Determination of terpenes in humid ambient air using ultraviolet ion mobility spectrometry

Atmospheric humidity causes the major problem using ion mobility spectrometers (IMS) under ambient conditions. Significant changes of the spectra are decreasing sensitivity as well as selectivity. Therefore, the influence of humidity on the IMS signal was investigated in case of direct introduction of the analyte into the ionisation chamber and in case of pre-separation by help of a multi-capillary column (MCC). For direct analyte introduction, a significant decrease of the total number of ions in the range of 28-42% with increasing relative humidity was found. Simultaneously additional peaks in the spectra were formed, thus complicating the identification of the analytes. In case of pre-separation of the analyte, the spectra do not change with increasing relative humidity, due to the successive appearance of the analyte and the water molecules in the ionisation chamber. Detection limits were found in the range of 5 μg/m³ (about 1 ppbv) for selected terpenes and—with pre-separation—independent on relative humidity of the analyte. Without pre-separation, detection limits are in the same range for dry air as carrier gas but in the range of 200-600 μg/m³ when relative humidity reaches 100%. Thus, MCC-UV ion mobility spectrometry is optimally capable for the detection of trace substances in ambient air (e.g. indoor air quality control, process control, odour detection) without further elaborate treatment of the carrier gas containing the analyte and independent on relative humidity.     

Determination of the non-constant component of the ion mobility using the spectrometer of ion mobility increment

A new method for determination of the non-constant component, alpha(E), of an ion mobility, k(E), is suggested. The method uses the relationship U(C) (US) that can be experimentally obtained with a spectrometer of ion mobility increment with planar drift chamber. (UC is a compensating voltage, U(S) is separating voltage amplitude.) A general equation for alpha(E) has been derived. We have explored the possibility of determination of alpha(E) from the experimental data for different types of US(t). In two specific cases, analytical solutions have been obtained.     

Process analysis using ion mobility spectrometry

Ion mobility spectrometry, originally used to detect chemical warfare agents, explosives and illegal drugs, is now frequently applied in the field of process analytics. The method combines both high sensitivity (detection limits down to the ng to pg per liter and ppb_v/ppt_v ranges) and relatively low technical expenditure with a high-speed data acquisition. In this paper, the working principles of IMS are summarized with respect to the advantages and disadvantages of the technique. Different ionization techniques, sample introduction methods and preseparation methods are considered. Proven applications of different types of ion mobility spectrometer (IMS) used at ISAS will be discussed in detail: monitoring of gas insulated substations, contamination in water, odoration of natural gas, human breath composition and metabolites of bacteria. The example applications discussed relate to purity (gas insulated substations), ecology (contamination of water resources), plants and person safety (odoration of natural gas), food quality control (molds and bacteria) and human health (breath analysis).     

Hydrocarbon detection using laser ion mobility spectrometry

A Laser Ion Mobility Spectrometer has been set up and trace detection experiments have been performed. We find that laser ionization almost selectively ionizes aromatic hydrocarbons. Aliphatic hydrocarbons are only laser-ionized in case these contain conjugated double bonds. As, in contrast to radioactive ion mobility spectrometry, background air constituents and air contaminants cannot be ionized, drift spectra are inherently simple and easily interpretable. We show that a laser ion mobility spectrometer can be operated in two basically different modes, either using tunable or fixed-frequency laser sources. In the tunable laser mode, aromatic hydrocarbons can be detected in the positive mode and distinguished from each other on account of their different excitation wavelengths and ion drift times. In the fixed-frequency mode, specially chosen and intentionally admitted aromatic hydrocarbons are laser ionized and the primary ionization is transferred to non-aromatic species by means of atmospheric pressure chemical ionization. In this latter mode of operation nitroglycerin and triacetone triperoxide, two non-aromatic high explosives, could be detected.     

Fingerprinting bacterial strains using ion mobility spectrometry

Ion mobility spectrometry (IMS) is currently in widespread use for the detection and identification of narcotic and explosive compounds without prior sample clean-up or concentration steps. IMS analysis is rapid, less than a minute, and sensitive, with detection limits in the nanogram to picogram range, depending on the target analyte. Our studies indicate that this technique has potential for detection of specific components of bacterial cells and for identification and differentiation of bacterial strains and species within a minute, and with no specialized test kits or reagents required. When microgram quantities of whole bacterial cells are thermally desorbed, complex positive or negative ion patterns (plasmagrams) are obtained. These plasmagrams differ reproducibly for different strains and species and for different conditions of growth, and can be used for the classification and differentiation of specific strains and species of bacteria, including pathogens. Methods for improved ion peak detection, most notably sequential sample desorption at stepped increases in temperature (programmed temperature ramping), are described.     

