Chris G. Gill

Characterization of a condensed-phase membrane introduction mass spectrometry (CP-MIMS) interface using a methanol acceptor phase coupled with electrospray ionization for the continuous on-line quantitation of polar, low-volatility analytes at trace levels in complex aqueous samples.

We report the development and application of a capillary hollow fibre membrane interface using methanol as an acceptor phase to deliver target analytes to an electrospray ionization source and a triple quadrupole mass spectrometer. Superior fluid handling systems lead to greater signal stability and membrane integrity for the continuous on-line monitoring of polar and charged analytes in complex aqueous samples with detection limits in the parts-per-trillion to parts-per-billion range. The system can be operated in either a continuous flow or a stopped acceptor flow mode - the latter giving rise to greater sensitivity. We report detection limits, enrichment factors and signal response times for selected analytes with polydimethylsiloxane and Nafion® polymer membrane interfaces. In addition, we demonstrate the use of this interface to detect pharmaceuticals and other contaminants in natural water and artificial urine. The improved sensitivity and analytical response times of our CP-MIMS system make it possible to continuously monitor dynamic chemical systems with temporal resolutions on the order of minutes. Presented is a comparison of the performance of CP-MIMS versus direct infusion electrospray ionization, demonstrating the potential advantages over direct infusion for trace analyte measurements in complex, high ionic strength samples. Furthermore, by continuously flowing a reaction mixture in a closed loop over the interface, we demonstrate the use of the system as an in situ reaction-monitoring platform for the chlorination of a model organic compound in aqueous solution.

Application of weakly ionized plasmas for materials sampling and analysis

The use of weakly ionized plasmas as spectroscopic sources for materials sampling and analysis is reviewed. Plasma sources currently used for this purpose include direct-current and alternating-current plasmas, inductively coupled plasmas, microwave-induced plasmas, surface-wave plasmas, capacitively coupled plasmas, capacitive microwave plasmas, glow discharges, flowing afterglows, theta pinch discharges, exploding films and wires, and laser-produced plasmas. The authors give a summary of relevant characteristics of some of the plasma sources. Included are the source, common method of application, approximate detection limit for that method, applicability for solid sampling, susceptibility to matrix effects, approximate cost, and the most common usage for the method. >

Selective laser ablation/ionization for ion trap mass spectrometry: resonant laser ablation

Laser ablation provides a clean, broadly applicable ionization source for ion trap mass spectrometry. However, the ion storage capacity of an ion trap mass spectrometer requires a degree of selectivity in either the ion generation or ion storage process to allow effective interrogation of minority components. This can be accomplished by low-intensity irradiation of the sample with laser pulses tuned to a one- or two-photon resonant transition in the analyte of interest. Resonant laser ablation is a multistep process involving evaporation and subsequent ionization of a solid sample component of interest. The leading edge of a tunable laser pulse vaporizes near-surface material, which forms a plume directly above the sample. The trailing edge of the pulse preferentially excites, and subsequently ionizes, the component that is in resonance with the incident photons. In this manuscript, we report on the use of resonant laser ablation with an ion trap mass spectrometer for high sensitivity, high selectivity generation of analyte ions from a solid sample.

Low-power resonant laser ablation of copper.

We emphasize two points: (l) the properties and mechanisms of very low-fluence ablation of copper surfaces and (2) the sensitivity and selectivity of resonant laser ablation (RLA). We present results for ablation of bulk copper and copper thin films; spot-size effects; the effects of surface-sample preparation and beam polarization; and an accurate measurement of material removal rates, typically ≤ 10(-3) Å at 35 mJ/cm(2). Velocity distributions were Maxwellian, with peak velocities ≈ 1-2 × 10(5) cm/s. In addition, we discuss the production of diffractionlike surface features, and the probable participation of nonthermal desorption mechanisms. RLA is shown to be a sensitive and useful diagnostic for studies of low-fluence laser-material interactions.

A Field-Portable Membrane Introduction Mass Spectrometer for Real-time Quantitation and Spatial Mapping of Atmospheric and Aqueous Contaminants

AbstractEnvironmental concentrations of volatile and semivolatile organic compounds (VOC/SVOCs) can vary dramatically in time and space under the influence of environmental conditions. In an industrial setting, multiple point and diffuse sources can contribute to fugitive emissions. Assessments and monitoring programs using periodic grab sampling provide limited information, often with delay times of days or weeks. We report the development and use of a novel, portable membrane introduction mass spectrometry (MIMS) system capable of resolving and quantifying VOC and SVOCs with high spatial and temporal resolution, in the field, in real-time. An electron impact ionization cylindrical ion trap mass spectrometer modified with a capillary hollow fiber polydimethylsiloxane membrane interface was used for continuous air and water sampling. Tandem mass spectrometry and selected ion monitoring scans performed in series allowed for the quantitation of target analytes, and full scan mode was used to survey for unexpected analytes. Predeployment and in-field external calibrations were combined with a continuously infused internal standard to enable real-time quantitation and monitor instrument performance. The system was operated in a moving vehicle with internet-linked data processing and storage. Software development to integrate MIMS and relevant meta-data for visualization and geospatial presentation in Google Earth is presented. Continuous quantitation enables the capture of transient events that may be missed or under-represented by traditional grab sampling strategies. Real-time geospatial maps of chemical concentration enable adaptive sampling and in-field decision support. Sample datasets presented in this work were collected in Northern Alberta in 2010–2012. Graphical Abstractᅟ

