v/v) trifluoroacetic acid and 150 degrees C) are compared to that of a sterically protected octadecylsilane (ODS) phase. The comparisons show that the long term stability of highly crosslinked DM-CMPES phases in acid is superior to the conventional phase. The HC-C8 phase is even more stable in acid than the HC-styrene heptamer DM-CMPES phase on which it is based. Additionally, the efficiency and peak shape of several prototypical bases under acidic (0.1% TFA, pH 2.0) elution conditions are discussed. The column dynamics and thermodynamic characteristics of the HC-C8 phase were investigated to demonstrate the chromatographic utility of this ultra-stable phase. Inverse size exclusion chromatography and flow studies of the HC-C8 and the sterically protected C18 stationary phases indicate the absence of pore plugging and quite good (nearly 100,000 plates/m) chromatographic efficiency. Further chromatographic investigations show that the HC-C8 stationary phase behaves as a typical reversed phase material. The HC-C8 stationary phase offers unique chromatographic selectivity for certain classes of analytes compared to both alkyl and phenyl bonded phases.     

Determination of nitroaromatic, nitramine, and nitrate ester explosives in soil by gas chromatography and an electron capture detector

Hazardous waste site characterization, forensic investigations, and land mine detection are scenarios where soils may be collected and analyzed for traces of nitroaromatic, nitramine, and nitrate ester explosives. These thermally labile analytes are traditionally determined by high-performance liquid chromatography (HPLC); however, commercially available deactivated injection port liners and wide-bore capillary columns have made routine analysis by gas chromatography (GC) possible. The electron-withdrawing nitro group common to each of these explosives makes the electron capture detector (ECD) suitable for determination of low concentrations of explosives in soil, water, and air. GC-ECD and HPLC-UV concentration estimates of explosives residues in field-contaminated soils from hazardous waste sites were compared, and correlation (r>0.97) was excellent between the two methods of analysis for each of the compounds most frequently detected: 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), 2,4-dinitrotoluene (2,4-DNT), 1,3-dinitrobenzene (1,3-DNB), 1,3,5-trinitrobenzene (TNB), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The analytes were extracted from soils with acetonitrile by 18 h of sonication in a cooled ultrasonic bath. Two soil-to-solvent ratios were evaluated: 2.00 g:10.00 ml and 25.0 g:50.0 ml. GC-ECD method detection limits were similar for the two soil-to-solvent ratios and were about 1 mug kg(-1) for the di- and trinitroaromatics, about 10 mug kg(-1) for the mono-nitroaromatics, 3 mug kg(-1) for RDX, 25 mug kg(-1) for HMX, and between 10 and 40 mug kg(-1) for the nitrate esters (nitroglycerine [NG] and pentaerythritol tetranitrate [PETN]). Spike recovery studies revealed artifacts introduced by the spiking procedure. Recoveries were low in some soils if the amount of soil spiked was large (25.0 g) compared to the volume of spike solution added (1.00 ml). Recoveries were close to 100% when 2.00-g soil samples were spiked with 1.00 ml of solution. Analytes most frequently found in soils collected near buried land mines were the microbial transformation products of TNT (2-amino-4,6-dinitrotoluene [2-Am-DNT] and 4-amino-2,6-dinitrotoluene [4-Am-DNT]), manufacturing impurities of TNT (2,4-DNT, 2,6-DNT, and 1,3-DNB), and TNT. The microbial reduction products of the isomers of DNT and of 1,3-DNB were also detected, but the ECD response to these compounds is poor.     

