Mobility Spectrometer Research Articles

Determination of ethylene by field asymmetric ion mobility spectrometry

The determination of ethylene with a field asymmetric ion mobility spectrometer, which can easily be constructed in-house, is described. The device makes use of a Krypton lamp for ionization. A rectangular pulse of 500 Vpp at 1 MHz was employed as separation waveform in the drift tube rather than the commonly used less efficient bisinusoidal waveform. The calibration curve for the range from 670 ppb(V/V) to 67 ppm(V/V) was found to be highly linear with a correlation coefficient of r = 0.9999. The limit of detection was determined as 200 ppb(V/V). The reproducibility was 4% (relative standard deviation). The device was found to be suitable for the determination of ethylene given off by fruit; 6 types of climacteric fruit were tested, namely apples, bananas, kiwi fruit, nectarines, pears and plums.

Recovery characteristics of different tube materials in relation to combustion products

Common challenge in gas analyzers such as Ion Mobility Spectrometers (IMS) integrated into a measurement system is the reduced analysis speed that is partially limited by the temporal carry-over of sample molecules. It is caused by adsorption and absorption of the molecules into the gas tubes of the analyzer. We studied the recovery times of common tube materials: polyether ether ketone (PEEK), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), polyethylene (PE), steel 316 L, parylene C coated steel and Silconert® coated steel from organic combustion products. The tests were performed in two temperatures, at 25 °C and at 70 °C. In addition, detailed analysis was performed for PTFE tube material at 33, 50, 70 and 100 °C to observe the temperature relation of desorption. Uncoated steel was found to have the best performance in increased temperature applications due lack of absorption. Major advantages from coatings compared to plane steel were not found. Plastics were found suitable materials in lower temperatures where adsorption exceeds absorption.

Temporal distribution of ions in ambient pressure drift tubes with turns

Ambient pressure DC-only drift tubes were constructed with one and two turns along the drift path using 3D printing and experimental data was compared to simulations. Turning was achieved using electrodes with 10°, 45° or 90° angles, arranged in various configurations. The performance of drift tubes comprised of nine (one turn) or eighteen (two turns) 10° electrodes was superior to those that achieved the same total angle but used 45° or 90° electrodes. Deviations in the spatial homogeneity of the electric field between the inside and outside of the turns in 45° and 90° electrode systems resulted in wide ion arrival time distributions. Drift tubes containing two turns in opposite directions improved ion arrival time distributions. Unlike the large reductions seen in performance using other geometries, a drift tube containing two opposite direction turns with 10° turning electrodes resulted in only a 1.4 times reduction in resolving power when compared to a straight drift tube of the same path length. Turned drift paths will allow for longer path lengths in a reduced size profile for drift tube ion mobility spectrometers operated at atmospheric pressure.

Novel ion drift tube for high-performance ion mobility spectrometers based on a composite material

Ion mobility spectrometers (IMS) are able to detect pptV-level concentrations of substances in gasses and in liquids within seconds. Due to the continuous increase in analytical performance and reduction of the instrument size, IMS are established nowadays in a variety of analytical field applications. In order to reduce the manufacturing effort and further enhance their widespread use, we have developed a simple manufacturing process for drift tubes based on a composite material. This composite material consists of alternating layers of metal sheets and insulator material, which are connected to each other in a mechanically stable and gastight manner. Furthermore, this approach allows the production of ion drift tubes in just a few steps from a single piece of material, thus reducing the manufacturing costs and efforts. Here, a drift tube ion mobility spectrometer based on such a composite material is presented. Although its outer dimensions are just 15 mm × 15 mm in cross section and 57 mm in length, it has high resolving power of Rp = 62 and detection limits in the pptV-range, demonstrated for ethanol and 1,2,3-trichloropropane.

Materials analyses of stone artifacts from the EBA to MBA Minoan Tholos tomb P at Porti, Greece (Crete), by means of Raman spectroscopy: Results and a critical assessment of the method