Monitoring the TiO2-photocatalyzed destruction of aqueous environmental contaminants at parts-per-trillion levels using membrane introduction mass spectrometry (MIMS).

Abstract Membrane introduction mass spectrometry (MIMS) was used to directly monitor the TiO2/UV-photocatalyzed destruction of acetophenone, toluene, and chloroform in H2O at ppm to pptr concentrations. The instrument response time was sufficiently rapid for these environmental contaminants (1–6 min) that “real-time” monitoring of their degradation was possible. This method was used to follow the loss of toluene at pptr levels and the concomitant formation of one of its primary photo-oxidation intermediates, methylphenol. These results illustrate the potential use of MIMS as a sensitive on-line measurement technique for monitoring photocatalytic destruction of trace organic contaminants in water at environmentally relevant levels.

Resonant laser ablation as a selective metal ion source for gas-phase ion molecule reactions

Resonant laser ablation (RLA) is used as a source to selectively generate multiple metal ion species from the same sample. The capability of rapidly changing metal ions for gas-phase ion chemistry studies is a significant advantage in ion-molecule chemistry. The simple experimental arrangement uses relatively modest laser pulse energies (≤ 25 µJ/pulse) from a tunable dye laser to desorb and selectively ionize different metal atoms from a multicomponent sample. In turn, this allows the chemistry of several components to be investigated without breaking vacuum or altering the experimental geometry. This work demonstrates the use of RLA as a selective source of several reagent metal ions for gas-phase ion chemistry investigations. In particular, the reactivity of acetone with Cr+, Fe+, Ni+, and Cu+ was examined for metal ions selectively created by RLA from a standard steel sample.

A semi-quantitative approach for the rapid screening and mass profiling of naphthenic acids directly in contaminated aqueous samples

We report the use of a direct sampling, online analytical approach for the determination of acid extractable naphthenic acids in complex aqueous samples, known as condensed phase membrane introduction mass spectrometry (CP-MIMS). The technique employs a capillary hollow fibre semi-permeable membrane probe configured for immersion into a pH adjusted sample. A continuously flowing methanol acceptor phase transfers naphthenic acids to an electrospray ionization source, operated in negative ion mode, whereupon they are analysed by mass spectrometry as [M-H](-) ions. High-resolution mass spectrometry is used to characterize the influence of sample pH on membrane transport of multiple components of complex naphthenic acid mixtures. We demonstrate the use of CP-MIMS for semi-quantitative analysis of real-world samples using selected ion monitoring and full scan mass spectra at unit mass resolution. The technique has also been employed to continuously monitor the temporal evolution in the mass profile and concentrations of individual naphthenic acid isomer classes in heterogeneous solutions during adsorption processes. Copyright

Measurement of spatial and temporal variation in volatile hazardous air pollutants in Tacoma, Washington, using a mobile membrane introduction mass spectrometry (MIMS) system

The objective of this study was to use membrane introduction mass spectrometry (MIMS), implemented on a mobile platform, in order to provide real-time, fine–scale, temporally and spatially resolved measurements of several hazardous air pollutants. This work is important because there is now substantial evidence that fine-scale spatial and temporal variations of air pollutant concentrations are important determinants of exposure to air pollution and adverse health outcomes. The study took place in Tacoma, WA during periods of impaired air quality in the winter and summer of 2008 and 2009. Levels of fine particles were higher in winter compared to summer, and were spatially uniform across the study area. Concentrations of vapor phase pollutants measured by membrane introduction mass spectrometry (MIMS), notably benzene and toluene, had relatively uniform spatial distributions at night, but exhibited substantial spatial variation during the day—daytime levels were up to 3-fold higher at traffic-impacted locations compared to a reference site. Although no direct side-by-side comparison was made between the MIMS system and traditional fixed site monitors, the MIMS system typically reported higher concentrations of specific VOCs, particularly benzene, ethylbenzene and naphthalene, compared to annual average concentrations obtained from SUMA canisters and gas chromatographic analysis at the fixed sites.

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

AbstractNegative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M – H]–) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M – H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization. Graphical Abstractᅟ