Detection of perfluorocarbons using ion mobility spectrometry

An ISAS custom-designed ion mobility spectrometer equipped with a ionization source is used for the sensitive detection of traces of perfluorocarbons (PFCs, C₅F₁₂ to C₉F₂₀) in air, a class of substances for which a growing interest for industrial and environmental applications arose within the last years. Mobility spectra of the PFCs are presented, compared and discussed with regard to the possibility of identifying these analytes; detection limits are determined to be in the upper ng l⁻¹ range. Using a specific PFC as an example, a way to prevent unwanted contributions of non-product ions, the difference mobility spectrum, is introduced and described. Advantages and possibilities of this technique are briefly discussed.     

Characterizing ion mobility and collision cross section of fatty acids using electrospray ion mobility mass spectrometry

This study investigated the ion mobility (IM) and the collision cross section (CCS) of fatty acids (FAs) using electrospray IM MS. The IM analysis of 18 FA ions showed intriguing differences among the saturated FAs, monounsaturated FAs, multi‐unsaturated FAs, and cis‐isomer/trans‐isomer with respect to the aliphatic tail chains. The length of aliphatic tail chain present in the ion structures had a strong influence on the differentiation of drift, while the number of double bond showed a weaker influence. The tiny drift differences between cis‐isomer and trans‐isomer were also observed. In the CCS measurements, two internal standards were involved in the mobility calibration and accuracy estimation. It insured our empirical CCS values were of high experimental precision (±0.35% or better) and accuracy (±0.25% or better). Moreover, the mass‐to‐charge ratio (m/z) – mobility plots obtained by ion mobility spectrometry with mass spectrometry analysis of FAs – was used to investigate the structural relationship between the molecules. Each series of FAs sharing a similar structure was aligned in the linear plot. Finally, the developed procedure was applied to the determination of FAs in rat adipose tissues, and it allowed the presence of 13 FAs to be confirmed with their exact masses and CCS values. These studies reveal the direct relationship between the behaviors in IM and the molecular structures and thus may provide further validations to the FA identification process. Copyright © 2015 John Wiley & Sons, Ltd.     

Gas-phase separation using a trapped ion mobility spectrometer

In the present work we describe the principles of operation, versatility and applicability of a trapped ion mobility spectrometer (TIMS) analyzer for fast, gas-phase separation of molecular ions based on their size-to-charge ratio. Mobility-based separation using a TIMS device is shown for a series for isobar pairs. In a TIMS device, mobility resolution depends on the bath gas velocity and analysis scan speed, with the particularity that the mobility separation can be easily tuned from low to high resolution (R?>?50) in accordance with the analytical challenge . In contrast to traditional drift tube IMS analyzer, a TIMS device can be easily integrated in a mass spectrometer without a noticeable loss in ion transmission or sensitivity, thus providing a powerful separation platform prior to mass analysis.     

Resolving interferences in negative mode ion mobility spectrometry using selective reactant ion chemistry

During the investigation of the degradation products of 2,4,6-trinitrotoluene (TNT) using ion mobility spectrometry (IMS), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (DCP) were found to have IMS responses which overlapped those of the TNT degradation products. It was observed that the Cl(-) reactant ion chemistry, often used for explosives analysis, was not always successful in resolving peak overlap of analytes and interferents. It is shown here that resolution of the analytes and interferences can sometimes be achieved using only air for the formation of reactant ions, at other times through the use of Br(-) as an alternative to Cl(-) for producing reactant ions, and also through the promotion of adduct stability by lowering the IMS temperature.     

Determination of ammonia in ethylene using ion mobility spectrometry.

A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated.     

The detection of nicotine in e-liquids using ion mobility spectrometry

Ion mobility spectrometry (IMS) is a well known field technique for the detection of various materials such as explosives and narcotics. IMS has been used for the detection and identification of nicotine, and this paper describes a simple preparation method and analysis using an Ionscan 500DT which could be used in a field environment for the detection of nicotine in e-liquids. E-liquids containing nicotine are presently a topic of much debate in many countries and their shipment across the Canadian border is prohibited. The method described here would allow border officers or any other operators of IMS instruments to use this technique to correctly determine the presence or absence of nicotine in the e-liquid; this would allow the timely importation of the e-liquids with no nicotine and restrict the laboratory analysis only to those liquids containing nicotine. The IMS method has been used on a number of samples received from manufacturers of e-liquids as well as samples seized at the border. The results of the IMS analysis correspond well with those obtained using a Gas Chromatograph – Mass Spectrometer (GC-MS) method of analysis for nicotine.     

