Fred P. M. Jjunju

In situ analysis of corrosion inhibitors using a portable mass spectrometer with paper spray ionization

Paper spray (PS) ambient ionization is implemented using a portable mass spectrometer and applied to the detection of alkyl quaternary ammonium salts in a complex oil matrix. These salts are commonly used as active components in the formulation of corrosion inhibitors. They were identified in oil and confirmed by their fragmentation patterns recorded using tandem mass spectrometry (MS/MS). The cations of alkyl and benzyl-substituted quaternary ammonium salts showed characteristic neutral losses of CnH2n (n carbon number of the longest chain) and C7H8, respectively. Individual quaternary ammonium compounds were detected at low concentrations (<1 ng μL(-1)) and over a dynamic range of ∼5 pg μL(-1) to 500 pg μL(-1) (ppb). Direct detection of these compounds in complex oil samples without prior sample preparation or pre-concentration was also demonstrated using a home-built miniature mass spectrometer at levels below 1 ng μL(-1).

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.

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.

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.

Development of a portable, low cost, plasma ionization source coupled to a mass spectrometer for surface analysis

This paper details the development of a handheld battery operated ambient ionization source that when coupled to a mass spectrometer is capable of in-situ, solid phase chemical analysis. There exists a plethora of proven techniques for ionizing liquid and gas phase analytes for mass analysis but due to a lack of volatility, solid phase analytes can be difficult to ionize and introduce directly from a surface to a mass spectrometer. Various ambient technologies have been developed for this purpose such as low temperature plasma (LTP), desorption electrospray ionisation (DESI) and direct analysis in real time (DART), but each of these technologies has associated drawbacks for miniaturization. The ionization device described weighs less than 600 g, can be operated for 6 hours continuously from battery power, requires no other inputs or sample preparation and has a touch screen interface for improved ease of use for non-specialist operators. This paper details the design considerations in its development as well as testing and procedures for integration with a mass spectrometer for chemical sensing.

Portable fluorescent sensing array for monitoring heavy metals in water

The availability of clean water is of fundamental importance to human health and survival, as a habitat for aquatic species, for farming and industrial use. Water quality is likely the most important factor in maintaining the health in both farmed and wild fish. Understanding water quality is critically important in facilities which reuse a large percentage of system water. Heavy metals can have a major impact on aquatic health and have a tendency to accumulate in the food chain. In this study we describe a novel fluorescence sensor for the detection of heavy metal ions in water. Fluorophores immobilized in a polymer membrane were excited using an array of LEDs and the fluorescent emission measured via a CCD camera. This novel portable device is comprised of a 3×3 array of sensing elements across which the water sample is pumped and the fluorescence image generated is used to determine the metal ion content. Herein we demonstrate this approach for the detection of Cu (II) ions in water.

A physical model for low-frequency electromagnetic induction in the near field based on direct interaction between transmitter and receiver electrons

A physical model of electromagnetic induction is developed which relates directly the forces between electrons in the transmitter and receiver windings of concentric coaxial finite coils in the near-field region. By applying the principle of superposition, the contributions from accelerating electrons in successive current loops are summed, allowing the peak-induced voltage in the receiver to be accurately predicted. Results show good agreement between theory and experiment for various receivers of different radii up to five times that of the transmitter. The limitations of the linear theory of electromagnetic induction are discussed in terms of the non-uniform current distribution caused by the skin effect. In particular, the explanation in terms of electromagnetic energy and Poynting’s theorem is contrasted with a more direct explanation based on variable filament induction across the conductor cross section. As the direct physical model developed herein deals only with forces between discrete current elements, it can be readily adapted to suit different coil geometries and is widely applicable in various fields of research such as near-field communications, antenna design, wireless power transfer, sensor applications and beyond.