Effect of Humidity on the Mobilities of Small Ions in Ion Mobility Spectrometry.

Ions in the ion mobility spectrometry (IMS) are mostly hydrated. A single peak in the drift time spectrum is usually generated by a mixture of ions differing in the number of attached water molecules. Under real IMS detector operating conditions, ions change their composition during movement in the drift region due to the changes in the number of water molecules attached to the ion. The impact of water vapor on the drift times of small ions at different temperatures was studied experimentally using an ion mobility spectrometer. The experiments were carried out for hydronium, ammonium, oxygen, chloride, bromide, and iodide ions. A theoretical model was developed, allowing us to calculate the effective mobility of ions for a given concentration of water vapor and temperature. The basic assumption adopted in this model was the linear dependence of the effective mobility coefficient on the mobility of ions with a certain degree of hydration. The weighting factors in this relationship are the abundances of individual types of ions. These parameters were determined by calculations based on the thermodynamics of the formation and disintegration of ionic clusters. From the known values of temperature, pressure, and humidity, the values of effective mobilities can be predicted quite accurately. The dependencies of reduced mobilities on the average degree of hydration were also determined. For these dependencies, the measurement points on the graphs are gathered along specific lines. This means that the average degree of hydration unambiguously determines the value of reduced mobility for a given type of ions.

Negative-mode ion mobility spectrometry-comparison of ion-molecule reactions and electron capture processes.

The presented work concerns the impact of ionization mechanisms of analytes on detection sensitivity in negative-mode ion mobility spectrometry. The main part of the work is research conducted for selected organic analytes using DT IMS in the negative mode of operation. In the negative mode of detection, two ionization mechanisms can be used: electron capture and ion-molecule reactions. The type of ionization mechanism depends on the carrier gas. The tests were carried out using two carrier gases: air and nitrogen. This allowed for a comparison of the ionization of analytes in the ion-molecule reaction mode with ionization in electron capture mode. Experiments were carried out for tetrachloromethane, trichloromethane, benzyl chloride, 1-chlorobutane, 1-chlorohexane, 1-chloropentane, tetrachlorethylene, 1-bromobutane, 1-bromopentane, 1-bromohexane, hexafluorobenzene, 2-chloroethyl ethyl sulfide (CEES), and methyl salicylate. Most of the tested substances were ionized with the formation of ionized halogen atoms (Br- or Cl-). It was found that among the tested substances, there are those whose effective ionization is possible with the use of both nitrogen and air as carrier gases, those ionized only in electron capture mode or in ion-molecule reaction mode. The important part of the work was an investigation on the effect of oxygen and water admixtures in carrier gases on the detection efficiency of selected organic compounds.

Studies on the Processes of Electron Capture and Clustering of Benzyl Chloride by Ion Mobility Spectrometry.

This paper presents the results of the study on the course of the benzyl chloride (BzCl) ionization process in a drift tube ion mobility spectrometer (DT IMS) in which nitrogen was used as the carrier gas. BzCl ionization follows the dissociative electron capture mechanism. The chloride ions produced in this process take part in the formation of cluster ions. Using DT IMS allows for estimation of the value of the electron attachment rate for BzCl and the equilibrium constant for the cluster ion formation. The basic experimental method used in this work was to analyze drift time spectra obtained for the introduction of the sample to the spectrometer with the drift gas. The theoretical interpretation of the results is based on the mathematical description of the ion transport. This description takes into account the phenomenon of diffusion, as well as the processes of formation and dissociation of ionic clusters occurring during the movement of ions in the drift section.

Application of Ion Mobility Spectrometry for Permeability Studies of Organic Substances through Polymeric Materials.

Drift tube ion mobility spectrometers (DT IMS) allow the concentration of different organic compounds to be measured. This gives the opportunity to use these detectors in measuring the penetration of various substances through polymer membranes. Permeation measurements of two substances (2-heptanone and dimethyl methylphosphonate (DMMP)) through a cylindrical silicone rubber membrane were carried out. The membrane separated the aqueous solution from the air. The analyte was introduced into water, and then its concentration in air on the opposite side of the membrane was recorded. Based on the dynamics of detector signal changes, the diffusion coefficients for both tested substances were determined. Determination of permeability coefficients was based on precise quantitative measurements, which took into account the non-linearity of the detector characteristics and the effect of water on detection sensitivity. The analysis of measurement results was based on a mathematical description of diffusion process.

Analysis of e-liquids for electronic cigarettes using GC-IMS/MS with headspace sampling.