Separation of peptides from detergents using ion mobility spectrometry

Mass spectrometry (MS) has dramatically evolved in the last two decades and has been the driving force of the spectacular expansion of proteomics during this period. However, the very poor compatibility of MS with detergents is still a technical obstacle in some studies, in particular on membrane proteins. Indeed, the high hydrophobicity of membrane proteins necessitates the use of detergents for their extraction and solubilization. Here, we address the analytical potential of high-field asymmetric waveform ion mobility spectrometry (FAIMS) for separating peptides from detergents. The study was focused on peptides from the human integral membrane protein CD9. A tryptic peptide was mixed with the non-ionic detergents Triton X-100 or beta-D-dodecyl maltoside (DDM) as well as with the ionic detergents sodium dodecyl sulfate (SDS) or sodium deoxycholate (SDC). Although electrospray ionization (ESI) alone led to a total suppression of the peptide ion signal on mass spectra with only detection of the detergents, use of FAIMS allowed separation and clear identification of the peptide with any of the detergents studied. The detection and identification of the target compound in the presence of an excess of detergents are then feasible. FAIMS should prove especially useful in the structural and proteomic analysis of membrane proteins.     

Detection of emissions from surfaces using ion mobility spectrometry

Emissions from surfaces (from furniture, wall paintings or floor coverings for instance) significantly influence indoor air quality and therefore the wellbeing or even the health of the occupants. Together with metabolites from mold they are responsible for the well-known “sick building syndrome”. Therefore, it is in the interest of the manufacturer as well as of the occupants to have a fast and accurate method for the detection of substances relevant to this syndrome in order to be able to monitor and control product quality and indoor air quality. The use of small and easy-to-transport ion mobility spectrometers that use UV light as the ionization source enables rapid in situ detection of such substances with high selectivity and sensitivity (detection limits in the lower ppb range). If a multicapillary column is used for preseparation as well, the selectivity is increased and the unwanted influence of humidity on the spectra can be eliminated, thus enabling the use of the instruments under normal ambient conditions. Furthermore, the use of air as carrier gas avoids the need for other sources of high-purity gas. An emission cell with a homogeneous and constant air flow over the surface to be investigated was developed in order to ensure reproducible results. Investigations of emissions from wooden surfaces with and without additional contamination as well as from complex mixtures are presented. The results demonstrate that relevant emissions can be identified and quantified with high sensitivity and selectivity in under five minutes. Therefore, the method is useful for indoor air quality monitoring, especially when miniaturized instruments are applied. Figure     

Resolution equations for high-field ion mobility

An extension of current mobility resolution equations as they apply to high-field ion mobility spectrometry is presented. The new resolution expression is applied to arrival time distributions for ions having a large range of ion mobilities and mass-to-charge ratios (m/z). The results indicate that the new equation can be utilized to predict the mobility resolution over a broader range of applied electric fields than previous ion mobility resolution expressions.     

Real-time monitoring traces of SF6 in near-source ambient air by ion mobility spectrometry

The leakage of sulphur hexafluoride (SF₆) gas threats the global climate changes and personnel safety. Monitoring the concentration of SF₆ in its application places is an industry regulation. In this study, ion mobility spectrometry (IMS) was developed for fast monitoring traces of SF₆ in near-source ambient air. Due to the water is an important part of the natural air and affects most atmospheric measurements, the operating parameters of IMS monitoring SF₆ were optimised for quantitative analysis of SF₆ at different relative humidity (RH). It is discovered two main product ions SF₆^? and SOF₄^? by IMS at different RH. The calibration curves of SF₆ were investigated by its relationship with the peak intensity of SOF₄^– for real application. The time resolution of the measurement was obtained less than 1 s and the limit of detection (LOD) achieved 0.16–0.68 ppm with a data averaging of 30 times. At last, the simulated application of monitoring SF₆ leakage was tested in the fume hood of our lab. The results showed a great potential application prospect of IMS in monitoring SF₆ in the ambient air of its application places.     

Kinetic study of proton-bound dimer formation using ion mobility spectrometry

A method to measure the rate constant for the formation of symmetrical proton-bound dimers at ambient pressure was proposed. The sample is continuously delivered to the drift region of an ion mobility spectrometer where it reacts with a swarm of monomer ions injected by the shutter grid. Dimer ions are formed in the drift tube and a tail appears in the ion mobility spectrum. The rate constant is derived from the mobility spectra. The proposed approach was typically examined for methyl isobutyl ketone (MIBK), 2,4-dimethyl pyridine (DMP), and dimethyl methyl phosphonate (DMMP). The rate constants measured in this study were: 0.25 × 10⁻⁹, 0.86 × 10⁻¹⁰, and 0.47 × 10⁻¹⁰ cm³ s⁻¹ for MIBK, DMP and DMMP, respectively. The logarithm of the measured rate constants were found to be almost independent of reciprocal temperature within 303 to 343 K, indicating that no activation energy is involved in the formation of proton-bound dimers.     