Electrochemical detection of ultratrace nitroaromatic explosives using ordered mesoporous carbon

A sensitive electrochemical sensor has been fabricated to detect ultratrace nitroaromatic explosives using ordered mesoporus carbon (OMC). OMC was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption measurements. Glassy carbon electrodes functionalized with OMC show high sensitivity of 62.7 μA cm⁻² per ppb towards 2,4,6-trinitrotoluene (TNT). By comparison with other materials such as carbon nanotubes and ordered mesoporous silica, it is found that the high performance of OMC toward sensing TNT is attributed to its large specific surface area and fast electron transfer capability. As low as 0.2 ppb TNT, 1 ppb 2,4-dinitrotoluene and 1 ppb 1,3-dinitrobenzene can be detected on OMC based electrodes. This work renders new opportunities to detect ultratrace explosives for applications of environment protections and home securities against chemical warfare agents.     

Retention and selectivity tests of silica-based and metal-oxide bonded stationary phases for RP-HPLC

Chromatographic properties of silica-, zirconia- and alumina-based columns with octadecyl-, polyethylene glycol- and pentafluorophenylpropyl-bonded stationary phases were tested. Selectivities of nine columns for LC were characterized using chromatographic methods including Walters, Engelhardt, Tanaka and Galushko hydrophobicity and silanol activity tests, measurements of methylene selectivity in various aqueous-methanol and aqueous-acetonitrile mobile phases and of gradient lipophilic capacity as a measure of the effect of the sample hydrophobicity on gradient-elution separations. A semi-empirical interaction indices model, assuming a predominant role of the solvophobic interactions of test compounds with different polarities, was compared with the linear free energy relationships approach taking into account selective polar interactions. The interaction indices model was applied to both non-polar stationary phases bonded on silica, alumina and zirconia supports, and to the non-modified adsorbents in the normal-phase LC. The retention data of isomeric naphthalene disulfonic acids were used to compare the attractive and repulsive ionic interactions of the columns in purely aqueous mobile phases. The results of the hydrophobicity and polarity tests were consistent, and allowed column characterization and classification. Silanol activity was important with octadecyl silica columns, but was relatively insignificant with bonded polyethylene glycol and pentafluorophenylpropyl phases on silica gel support. Polar interactions with the alumina and zirconia support materials significantly affect the retention.     

Selective extraction of nitroaromatic explosives by using molecularly imprinted silica sorbents

Two molecularly imprinted silicas (MISs) were synthesized and used as selective sorbents for the extraction of nitroaromatic explosives in post-blast samples. The synthesis of the MISs was carried out with phenyltrimethoxysilane as monomer, 2,4-dinitrotoluene (2,4-DNT) as template and triethoxysilane as cross-linker by a sol–gel approach in two molar ratios: 1/4/20 and 1/4/30 (template/monomer/cross-linker). Non-imprinted silica sorbents were also prepared following the same procedures without introducing the template. An optimized procedure dedicated to the selective treatment of aqueous samples was developed for both MISs for the simultaneous extraction of the template and other nitroaromatic compounds commonly used as explosives. The capacity of the MISs was measured by the extraction of increasing amounts of 2,4-DNT in pure water and is higher than 3.2 mg/g of sorbent for each MIS. For the first time, four nitroaromatic compounds were selectively extracted and determined simultaneously with extraction recoveries higher than 79%. The potential of these sorbents was then highlighted by their use for the clean-up of post-blast samples (motor oil, post-mortem blood, calcined fragments, etc.). The results were compared to those obtained using a conventional sorbent, thus demonstrating the interest of the use of these MISs as selective sorbents.     

Application of silica-based hyper-crosslinked sulfonate-modified reversed stationary phases for separating highly hydrophilic basic compounds