Detailed analytical work based on mobile Raman microspectroscopy has been performed on a mortuary assemblage, comprising a group of 59 stone artifacts (vessels, implements and figurines) excavated in one of the richest burial sites in south-central Crete, Tholos tomb P at the Minoan site of Porti (ca. 2700–1700 BCE). Mineral identification was possible for over half of the objects examined and the results expand our understanding, originally obtained on the basis of visual and microscopic characterization of the objects. Patterns of variability in the stones investigated are correlated with the typological repertoire of the final products and compared with data from the neighboring site of Apesokari; further inferences on craft specialization issues are finally drawn. In all, the data obtained lead us to suggest that stone vessel manufacture at Porti was predominantly focused on the exploitation of local softstone outcrops. This hypothesis agrees with the current knowledge concerning the geological formation of the Asterousia area, on the northern fringes of which the site of Porti is located. In parallel, the capacity of mobile Raman microspectrometry to contribute to stone object characterization as regards their mineral composition is discussed along with advantages and limitations of the methodology followed. Raman analysis is preformed quickly, non-invasively, directly on the object and over several spots across its surface for probing heterogeneous mineral distributions. The mobile spectrometer permits measurements to be conducted on location, namely within the museum study facilities. A major limitation with respect to obtaining clean analytical information resulted from strong fluorescence emission observed in some of the measurements, which interfered with the Raman scattering signal. These emissions were attributed to organic materials present on the stone surface either as environmental contamination or as a result of previous, often undocumented, conservation treatments. Finally, the need to collect and thoroughly characterize local stone outcrops as well as archaeological stone objects has become evident and building a representative Raman spectral database will certainly facilitate future studies.

Stepwise optimization of a Flexible Microtube Plasma (FµTP) as an ionization source for Ion Mobility Spectrometry

The ionization source is the central system of analytical devices such as mass spectrometers or ion mobility spectrometers. In this study, a recently developed flexible microtube plasma (FμTP) is applied as an ionization source for a custom-made drift tube ion mobility spectrometer (IMS) for the first time. The FµTP is based on a highly miniaturized, robust and a small-footprint dielectric barrier discharge design with an outstanding ionization efficiency. In this study, the experimental setup of the FµTP was further improved upon to achieve optimal coupling conditions in terms of the ion mobility spectrometry sensitivity and the plasma gas consumption. One major focus of this study was the adjustment of the electrical operation parameters, in particular, the high voltage amplitude, frequency and duty cycle, in order to minimize the electric field disturbances and yield higher signals. Additionally, the consumption of helium plasma gas was reduced by refining the FµTP. It was found that the ionization efficiency could be significantly enhanced by increasing the plasma high voltage and through application of a duty cycle up to 90:10. Plasma gas flows could be reduced down to 3 mL min-1 by increasing the plasma high voltage amplitude. Furthermore, a smaller wire electrode design enables the operation of the FµTP with nitrogen and clean air. Moreover, detection limits of a homologous series of ketones in the range of 330 pptv (N2-FµTP, 2-decanone) down to 20 pptv (He-FµTP, 2-octanone) could be reached in the optimized setup. To sum up, this feasibility study demonstrates the potential of the optimized FµTP as a powerful ionization source for ion mobility spectrometry especially with regard to ionization efficiency.

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.

Application of MIL-53(Al) prepared from waste materials for solid-phase microextraction of propranolol followed by corona discharge-ion mobility spectrometry (CD-IMS)

In this study, MIL-53(Al) metal-organic framework was prepared from waste raw materials. A polyethylene terephthalate (PET) plastic bottle was used as the source of terephthalic acid, and an aluminium beverage can was applied as the precursor of aluminium salt. The activated MIL-53(Al) was immobilized onto a stainless steel probe of the ion mobility spectrometer (IMS), and the coated probe was used for solid-phase microextraction of propranolol from biological samples before determination. The effect of the different parameters such as pH, ionic strength, and stirring rate of the sample, extraction time, and temperature was studied on the extraction efficiency of propranolol. The linearity was obtained ranging from 5−200 μg L−1 with a determination coefficient (R2) of 0.9988, and the detection limit was calculated 1.7 μg L−1 in the water sample. The relative standard deviations of the method were in the range of 2.5–12.2 %. Finally, the method was utilized for determination of propranolol in the tablet sample.

Evaluation of Trapped Ion Mobility Spectrometry Source Conditions Using Benzylammonium Thermometer Ions.

