Sarfaraz U. A. H. Syed

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.

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.

Effect of an Axial Magnetic Field on the Performance of a Quadrupole Mass Spectrometer

We consider the case of a quadrupole mass spectrometer (QMS) in which a static magnetic field is applied axially in the z-direction along the length of the mass filter. The theoretical approach assumed in the model is that the QMS contains hyperbolic rods as electrodes and that the magnetic field acts over the full length of the mass filter assembly. Initial experimental results with argon and helium for a low-resolution instrument confirm the predicted theoretical trends. The analysis also predicts for which values of operating parameters an enhancement of the instrument resolution is achieved when an axial magnetic field is applied. The model predicts instrument resolution R > 3000 for a QMS with a 200 mm long mass filter via application of an axial magnetic field.

Factors Influencing the QMF Resolution for Operation in Stability Zones 1 and 3

AbstractThis study uses a computer model to simulate a quadrupole mass filter (QMF) instrument under different operating conditions for Mathieu stability zones 1 and 3. The investigation considers the factors that limit the maximum resolution (Rmax), which can be obtained for a given QMF for a particular value of scan line. Previously, QMF resolution (R) has been found to be dependent on number (N) of radio frequency (rf) cycles experienced by the ions in the mass filter, according to R = Nn/K, where n and K are the constants. However, this expression does not predict the limit to QMF resolution observed in practice and is true only for the linear regions of the performance curve for QMF operation in zone 1 and zone 3 of the stability diagram. Here we model the saturated regions of the performance curve for QMF operation in zone 1 according to R = q(1 – 2cN)/∆q, where c is a constant and ∆q is the width of the intersection of the operating scan line with the stability zone 1, measured at q-axis of the Mathieu stability diagram. Also by careful calculations of the detail of the stability tip of zone 1, the following relationship was established between Rmax and percentage U/V ratio: Rmax  = q/(0.9330-0.00933U/V). For QMF operation in zone 3 the expression R = a – bcN simulates well the linear and saturated regions of the performance curve for a range of operational conditions, where a, b, and c are constants.

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

An ambient detection system for visualization of charged particles generated with ionization methods at atmospheric pressure

RATIONALE With the current state-of-the-art detection of ions only taking place under vacuum conditions, active pixel detectors that operate under ambient conditions are of particular interest. These detectors are ideally suited to study and characterize the charge distributions generated by ambient ionization sources. METHODS The direct imaging capabilities of the active pixel detector are used to investigate the spatial distributions of charged droplets generated by three ionization sources, named electrospray ionization (ESI), paper spray ionization (PSI) and surface acoustic wave nebulization (SAWN). The ionization spray (ESI/PSI) and ionization plume (SAWN) originating from each source are directly imaged. The effect of source parameters such as spray voltage for ESI and PSI, and the angle of the paper spray tip on the charge distributions, is investigated. Two types of SAWN liquid interface, progressive wave (PW) and standing wave (SW), are studied. RESULTS Direct charge detection under ambient conditions is demonstrated using an active pixel detector. Direct charge distributions are obtained of weak, homogeneous/focused and dispersed spray plumes by applying low, intermediate and high spray potentials, respectively, for ESI. Spray plume footprints obtained for various angles of PSI shows the possibility to focus the ion beam as a function of the paper angle. Differences between two designs of the SAWN interface are determined. Droplet charge flux changes are illustrated in a way similar to a total ion chromatogram. CONCLUSIONS The use of this active pixel detector allows the rapid characterization and optimization of different ambient ionization sources without the actual use of a mass spectrometer. Valuable illustrations are obtained of changes in spatial distribution and number of charges detected for ESI, PSI and SAWN ion plumes. Copyright