Electronic cigarettes (e-cigarettes) are continuously increasing in popularity due to being considered healthier compared with traditional cigarettes. Based on the European directive 2014/40/EU [1] the German legislation restricts the usage of potential harmful substances in these tobacco related products [2,3]. The aim of this work was to establish a method for the detection and quantification of selected substances covered by the above regulation. For this purpose, one-of-a-kind gas chromatograph with ion mobility spectrometer (GC-IMS) was used. Instrument was parallelly coupled with conventional chromatograph equipped with quadrupole mass spectrometer (GC-MS). Headspace (HS) was used as a sample preparation technique. During initial tests both systems were correlated by using a mixture of simple carbonyl compounds. The identification of the selected analytes was performed by mass spectrometry and calibration curves for the quantification were recorded. For all tested substances the limit of detection (LOD) and limit of quantification (LOQ) were determined. The LOD ranges are from 8 to 70 µg/L, the LOQ are from 25 to 200 µg/L. For testing the usability of the developed method 20 samples of commercially available refills for e-cigarettes (e-liquids), produced in Germany and Poland, were analyzed. Substances listed in the directive were found in all samples. In two of them an according to the regulations forbidden substance (estragole) was detected.

Ion mobility spectrometers and electron capture detector - A comparison of detection capabilities.

Electron capture detectors (ECDs) and detectors used in ion mobility spectrometry (IMS) have been successfully used for the detection of numerous compounds including hazardous substances. The general principles of their operations are similar and based on sample component ionization and measurement of the signal using the differences in the mobility of electric charge carriers. Differences in sensitivity result from various parameters of these instruments. Value of electric field intensity in ionic reactors have an influence on ionization process. The main goal of the performed tests was to compare the analytical properties of ECD and two types of IMS detectors: a drift tube spectrometer (DT IMS) and a differential mobility spectrometer (DMS). In the work performed, the efficiency of ionization and the response of detectors to selected analytes were compared. ECD, DT IMS and DMS were equipped with 63-Ni radioactive sources. Analytes have been ionized via electron capture process or dissociative electron transfer. Results obtained for oxygen and chloro-substituted organic compounds (carbon tetrachloride, benzyl chloride, chloroform, 2-chloroethyl ethyl sulfide) were used to calculate the relative signal and to compare the ionization efficiency for three detectors. The phenomena observed experimentally were related to energy dependencies and electron capture cross-sections of analytes. The efficiency of ionization in DT IMS was also compared for electron capture when nitrogen was used as the carrier gas, and when the ionization process was based on the collisions of the analyte molecules with the O2- with the use of air.

Nitrogen oxides as dopants for the detection of aromatic compounds with ion mobility spectrometry.

Limits of detection (LODs) in ion mobility spectrometry (IMS) strictly depend on ionization of the analyte. Especially challenging is ionization of compounds with relatively low proton affinity (PA) such as aromatic compounds. To change the course of ion-molecule reactions and enhance the performance of the IMS spectrometer, substances called dopants are introduced into the carrier gas. In this work, we present the results of studies of detection using nitrogen oxides (NOx) dopants. Three aromatic compounds, benzene, toluene, toluene diisocyanate and, for comparison, two compounds with high PA, dimethyl methylphosphonate (DMMP) and triethyl phosphate (TEP), were selected as analytes. The influence of water vapour on these analyses was also studied. Experiments were carried out with a generator of gas mixtures that allowed for the simultaneous introduction of three substances into the carrier gas. The experiments showed that the use of NOx dopants significantly decreases LODs for aromatic compounds and does not affect the detection of compounds with high PA. The water vapour significantly disturbs the detection of aromatic compounds; however, doping with NOx allows to reduce the effect of humidity. Graphical Abstract Two possible ionization mechanisms of aromatic compounds in ion mobility spectrometry: proton transfer reaction and adduct formation.

Quantitative response of IMS detector for mixtures containing two active components.

This study describes the relationship between the output signal of the ion mobility spectrometry (IMS) detector and the concentrations of two compounds being simultaneously introduced into the reaction section. Investigations were performed for three pairs of compounds, that is, dimethyl methylphosphonate (DMMP) and acetone, methyl tert-butyl ether (MTBE), and acetone, as well as trimethylamine (TMA) and n-nonylamine (NA). Vapors of the investigated compounds were produced in a two-channel generator with permeation sources and a dilution system based on mass-flow controllers. The generator design and the method of concentration determination are discussed in this paper. It was found that admixture can differently influence detection of an analyte. The presence of acetone does not effect the signal corresponding to dimer ions of DMMP. For pairs MTBE + acetone and TMA + NA characteristic peaks of analyte ions diminish with growing concentration of admixture, however, the detection based on the peak of the asymmetric dimer containing proton-bound molecules of both compounds is effective. For the detection of TMA in the presence of NA, the signal generated by the asymmetric dimer ions is meaningfully higher than the signals of monomer or dimer TMA ions measured without the NA admixture. The course of calibration dependencies was analyzed on the basis of a simple mathematical model of the reaction region. This model provided an estimation of the intensity of the signal for a given ionic species for definite concentration of analyte.

Efficiency of hydroxyl radical formation and phenol decomposition using UV light emitting diodes and H2O2.

