Detection of hexamethonium-perchlorate association complexes using NACE-MS.

Perchlorate (ClO(4) (+)) and other chlorine oxide anions were observed to complex weakly with hexamethonium (1,6-bis-(trimethylammonium)-hexane) in both aqueous and polar nonaqueous solvents. The resultant positively charged complexes were resolved by NACE using 2-propanol/acetone electrolytes prior to mass spectrometric detection using an Agilent(3D)CE system coupled to a Bruker Esquire 3000+ quadrupole IT mass detector. Using electrokinetic injection, the method detection limit for perchlorate in nonaqueous media was 10 microg/L. The isotope patterns due to the presence of (35)Cl and (37)Cl in complex mass spectra allowed for unambiguous identification of perchlorate, chlorate (ClO(3) (+)), chlorite (ClO(2) (+)), and chloride (Cl(+)) in photoreaction samples.

Interlaboratory study of a NACE method for the determination of R-timolol content in S-timolol maleate: assessment of uncertainty.

Analyses of statistical variance were applied to evaluate the precision and practicality of a CD-based NACE assay for R-timolol after enantiomeric separation of R- and S-timolol. Data were collected in an interlaboratory study by 11 participating laboratories located in Europe and North America. General qualitative method performance was examined using suitability descriptors (i.e. resolution, selectivity, migration times and S/N), while precision was determined by quantification of variances in the determination of R-timolol at four different impurity levels in S-timolol maleate samples. The interlaboratory trials were designed in accordance with the ISO guideline 5725-2. This allowed estimating for each sample, the different variances, i.e. between-laboratory (s2(Laboratories)), between-day (s2(Days)) and between-replicate (s2(Replicates)). The variances of repeatability (s2r) and reproducibility (s2R) were then calculated. The estimated uncertainty, derived from the precision estimates, seems to be concentration-dependent above a given threshold. This example of R-timolol illustrates how a laboratory can evaluate uncertainty in general.

Detection of nitroaromatic and cyclic nitramine compounds by cyclodextrin assisted capillary electrophoresis quadrupole ion trap mass spectrometry.

An Agilent 3DCE capillary electrophoresis system using sulfobutylether-beta-cyclodextrin (SB-beta-CD)-ammonium acetate separation buffer pH 6.9 was coupled to a Bruker Esquire 3000+ quadrupole ion trap mass detector via a commercially available electrospray ionization interface with acetonitrile sheath flow. The CE-MS system was applied in negative ionization mode for the resolution and detection of nitroaromatic and polar cyclic or caged nitramine energetic materials including TNT [2,4,6-trinitrotoluene, formula mass (FW) 227.13], TNB (1,3,5-trinitrobenzene, FW 213.12), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine, FW 222.26) HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, FW 296.16), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, FW 438.19). The CE-MS system conformed to the high-performance liquid chromatography with ultraviolet absorbance detection (HPLC-UV) and HPLC-MS reference methods for the identification of energetic contaminants and their degradation products in soil and marine sediment samples.

Sorption and degradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine in soil.

The sorption/desorption and long-term fate of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was examined using sterilized and nonsterilized soils. Two soils were used that differ mainly by the amount of total organic carbon (TOC): an agricultural topsoil (VT, 8.4% TOC) and a sandy soil (SSL, 0.33% TOC). The adsorption isotherms performed at room temperature were well-described by a linear model, which led to sorption distribution coefficients of 2.5 and 0.7 L kg(-1) for VT and SSL soils, respectively. The organic content of soil did not significantly affect HMX sorption. Over a period of 20 weeks, HMX degraded (60% disappearance) in static anaerobic nonsterile VT soil preparations. In separate experiments using UL-[14C]-HMX, 19% mineralization (liberated 14CO2) was obtained in 30 weeks. In addition, four nitroso derivatives of HMX were detected. Knowing the sorption/desorption behavior and the long-term fate of HMX in soil will help assess the effectiveness of natural attenuation for HMX removal.

Cyclodextrin-assisted capillary electrophoresis for determination of the cyclic nitramine explosives RDX, HMX and CL-20 comparison with high-performance liquid chromatography.

A sulfobutyl ether-beta-cyclodextrin-assisted electrokinetic chromatographic method was developed to rapidly resolve and detect the cyclic nitramine explosives 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and their related degradation intermediates in environmental samples. Development of the electrophoretic method required the measurement of the aqueous solubility of CL-20 which was determined to be 3.59 +/- 0.74 mg/l at 25 degrees C (95% confidence interval, n=3). The performance of the method was then compared to results obtained from existing high-performance liquid chromatography methods including US Environmental Protection Agency method 8330.

Accumulation of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) in indigenous and agricultural plants grown in HMX-contaminated anti-tank firing-range soil.

To investigate their potential for phytoremediation, selected agricultural and indigenous terrestrial plants were examined fortheir capacity to accumulate and degrade the explosive octahydro-1 ,3,5,7-tetra nitro-1,3,5,7-tetrazocine (HMX). Plant tissue and soil extracts were analyzed for the presence of HMX and possible degradative metabolites using high-performance liquid chromatography with diode-array UV detection (HPLC-UV), micellar electrokinetic chromatography with diode-array UV detection (MEKC-UV), and HPLC with electrospray ionization mass spectrometry (LC-MS). The pattern of HMX accumulation for alfalfa (Medicago sativa), bush bean (Phaseolus vulgaris), canola (Brassica rapa), wheat (Triticum aestivum), and perennial ryegrass (Loliumperenne) grown in a controlled environment on contaminated soil from an anti-tank firing range was similar to that observed for plants (wild bergamot (Monarda fistulosa), western wheat grass (Agropyron smithii), brome grass (Bromus sitchensis), koeleria (Koeleria gracilis), goldenrod (Solidago sp.), blueberry (Vaccinium sp.), anemone (Anemone sp.), common thistle (Circium vulgare), wax-berry (Symphoricarpos albus), western sage (Artemisia gnaphalodes), and Drummond's milk vetch (Astragalus drummondii)) collected from the range. No direct evidence of plant-mediated HMX (bio)chemical transformation was provided by the available analytical methods. Traces of mononitroso-HMX were found in contaminated soil extracts and were also observed in leaf extracts. The dominant mechanism for HMX translocation and accumulation in foliar tissue was concluded to be aqueous transpirational flux and evaporation. The accumulation of HMX in the leaves of most of the selected species to levels significantly above soil concentration is relevant to the assessment of both phytoremediation potential and environmental risks.