The separation and determination of hydrophilic basic compounds are of great importance in many fields including clinical and biological research, pharmaceutical development and forensic analysis. However, the most widely used analytical separation technique in these disciplines, reversed-phase liquid chromatography (RPLC), usually does not provide sufficient retention for several important classes of highly hydrophilic basic compounds including catecholamines, many drug metabolites and many drugs of abuse. Commonly eluents having little or no organic modifier and/or strong ion pairing agents must be used to achieve sufficient retention and separation. Use of highly aqueous eluents can lead to column failure by dewetting, resulting in poor retention, low selectivity and irreproducibility and slow recovery of performance. The use of a strong ion pairing agent to increase retention renders the separation incompatible with mass spectrometric detection and complicates preparative separations. This paper describes the successful applications of a novel type of silica-based, hyper-crosslinked, sulfonate-modified reversed stationary phase, denoted as (-)SO(3)-HC-C(8)-L, for the separation of highly hydrophilic cations and related compounds by a hydrophobically assisted cation-exchange mechanism. Compared to conventional reversed-phases, the (-)SO(3)-HC-C(8)-L phase showed significantly improved retention and separation selectivity for hydrophilic amines. Concurrently, due to the presence of both cation-exchange and reversed-phase retention mechanisms and the high acid stability of hyper-crosslinked phases, the separation can be optimized by changing the type or concentration of ionic additive or organic modifier, and by varying the column temperature. In addition, gradients generated by programming the concentration of either the ionic additive or the organic modifier can be applied to reduce the analysis time without compromising resolution. Furthermore, remarkably different chromatographic selectivities, especially toward cationic solutes, were observed upon comparing the (-)SO(3)-HC-C(8)-L phase with conventional reversed-phases. We believe that the combination of these two types of stationary phases will be very useful in two-dimensional liquid chromatography.     

Use of porous graphitic carbon for the analysis of nitrate ester, nitramine and nitroaromatic explosives and by-products by liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry

A new LC/MS method was developed for the analysis of sixteen different analytes including the most common organic explosives encountered in forensic investigations. The separation was achieved using a porous graphitic carbon (PGC) column with a binary gradient elution. Molecular modeling suggested a possible interpretation for the elution order of explosive compounds on PGC. The introduction of ammonium formate in the mobile phase resulted in the formation of characteristic adduct ions thus enhancing the mass spectrometric detection of nitrate ester and nitramine compounds. Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) were compared in terms of sensitivity. The final LC/APCI-MS method allowed easy identification of investigated compounds with limits of detection ranging from 0.04 to 1.06 ng/microl. The analysis of simulated forensic samples confirmed the performance of the method.     

Effect of reagents mixing on the thermal behavior of sol-gel precursors for silica-based nanocomposite thin films

The paper presents, based on TG-DTG-DSC data, some results of the thermal decomposition of some complex sol-gel precursors used for the deposition of mesoporous ZnO/SiO₂ nanocomposite thin films for gas sensing applications. The effect chemical composition of the sol and reagents mixing during the sol preparation is discussed. The chemical nature of ZnO source (zinc acetate solid salt, zinc acetate alcoholic solution or ZnO nanopowder) used for the sol preparation significantly affects the thermal decomposition of complex precursor and the microstructure and properties of the nanocomposite thin films.     

High-performance anion-exchange chromatography of proteins using aza-ether bonded silica-based phases

The use of wide-pore silica-based hydrophilic aza-ether bonded phases for the chromatographic separation of proteins under anion-exchange conditions was studied. Polyether silanes containing terminal morpholine or piperazine derivatives are synthesized for attachment to the silica surface and provide a flexible approach to bonded phase design. In one instance, a quaternized amine support may be prepared by further derivatization of the methylpiperazine bonded phase. The supports provide high-performance anion-exchange chromatographic separations of proteins using gradients of increasing salt content, e.g., to 1.0 M sodium acetate at pH 7.0. The salt type and concentration can be varied to control protein retention while the buffer system used at pH 7.0 exerts a minimal influence on the separation. The anion exchangers may be reproducibly prepared and exhibit chromatographic retention stability at pH 7.5 for at least 2 months of operation. Acceptable capacity for protein on the bonded phase is demonstrated with high recovery of solute mass. The flexibility in anion exchanger design provides a probe of bonded ligand hydrophobic effects which can contribute in an undefined and deleterious manner to the desired ion-exchange separation. Taken together, these results provide a greater insight into the operating characteristics of anion exchangers, especially with regard to competing retention mechanisms.