Interference of chlorofluorocarbon (CFC)‐containing inhalers with measurements of volatile compounds using selected ion flow tube mass spectrometry

Selected ion flow tube mass spectrometry (SIFT-MS) is a sensitive technique capable of measuring volatile compounds (VCs) in complex gas mixtures in real time; it is now being applied to breath analysis. We investigated the effect of inhalers containing chlorofluorocarbons (CFCs) on the detection and measurement of haloamines in human breath. SIFT-MS mass scans (MS) and selected ion monitoring (SIM) scans were performed on three healthy non-smoking volunteers before and after inhalation of the following medications: Combivent™ metered-dose inhaler (MDI) (CFC-containing); Ventolin™ MDI (CFC-free); Atrovent™ MDI (CFC-free), Beclazone™ MDI (CFC-containing); Duolin™ nebuliser. In addition, the duration of the persistence of the mass/charge ratios was measured for 20 h. Inhalers containing CFCs generated large peaks at m/z 85, 87, 101, 103 and 105 in vitro and in vivo, consistent with the predicted product ions of CFCs 12, 114 and 11. No such peaks were seen with Duolin™ via nebuliser, or CFC-free MDIs. We conclude that measurement of VCs, such as haloamines, with product ions of similar m/z values to the ions found for CFCs would be significantly affected by the presence of CFCs in inhalers. This issue needs to be accounted for prior to the measurement of VCs in breath in people using inhalers containing CFCs. Copyright © 2009 John Wiley & Sons, Ltd.     

Magnetic Resonance Imaging of Hydrodynamic Dispersion in a Saturated Porous Medium

By using nuclear magnetic resonance imaging (NMRI) we have been able to analyse dispersion at the microscopic scale during steady-state flow through water-saturated glass beads. The flow rate through the porous medium was chosen high enough in order to neglect the influence of molecular diffusion on dispersion. Velocity statistics were measured, by NMRI, within slices of increasing thickness perpendicular to the direction of flow. It took more than two bead diameters before a representative elementary volume (REV) for the mean velocity was reached. This was in a region in the middle of the column that was not influenced by the boundary conditions. There the velocity variance decreased exponentially as a function of the slice thickness, due we consider to the formation of an interconnecting streamline network. The exponential decrease in the velocity variance reflects the transition from a local pattern of stochastic–convective flow to a convective–dispersion regime at the scale of the REV. We found that the point-like preferential influx and efflux boundary condition increased velocity variances and thus enhanced longitudinal hydrodynamic dispersion. Using the transverse correlation length of longitudinal velocity variance, we derived a mean transverse dispersivity that agreed well with Saffmans (1959) model. So we have been able to provide for the first time a direct observation verification of a part of Saffmans (1959) conjectures. By NMRI we observed this value to be independent of the observation scale of the slice thickness.     

Determination of isotopically labelled monoesterphthalates in urine by high performance liquid chromatography-mass spectrometry

A method of analysis for monoesters of phthalic acid ('monoesterphthalates') in human urine has been developed. The method was needed to determine the hydrolysis and excretion efficiency of isotopically-labelled phthalate diesters ('phthalates') when they were fed to volunteers as part of a biomarker study to estimate total exposure to phthalates. The targeted substances were 13C-monobutylphthalate (MBP), 2H4-monobutylphthalate (MBP), 2H4-monobenzylphthalate (MBeP), 13C-monocyclohexylphthalate (MCHP), 13C-monoethylhexylphthalate (MEHP), and 13C-monoisodecylphthalate (MIDP). The monoesters in urine were deconjugated enzymatically, extracted into solvent, and then determined by high performance liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionisation in the negative ion mode. The limits of determination were 10 ng ml(-1) for MBP, MCHP, MBeP and MEHP, and 40 ng ml(-1) for MIDP. The recovery from urine spiked at 100 ng ml(-1) was in the range from 70 to 85% except for MIDP which was lower at 55%. The between-batch reproducibility of the analysis was in the range 8 to 17% (n = 6 batches on separate days).     

Development and validation of a rapid headspace gas chromatography-mass spectrometry method for the determination of diethyl ether and acetone residues in Tween extracts of shellfish intended for mouse bioassay for diarrhoetic toxins

A validated analytical method using headspace capillary gas chromatography with mass spectrometric detection, which utilises deuterated analogues of the target analytes as internal standards has been developed and applied to the determination of acetone and diethyl ether in Tween extracts of cockles (Cerastoderma edule) and mussels (Mytilus edulis) destined for mouse bioassay for lipophilic toxins. The optimal conditions for headspace incubation were 50 degrees C for 6 min. The limits of detection and quantitation for both DEE and acetone were 2 and 7 microg/mL, respectively, based on signal to noise ratios of 3 and 10, respectively. The linear dynamic range of the instrument was 0 to ca. 4000 microg/mL for both acetone (r(2)=0.995) and DEE (r(2)=0.999). Tween extracts of cockle spiked with acetone and DEE at 3925 and 3570 microg/mL, respectively, gave mean (n=3) recovery figures of 101% (RSD=13.1%) for acetone and 90% (RSD=7.3%) for DEE in cockle matrix. The corresponding figures obtained from spiked mussel matrix were 114% (RSD=5.7%) for acetone and 95% (RSD=6.7%) for DEE, respectively, which were within acceptable range.