A novel process combining hydrogen peroxide (H2O2) and radiation emitted by ultraviolet light emitting diodes (UV LEDs) has been investigated. The UV LEDs were used as UV-C light sources emitting radiation in the range 257-277 nm for decomposition of the model substance phenol in water. In addition, the effect of H2O2 to phenol molar ratio and initial phenol concentration was examined. Two parameters, the decomposition efficiency of phenol and characterization of hydroxyl radical (HO*) production from H2O2 when illuminated with UV radiation, were selected to provide detailed information regarding the performance of the UV LEDs in the treatment process. A new concept was introduced to characterize and describe the production of HO* radicals produced when photons were absorbed by H2O2 molecules. The phenol decomposition efficiency at the initial concentration of 100 mg/L was the most pronounced at the lowest emitted wavelength. A significant correlation was found between the phenol decomposition efficiency and the photons absorbed by H2O2 (i.e. formation of radicals).

Fast detection of methyl tert-butyl ether from water using solid phase microextraction and ion mobility spectrometry.

Methyl tert-butyl ether (MTBE) is commonly used as chemical additive to increase oxygen content and octane rating of reformulated gasoline. Despite its impact on enhancing cleaner combustion of gasoline, MTBE poses a threat to surface and ground water when gasoline is released into the environment. Methods for onsite analysis of MTBE in water samples are also needed. A less common technique for MTBE detection from water is ion mobility spectrometry (IMS). We describe a method for fast sampling and screening of MTBE from water by solid phase microextraction (SPME) and IMS. MTBE is adsorbed from the head space of a sample to the coating of SPME fiber. The interface containing a heated sample chamber, which couples SPME and IMS, was constructed and the SPME fiber was introduced into the sample chamber for thermal desorption and IMS detection of MTBE vapors. The demonstrated SPME-IMS method proved to be a straightforward method for the detection of trace quantities of MTBE from waters including surface and ground water. We determined the relative standard deviation of 8.3% and detection limit of 5 mg L(-1) for MTBE. Because of short sampling, desorption, and detection times, the described configuration of combined SPME and IMS is a feasible method for the detection of hazardous substances from environmental matrices.

Processing of the signal from detectors used in ion mobility spectrometry.

The output signal generated by detectors used in ion mobility spectrometry (IMS) is a time-dependent, small ionic current. To be able to take full advantage of information contained in this signal, adequate procedures of signal processing need to be utilized. Methods of spectrum filtration, peak separation, base-line correction as well as one- and two-dimensional integration applied in quantitative analysis are described. The effectiveness of the chosen methods was demonstrated on examples of experimental results obtained by IMS. Measurements were performed for spectra of reactant ions and sample ions generated by acetone, methyl tert-butyl ether (MTBE), dimethyl methylphosphonate (DMMP) and benzene. It was demonstrated that the proposed methods considerably improve the quality of the spectra, increase the selectivity of detection and reduce the uncertainty of quantitative measurements.

A study of the performance of an ion shutter for drift tubes in atmospheric pressure ion mobility spectrometry: computer models and experimental findings.

Ion mobility spectra are initiated when ions, derived from a sample, are pulsed or injected through ion shutters into a drift region. The effect on signal intensity from electric fields arising from the shutter grids (E(s)) and a superimposed electric field of the drift tube (E(d)) was determined experimentally and simulated computationally for ion motion at ambient pressure. The combination of these two fields influenced shutter performance in three ways: (1) intensity of an ion peak was suppressed by increased current in the baseline due to continuous leakage of ions into the drift region from insufficient E(s) to block ion motion when needed, at a given value of E(d); (2) the ion shutter provided maximum peak intensity with some optimal ratio of E(s)/E(d) when ions were fully blocked except using the injection time; (c) the signal intensity was reduced when the blocking voltage of the ion shutter exceeded this optimal E(s)/E(d) ratio from ion depletion at the shutter grids. The optimal ratio from the computer models was equal to 1.50, whereas a value of 2.50 was obtained from the experimental findings. This difference was attributed to nonideal geometry with the grids of the shutter and the conducting elements in the drift tube establishing both E(s) and E(d). As both the experimental and modeling results demonstrated, a mobility dependence of ion yield from the ionization source was found to cause a mobility dependent ion signal at the collector electrode.

Ion mobility spectrometers with doped gases.

Ion mobility spectrometry (IMS) is an instrumental technique used successfully for the detection of wide range of organic compounds in the gas phase. In this paper, advances in using special substances called dopants for gases flowing through IMS detectors are reviewed. These substances influence the ion-molecule chemistry in sample ionisation region as well as change conditions for the drift of ions. Improved selectivity and sensitivity of detection can be obtained by the use of dopants. In some cases, especially when measurements are conducted in the presence of different substances disturbing detection, the use of dopants is indispensable. The theory of the function of dopants is based on the knowledge of ion-molecule reactions. Fundamental information about these reactions is presented here. Mechanisms of changing the composition of ions produced in reactant section of IMS detector are explained on this basis. The most commonly used dopants are acetone and ammonia for positive mode and chloride for negative mode IMS. Other substances, such as higher ketones, organophosphorous compounds or methyl salicylate are used for special purposes and are selected for given analytical problem. Particular examples for the application of these substances are described.