A key aspect of reduced pressure ion mobility spectrometry (IMS) experiments is to identify experimental conditions that minimize the role of collisional energy transfer that allows for assessing effective ion-neutral collision cross sections of metabolites, peptides, and proteins in "native-like" or compact states. Across two separate experimental campaigns using a prototype trapped ion mobility spectrometer (TIMS) coupled to a time-of-flight mass spectrometer, we present independent findings that support the results recently published by Morsa et al. using a different set of thermometer ions (Morsa et al. Anal. Chem. 2020, 92 (6), 4573-4582). First, using five para-substituted benzylammonium ions, we conducted survival yield experiments to assess ion internal energy across different experimental settings. Results from the present set of experiments illustrate that greater ion heating occurs at lower pressures and higher voltage settings applied to the TIMS. At the "softest" settings where the benzylammonium thermometer ions have an effective average energy of 1.73 eV, we observe the majority of bradykinin in the compact state. Under more extreme operating conditions where the energy of the benzylammonium ions varies from 1.83 to 1.86 eV, the bradykinin transitions from the compact to the elongated state. In addition to independently confirming the findings of Morsa et al., we also report the mobilities for the benzylammonium parent and fragment ions using the tandem drift-tube-TIMS calibration procedure described by Naylor et al. ( J. Am. Soc. Mass Spectrom. 2019, 30 (10), 2152-2162).

Sub-ambient pressure IR-MALDI ion mobility spectrometer for the determination of low and high field mobilities.

A new ion mobility (IM) spectrometer, enabling mobility measurements in the pressure range between 5 and 500mbar and in the reduced field strength range E/N of 5-90 Td, was developed and characterized. Reduced mobility (K0) values were studied under low E/N (constant value) as well as high E/N (deviation from low field K0) for a series of molecular ions in nitrogen. Infrared matrix-assisted laser desorption ionization (IR-MALDI) was used in two configurations: a source working at atmospheric pressure (AP) and, for the first time, an IR-MALDI source working with a liquid (aqueous) matrix at sub-ambient/reduced pressure (RP). The influence of RP on IR-MALDI was examined and new insights into the dispersion process were gained. This enabled the optimization of the IM spectrometer for best analytical performance. While ion desolvation is less efficient at RP, the transport of ions is more efficient, leading to intensity enhancement and an increased number of oligomer ions. When deciding between AP and RP IR-MALDI, a trade-off between intensity and resolving power has to be considered. Here, the low field mobility of peptide ions was first measured and compared with reference values from ESI-IM spectrometry (at AP) as well as collision cross sections obtained from molecular dynamics simulations. The second application was the determination of the reduced mobility of various substituted ammonium ions as a function of E/N in nitrogen. The mobility is constant up to a threshold at high E/N. Beyond this threshold, mobility increases were observed. This behavior can be explained by the loss of hydrated water molecules.

Flexible Drift Tube for High Resolution Ion Mobility Spectrometry (Flex-DT-IMS).

This paper describes, in detail, the development of a novel, low-cost, and flexible drift tube (DT) along with an associated ion mobility spectrometer system. The DT is constructed from a flexible printed circuit board (PCB), with a bespoke “dog-leg” track design, that can be rolled up for ease of assembly. This approach incorporates a shielding layer, as part of the flexible PCB design, and represents the minimum dimensional footprint conceivable for a DT. The low thermal mass of the polyimide substrate and overlapping electrodes, as afforded by the dog-leg design, allow for efficient heat management and high field linearity within the tube–achieved from a single PCB. This is further enhanced by a novel double-glazing configuration which provides a simple and effective means for gas management, minimizing thermal variation within the assembly. Herein, we provide a full experimental characterization of the flexible DT ion mobility spectrometer (Flex-DT-IMS) with corresponding electrodynamic (Simion 8.1) and fluid dynamic (SolidWorks) simulations. The Flex-DT-IMS is shown to have a resolution >80 and a detection limit of low nanograms for the analysis of common explosives (RDX, PETN, HMX, and TNT).

Liquid-Phase Ion Trap for Ion Trapping, Transfer, and Sequential Ejection in Solutions

In this study, a new method/mechanism to manipulate ions in solution was developed, based on which liquid-phase ion trap was built. In this liquid-phase ion trap, ion manipulations conventionally performed in a quadrupole ion trap or in a trapped ion mobility spectrometer placed in a vacuum were achieved in solutions. Through theoretical derivation and numerical simulation, it is found that ions have different motional characteristics than those in vacuum. Instead of a radio frequency quadrupole electric field, tunable DC electric fields together with a constant liquid flow were applied to control ion motions in solution. Different ions could be trapped and focused in a potential well, and ion densities could be increased by over 100-fold. By adjusting the DC electric field of the potential well, trapped ions could be transferred into another trapping region or sequentially released for detection. Ions released from the liquid-phase ion trap were then detected by a mass spectrometer interfaced with an electrospray ionization source. Since the ion manipulation mechanism in solution is different and complementary to that in vacuum, the use of a liquid-phase ion trap could also boost detection sensitivity and the mixture analysis capability of a mass spectrometer.

