Simon Maher

Analysis of Polycyclic Aromatic Hydrocarbons Using Desorption Atmospheric Pressure Chemical Ionization Coupled to a Portable Mass Spectrometer

AbstractDesorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[k]fluoranthene, dibenz[a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules. Graphical Abstractᅟ

Screening and Quantification of Aliphatic Primary Alkyl Corrosion Inhibitor Amines in Water Samples by Paper Spray Mass Spectrometry

Direct analysis and identification of long chain aliphatic primary diamine Duomeen O (n-oleyl-1,3-diaminopropane), corrosion inhibitor in raw water samples taken from a large medium pressure water tube boiler plant water samples at low LODs (<0.1 pg) has been demonstrated for the first time, without any sample preparation using paper spray mass spectrometry (PS-MS). The presence of Duomeen O in water samples was confirmed via tandem mass spectrometry using collision-induced dissociation and supported by exact mass measurement and reactive paper spray experiments using an LTQ Orbitrap Exactive instrument. Data shown herein indicate that paper spray ambient ionization can be readily used as a rapid and robust method for in situ direct analysis of polymanine corrosion inhibitors in an industrial water boiler plant and other related samples in the water treatment industry. This approach was applied for the analysis of three complex water samples including feedwater, condensate water, and boiler water, all collected from large medium pressure (MP) water tube boiler plants, known to be dosed with varying amounts of polyamine and amine corrosion inhibitor components. Polyamine chemistry is widely used for example in large high pressure (HP) boilers operating in municipal waste and recycling facilities to prevent corrosion of metals. The samples used in this study are from such a facility in Coventry waste treatment facility, U.K., which has 3 × 40 tonne/hour boilers operating at 17.5 bar.

Direct Analysis and Quantification of Metaldehyde in Water using Reactive Paper Spray Mass Spectrometry

Metaldehyde is extensively used worldwide as a contact and systemic molluscicide for controlling slugs and snails in a wide range of agricultural and horticultural crops. Contamination of surface waters due to run-off, coupled with its moderate solubility in water, has led to increased concentration of the pesticide in the environment. In this study, for the first time, rapid analysis (<~1 minute) of metaldehyde residues in water is demonstrated using paper spray mass spectrometry (PS-MS). The observed precursor molecular ions of metaldehyde were confirmed from tandem mass spectrometry (MS/MS) experiments by studying the fragmentation patterns produced via collision-induced dissociation. The signal intensity ratios of the most abundant MS/MS transitions for metaldehyde (177 → 149 for protonated ion) and atrazine (221 → 179) were found to be linear in the range 0.01 to 5 ng/mL. Metaldehyde residues were detectable in environmental water samples at low concentration (LOD < 0.1 ng/mL using reactive PS-MS), with a relative standard deviation <10% and an R2 value >0.99, without any pre-concentration/separation steps. This result is of particular importance for environmental monitoring and water quality analysis providing a potential means of rapid screening to ensure safe drinking water.

Mapping the Stability Diagram of a Quadrupole Mass Spectrometer with a Static Transverse Magnetic Field Applied

AbstractPrevious experimental and theoretical work identified that the application of a static magnetic (B) field can improve the resolution of a quadrupole mass spectrometer (QMS) and this simple method of performance enhancement offers advantages for field deployment. Presented here are further data showing the effect of the transverse magnetic field upon the QMS performance. For the first time, the asymmetry in QMS operation with Bx and By is considered and explained in terms of operation in the fourth quadrant of the stability diagram. The results may be explained by considering the additional Lorentz force (v x B) experienced by the ion trajectories in each case. Using our numerical approach, we model not only the individual ion trajectories for a transverse B field applied in x and y but also the mass spectra and the effect of the magnetic field upon the stability diagram. Our theoretical findings, confirmed by experiment, show an improvement in resolution and ion transmission by application of magnetic field for certain operating conditions. Figureᅟ

A Method of Computing Accurate 3D Fields of a Quadrupole Mass Filter and Their Use for Prediction of Filter Behavior

A method is described that enables the three-dimensional fields of a simple quadrupole mass filter (QMF) to be determined to a high accuracy. The technique produces accurate field values in the fringe field region as well as in the center of the filter. Using fields obtained typical filter performance is determined and shown to differ from that predicted when fringe fields are ignored. The computed performance shows features obtained experimentally and displays more complex variation with ion mass and other parameters than when fringe fields are ignored.

Quadrupole mass filter operation under the influence of magnetic field.

This work demonstrates resolution enhancement of a quadrupole mass filter (QMF) under the influence of a static magnetic field. Generally, QMF resolution can be improved by increasing the number of rf cycles an ion experiences when passing through the mass filter. In order to improve the resolution, the dimensions of the QMF or the operating parameters need to be changed. However, geometric modifications to improve performance increase the manufacturing cost and usually the size of the instrument. By applying a magnetic field, a low-cost, small footprint instrument with reduced power requirements can be realized. Significant improvement in QMF resolution was observed experimentally for certain magnetic field conditions, and these have been explained in terms of our theoretical model developed at the University of Liverpool. This model is capable of accurate simulation of spectra allowing the user to specify different values of mass spectrometer dimensions and applied input signals. The model predicts enhanced instrument resolution R>26,000 for a CO2 and N2 mixture with a 200-mm long mass filter operating in stability zone 3 via application of an axial magnetic field.