An NO+ reactant ion source for ion mobility spectrometry

The major reactant ion in conventional ion mobility spectrometry (IMS) is the hydronium ion, H₃O⁺ which is produced in the usual ionization sources such as corona discharge or radioactive sources. Using the hydronium reactant ion, mostly the analytes with proton affinity higher than that of water are ionized. A broader range of compounds can be detected by IMS if other alternative ionization channels, such as charge transfer from NO⁺, are employed. In this work we introduce a simple and novel method for producing NO⁺ as the major reactant ion in IMS. This was achieved by adding neutral NO to the corona discharge ionization source. The neutral NO was prepared via an additional discharge in an air stream, flowing into the corona discharge source. A curtain plate was mounted in front of the corona discharge to prevent the influence of the analyte on the production of NO⁺. Using this technique, the reactant ion could easily and quickly switch between the H₃O⁺ and NO⁺. The performance of the new source was evaluated by recording ion mobility spectra of test compounds with both H₃O⁺ and NO⁺ reactant ions.     

Analysis of biogenic amines using corona discharge ion mobility spectrometry

A new method based on corona discharge ion mobility spectrometry (CD-IMS) was developed for the analysis of biogenic amines including spermidine, spermine, putrescine, and cadaverine. The ion mobility spectra of the compounds were obtained with and without n-Nonylamine used as the reagent gas. The high proton affinity of n-Nonylamine prevented ion formation from compounds with a proton affinity lower than that of n-Nonylamine and, therefore, enhanced its selectivity. It was also realized that the ion mobility spectrum of n-Nonylamine varied with its concentration. A sample injection port of a gas chromatograph was modified and used as the sample introduction system into the CD-IMS. The detection limits, dynamic ranges, and analytical parameters of the compounds with and without using the reagent gas were obtained. The detection limits and dynamic ranges of the compounds were about 2 ng and 2 orders of magnitude, respectively. The wide dynamic range of CD-IMS originates from the high current of the corona discharge. The results revealed the high capability of the CD-IMS for the analysis of biogenic amines.     

Improving the efficiency of ion mobility spectrometry analyses by using multivariate calibration

The simplicity, sensitivity and expeditiousness of ion mobility spectrometry (IMS) make it especially useful for the determination of active principal ingredients (APIs) present at low concentrations in pharmaceuticals. However, the poor resolution of this technique precludes the identification and/or determination of substances with similar molecular weights, which exhibit also similar drift times and give overlapped peaks as a result. Oral contraceptives are pharmaceutical formulations containing two APIs of similar molecular weights at very low concentrations which therefore give strongly overlapped peaks hindering their determination by IMS. In this work, we assessed the potential of IMS for detecting and quantifying the contraceptives ethinylestradiol (ETE) and desogestrel (DES) in commercial tablets. To this end, we used various chemometric techniques including a second-derivative (TN2D) algorithm and the more powerful choice Multivariate Curve Resolution (MCR) to improve the resolution of IMS and enable the determination of both APIs. Quantitation was based on PLS1 models for each API. The models constructed involve a single PLS factor with a Y-explained variance above 98.4%, obtaining a RMSEP of 0.34 and 0.63 for ETE and DES, respectively. The ensuing method, which was validated for use in routine analyses, is quite expeditious (analyses take less than 1 min) and uses very small amounts of sample (a few microliters). Based on the results, IMS has a great potential for the qualitative and quantitative determination of APIs in low doses.     

An open source ion gate pulser for ion mobility spectrometry

Excluding the ion source, an ion mobility spectrometer is fundamentally comprised of drift chamber, ion gate, pulsing electronics, and a mechanism for amplifying and recording ion signals. Historically, the solutions to each of these challenges have been custom and rarely replicated exactly. For the IMS research community few detailed resources exist that explicitly detail the construction and operation of ion mobility systems. In an effort to address this knowledge gap we outline a solution to one of the key aspects of a drift tube ion mobility system, the ion gate pulser. Bradbury-Nielsen or Tyndall ion gates are found in nearly every research-grade and commercial IMS system. While conceptually simple, these gate structures often require custom, high-voltage, floating electronics. In this report we detail the operation and performance characteristics of a wifi-enabled, MOSFET-based pulser design that uses a lithium-polymer battery and does not require high voltage isolation transformers. Currently, each output of this circuit follows a TTL signal with ~20 ns rise and fall times, pulses up to +/? 200 V, and is entirely isolated using fiber optics. Detailed schematics and source code are provided to enable continued use of robust pulsing electronics that ease experimental efforts for future comparison.