Diffusional transfer function for the scanning electrical mobility spectrometer (SEMS)

The scanning electrical mobility spectrometer (SEMS), or scanning mobility particle sizer (SMPS), uses the differential mobility analyzer (DMA) operated in scanning mode to measure particle size di...

An HS-GC-IMS Method for the Quality Classification of Virgin Olive Oils as Screening Support for the Panel Test.

Sensory evaluation, carried out by panel tests, is essential for quality classification of virgin olive oils (VOOs), but is time consuming and costly when many samples need to be assessed; sensory evaluation could be assisted by the application of screening methods. Rapid instrumental methods based on the analysis of volatile molecules might be considered interesting to assist the panel test through fast pre-classification of samples with a known level of probability, thus increasing the efficiency of quality control. With this objective, a headspace gas chromatography-ion mobility spectrometer (HS-GC-IMS) was used to analyze 198 commercial VOOs (extra virgin, virgin and lampante) by a semi-targeted approach. Different partial least squares-discriminant analysis (PLS-DA) chemometric models were then built by data matrices composed of 15 volatile compounds, which were previously selected as markers: a first approach was proposed to classify samples according to their quality grade and a second based on the presence of sensory defects. The performance (intra-day and inter-day repeatability, linearity) of the method was evaluated. The average percentages of correctly classified samples obtained from the two models were satisfactory, namely 77% (prediction of the quality grades) and 64% (prediction of the presence of three defects) in external validation, thus demonstrating that this easy-to-use screening instrumental approach is promising to support the work carried out by panel tests.

Rapid online analysis of trace elements in steel using a mobile fiber-optic laser-induced breakdown spectroscopy system

A mobile fiber-optic laser-induced breakdown spectrometer (FO-LIBS) prototype was developed to rapidly detect a large quantity of steel material online and quantitatively analyze the trace elements in a large-diameter steel tube. Twenty-four standard samples and a polynomial fitting method were used to establish calibration curve models. The R2 factors of the calibration curves were all above 0.99, except for Cu, indicating the elements’ strong self-absorption effect. Five special steel materials were rapidly detected in the steel mill. The average absolute errors of Mn, Cr, Ni, V, Cu, and Mo in the special steel materials were 0.039, 0.440, 0.033, 0.057, 0.003, and 0.07 wt%, respectively, and their average relative errors fluctuated from 2.9% to 15.7%. The results demonstrated that the performance of this mobile FO-LIBS prototype can be compared with that of most conventional LIBS systems, but the more robust and flexible characteristics of the FO-LIBS prototype provide a feasible approach for promoting LIBS from the laboratory to the industry.

U-Shaped Mobility Analyzer: A Compact and High-Resolution Counter-Flow Ion Mobility Spectrometer

In recent years, there has been a rapid increase in the use of counter-flow-type ion mobility spectrometers (IMS) due to their improved resolution and functionality. In this study, we developed a new type of counter-flow ion mobility device named the U-shaped mobility analyzer (UMA) for coupling with a mass spectrometer, where the analyte ions could travel along a gas flow in the first channel of the UMA device and then against a gas flow in the second channel of the device. Hence, a mobility band-pass filter was formed by setting different electric fields in the two channels, which enables high-resolution mobility selection of analyte ions. A resolution of ca. 180 was achieved for singly charged small organic molecules, and a resolution of up to ca. 370 was achieved for multiply charged +15 myoglobin. It was thus demonstrated that this filtering function can greatly enhance the dynamic range of an IMS-MS instrument, particularly favoring targeted analysis in complex matrices. Alternatively, the analyte ions could be operated in a so-called trap-scan mode in which ions were trapped first in one of the channels and released sequentially for mobility analysis with an even higher resolution (ca. 210 for singly charged small organic molecules and ca. 590 for +15 myoglobin). Overall, this new UMA device would enable many new applications in omics studies with its high resolution and dynamic range, especially when using the filter-scan mode for scrutinizing analytes with very low concentrations under high chemical backgrounds.