Evaluation of Electron Beam Deflections across a Solenoid Using Weber-Ritz and Maxwell-Lorentz Electrodynamics

The deflection of charged particle beams by electric and/or magnetic fields is invariably based on the field centred approach associated with Maxwell-Lorentz and incorporated into the Lorentz force formula. Here we present an alternative method of calculation based on the force formula of Weber-Ritz and which does not involve, directly, the field entities E and B. In this study we evaluate the deflection of an electron beam by a long solenoid carrying direct current and positioned centrally across the beam. The experiment has some bearing on the Aharonov-Bohm effect in that our calculations indicate that even for very long solenoids the classical force on the beam remains finite. The standard interpretation of the effect is, however, in terms of quantum mechanics and vector potential. Experimental measurements have been made of electron beam deflections by three solenoids, 0.25 m, 0.50 m and 0.75 m long; each solenoid is doubly wound with the same winding density (2600 turns per metre) and carrying the same current of 5.00 A d.c.. Our results indicate that, within the limits of experimental error, both Weber-Ritz and Maxwell-Lorentz theories correlate with measurements for the longer solenoids. However in the case of the shortest solenoid, the lack of uniformity of the magnetic field, leads to significant error in the calculation of beam deflection by the Lorentz force. By contrast in a Weber-Ritz calculation a precise value of beam deflection is obtained by equating the impulse of the non uniform beam force to the vertical momentum change of the electron. This is a fundamentally different approach which uses a statistical summation of forces on the beam in terms of relative velocities between moving electrons and involves a direct computation of the vertical force on the beam due to the circling solenoid current. This method has distinct advantages in terms of economy; that is, it does not involve directly field entities E and B, nor the leakage flux from the solenoid or the vector potential.

Experimental investigation of the 2D ion beam profile generated by an ESI octopole-QMS system.

AbstractIn this paper, we have employed an ion imaging approach to investigate the behavior of ions exiting from a quadrupole mass spectrometer (QMS) system that employs a radio frequency octopole ion guide before the QMS. An in-vacuum active pixel detector (Timepix) is employed at the exit of the QMS to image the ion patterns. The detector assembly simultaneously records the ion impact position and number of ions per pixel in every measurement frame. The transmission characteristics of the ion beam exiting the QMS are studied using this imaging detector under different operating conditions. Experimental results confirm that the ion spatial distribution exiting the QMS is heavily influenced by ion injection conditions. Furthermore, ion images from Timepix measurements of protein standards demonstrate the capability to enhance the quality of the mass spectral information and provide a detailed insight in the spatial distribution of different charge states (and hence different m/z) ions exiting the QMS.

Direct Ion Imaging Approach for Investigation of Ion Dynamics in Multipole Ion Guides

A key requirement of electrospray ionization (ESI) and other techniques facilitating ionization at elevated pressures is the efficient transport of free gas-phase ions into the high vacuum region of the mass spectrometer. Radio frequency (RF) multipole ion guides that allow for collisional cooling are one of the most popular means of achieving this. However, their performance is highly dependent on several experimental factors, including pressure and various electrode potentials along the ion path. To experimentally visualize these effects, we have employed a position-sensitive detector at the exit of a quadrupole mass spectrometer (QMS) instrument operated in RF only mode that employs an RF only octopole as a collisional cooling ion guide. This allows the spatial distribution of the ions, and its dependence on experimentally determined conditions, to be directly visualized at the exit of the quadrupole. This investigation provides a detailed insight into the ion dynamics occurring inside multipole ion guides. This knowledge can directly be applied to instrument development and to improve the ion transmission efficiency and, thus, sensitivity. Numerical simulations using custom-developed trajectory simulation software are compared and contrasted with the experimental observations.

Quadrupole Mass Filter: Design and Performance for Operation in Stability Zone 3

AbstractThe predicted performance of a quadrupole mass filter (QMF) operating in Mathieu stability zone 3 is described in detail using computer simulations. The investigation considers the factors that limit the ultimate maximum resolution (Rmax) and percentage transmission (%Tx), which can be obtained for a given QMF for a particular scan line of operation. The performance curve (i.e., the resolution (R) versus number (N) of radio frequency (rf) cycles experienced by the ions in the mass filter) has been modeled for the upper and lower tip of stability zone 3. The saturation behavior of the performance curve observed in practice for zone 3 is explained. Furthermore, new design equations are presented by examining the intersection of the scan line with stability zone 3. Resolution versus transmission characteristics of stability zones 1 and 3 are compared and the dependence of performance for zones 1 and 3 is related to particular instrument operating parameters. Figureᅟ