IMS Instrumentation I: Isolated data acquisition for ion mobility spectrometers with grounded ion sources

The drift voltage required for operating ion mobility spectrometers implies high voltage isolation of either the ion source or the detector. Typically, the detector is grounded due to the sensitivity of the small ion currents to interferences and thus higher requirements for signal integrity than the ion source. However, for certain ion sources, such as non-radioactive electron emitters or electrospray ionization sources, or for coupling with other instruments, such as gas or liquid chromatographs, a grounded ion source is beneficial. In this paper, we present an isolated data acquisition interface using a 16 bit, 250 kilosamples per second analog to digital converter and fiber optic transmitters and receivers. All spectra recorded via this new data acquisition interface and with a grounded ion source show the same peak shapes and noise when compared with a grounded detector, allowing additional freedom in design.

Positive Reactant Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS).

In contrast to classical Ion Mobility Spectrometers (IMS) operating at ambient pressure, the High Kinetic Energy Ion Mobility Spectrometer (HiKE-IMS) is operated at reduced pressures of between 10 and 40 mbar and higher reduced electric field strengths of up to 120 Td. Thus, the ion-molecule reactions occurring in the HiKE-IMS can significantly differ from those in classical ambient pressure IMS. In order to predict the ionization pathways of specific analyte molecules, profound knowledge of the reactant ion species generated in HiKE-IMS and their dependence on the ionization conditions is essential. In this work, the formation of positive reactant ions in HiKE-IMS is investigated in detail. On the basis of kinetic and thermodynamic data from the literature, the ion-molecule reactions are kinetically modeled. To verify the model, we present measurements of the reactant ion population and its dependence on the reduced electric field strength, the operating pressure, and the water concentration in the sample gas. All of these parameters significantly affect the reactant ion population formed in HiKE-IMS.

An intercomparison exercise of good laboratory practices for nano-aerosol size measurements by mobility spectrometers

An intercomparison campaign on nanoparticle size measurement was organized in the frame of the French nanoMetrology club. The aim of this study is to make an inventory of the metrological capabilities of all measurement techniques in France involved in the “nano” size range, including the SMPS (scanning mobility particle sizer) concerning aerosol metrology. For this study, four samples have been proposed, namely (1) a SiO2 colloidal suspension (FD304) consisting of a monomodal population, (2) two samples consisting of two nanoparticle populations of SiO2 having proportions to be determined, and (3) a TiO2 colloidal suspension. Ten SMPS associated with five participants around a common experimental setup were performed in link with a control SMPS to have simultaneous measurements with a same instrument in each laboratory in parallel with the SMPS used by each partner. This article presents SMPS results of this study associated with the description of the experimental setup and the sample preparation protocol with an identified schedule and comparison with SEM measurements. The present paper does not focus on the actual capability of the tested mobility spectrometers, but aims to highlight the good laboratory practices using their own but common resources in terms of aerosol generation and measurement setups.

Imaging VOC distribution in cities and tracing VOC emission sources with a novel mobile proton transfer reaction mass spectrometer

Volatile organic compounds (VOCs) are important precursors of ozone (O3) and secondary organic aerosols (SOAs). Tracing VOC pollution sources is important for controlling VOC emissions and reducing O3 and SOAs. We built a novel mobile proton transfer reaction mass spectrometry (M-PTR-MS) instrument to image the distribution of VOCs and trace their emission sources in cities and industrial parks. The M-PTR-MS is composed of a vibration-resistant proton transfer reaction mass spectrometry (PTR-MS) with a global positioning system receiver, modified box vehicle, and geographic information system (GIS) software. The PTR-MS, mounted on a vehicle, sends VOC data and vehicle position information to the GIS software. These data are used to image the space distribution of VOCs in real time while the vehicle platform is in motion and the VOC sources are precisely traced using the GIS. The spatial data resolution of the M-PTR-MS is typically 0.8 m. The limits of detection, sensitivity, and repeatability of the M-PTR-MS are 43.5 ppt, 347 counts ppb−1, and 2.4% (RSD, n = 5), respectively. The intensity of reagent ions is stable over 8 h (RSD = 0.45%). Compared with commercial PTR-MS equipment, the M-PTR-MS demonstrated high consistency, with a correlation coefficient of 92.665%. Several field experiments were conducted in China using the M-PTR-MS. In one field experiment, the VOC distribution along three different routes was surveyed; the navigation monitoring lasted 1.8 h over a distance of 26.7 km at an average speed of 15 km h−1. The VOC sources in an industrial park were identified by analyzing the components near different factories. The main species from a VOC source in an underground garage was related to paint. The M-PTR-MS instrument can be used by environmental protection agencies to trace VOC pollution sources in real time, and by researchers to survey VOC emissions in regions of concern.