Corrective correlation method for the analysis of gases by plasma/laser-excited fluorescence spectrometry

Traces of gaseous impurities in permanent gases can be quantitatively determined by recording their fluorescence produced in a dual process of excitation in a plasma discharge combined with excitation in a resonant field of laser radiation. However, variations in the composition of the gas samples can cause systematic errors of determination. Such errors can be corrected using a correlation relationship established between the fluorescence intensity and concentrations of components of the sample. As an example, the possibility of accurate determination of low neon concentrations in a sample of helium containing an undetermined amount of argon is presented. The correlation relationship between the level of the saturated fluorescence of neon and the saturation parameter (spectral density of laser power required to reach the 50% level of neon fluorescence intensity relative to the level of the completely saturated fluorescence) over a broad argon content range in helium was established and used. The objective was to neutralize possible obscuring impacts of unknown uncontrolled impurities that may or may not be present in a gas sample on the analytical results.     

Structure and dynamics of phthalocyanine-argonn (n = 1-4) complexes studied in helium nanodroplets

Van der Waals clusters of phthalocyanine with 1-4 argon atoms formed inside superfluid helium nanodroplets have been investigated by recording fluorescence excitation spectra as well as emission spectra. The excitation spectra feature a multitude of sharp lines when recorded in superfluid helium droplets in contrast to the respective spectra measured in a seeded supersonic beam (Cho et al. Chem. Phys. Lett. 2000, 326, 65). The pickup technique used for doping of the phthalocyanine and the argon into the droplets allows for nondestructive analysis of the cluster sizes. Alternation of the pickup sequence gives information on the binding site of the argon atoms. The investigation of dispersed emission spectra in helium droplets can be used as a special tool for the identification of 0(0)0 transitions within the variety of sharp lines seen in the excitation spectra. Thus, different isomers of the clusters can be distinguished. Moreover, the emission spectra reveal information on dynamic processes such as vibrational predissociation of the van der Waals complexes and interconversion among isomeric species. The binding energy of the phthalocyanine-argon1 complex in helium droplets was estimated to be at most 113 cm-1.     

Analytical interference effects on laser-induced fluorescence of ethylene by selected molecular species

The interference of numerous compounds on the laser-induced fluorescence of ethylene at 10.6-mm was studied. The compounds studied were methane, propane, hexane, heptane, propylene, 1-butene, acetylene, benzene, cyclohexane, acetone, chloroform, carbon tetrachloride, methanol, ethanol, sulfur dioxide, nitrogen dioxide, nitric oxide, carbon dioxide, water, argon, helium, nitrogen, and air. Only some of these, in low concentrations, interfered at atmospheric pressure, but most interfered in evacuated systems. Compounds which absorbed the excitation 10.6μm radiation enhanced the fluorescence signals of ethylene, while non-absorbing compounds generally did not interfere. The quenching efficiencies of helium, argon, nitrogen, and methane on excited ethylene molecules were determined, and compared to values calculated from published data; good agreement was found except for methane. Quenching experiments with higher concentrations of added compounds were also performed.     

Design analysis of a laser ablation cell for inductively coupled plasma mass spectrometry by numerical simulation

A laser ablation setup including outer chamber, sample tube, sample holder and transport tubing was modelled and optimized using advanced computational fluid dynamics techniques. The different components of the setup were coupled and the whole device was modelled at once. The mass transport efficiency and transit times of near infrared femtosecond (fs) laser generated brass aerosols in pure argon and helium–argon mixtures were calculated at experimentally optimized conditions and a transient signal was constructed. The use of helium or argon did not influence the mass transport efficiency, but the signal structure changed. The signal fine structure was retrieved and experimentally validated. Bimodal peak structures were observed that seemed to originate from turbulent effects in the tubing connecting a Y-connector and the injector.     

碰撞气体的种类和压力对离子阱质谱性能的影响

基于数字离子阱技术,研究了离子阱质谱分析实验过程使用的碰撞气体种类及压力对离子阱质谱性能,如质量分辨能力、信号强度、串级质谱分析,以及低质量截止效应等的影响.实验过程中,在离子的激发和碰撞诱导解离阶段,分别采用质量数不等的氦气(质量数=4 amu)、氮气(质量数=28 amu)、氩气(质量数=40 amu)等作为碰撞气体,以及不同的气体压力,研究了它们对质谱性能的影响.结果表明,当采用质量数较大的氩气作为碰撞气体时,可以有效改善低质量数截止效应和提高离子碰撞过程中的能量转移效率,同时提高离子捕获和解离效率,但是质量分辨率会明显降低.在获得较高质量分辨率方面,氦气作为碰撞气体时效果最好.在气压相同的情况下,质量数大的碰撞气体有利于提高串级质谱分析效率,即获得更多碎片离子峰和更多有关母体离子结构的信息.     

Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.     

Non-thermal features of atmospheric-pressure argon and helium microwave-induced plasmas observed by laser-light Thomson scattering and Rayleigh scattering

Laser-light Thomson scattering and Rayleigh scattering have been measured from a microwave-induced plasma sustained at atmospheric pressure, using both argon and helium as a support gas. The measurements were performed at several spatial positions in each plasma, and at forward microwave power levels of 350 W for argon, and at 350 W and 100 W for helium. It was found from these measurements that both argon and helium plasmas deviate substantially from local thermodynamic equilibrium (LTE), Measured electron temperatures range from 13 000–21 500 K, whereas gas temperatures are generally lower by a factor of 2 to 10, depending on the support gas and the spatial position in the discharge. At the same forward microwave power, the electron temperature of the helium plasma is about 3500–7000 K higher than that of the argon plasma. Yet, the argon plasma has a higher electron number density than the helium plasma. Electron number densities in both argon and helium plasmas are roughly two to three orders of magnitude lower than what LTE would predict, based on the measured electron temperatures and the Saha Equation. Even more interestingly, signals in the far-wing portion of the Thomson-scattering spectrum were found to be significantly higher than are predicted by a fitted Maxwellian curve, indicating that there exists an over-population of high-energy electrons. It is concluded that, compared to the inductively coupled plasma, the microwave-induced plasma is highly non-thermal and remains in an ionizing mode in the analytical zone.     

Cathode erosion in inert gases: The importance of electrode contamination

Experimental results are presented for electrode erosion on copper electrodes in magnetically rotated arcs in argon and helium. Measurements were also made of the arc voltage and velocity. The effects due to the contamination of the electrode surface by either a native contaminant layer (copper oxide and carbon traces) or the continuous injection of very small amounts of various diatomic gases (nitrogen, oxygen, chlorine, and carbon monoxide) into the inert plasma gases were determined. The erosion rates for pure argon were significantly higher than those for pure helium (13.5 g/C for argon and 1 g/C for helium) and with both gases, very high arc velocities were measured initially (>60 m/s for argon and >160 m/s for helium) when a natural contaminant layer was still present on the cathode. The removal of this layer resulted in lower velocities (2m/s for argon and 20m/s for helium) and higher erosion rates. The removal of the layer was much faster with argon, due possibly to higher electrode surface current densities for argon arcs.     

Molecular kinetic aspects of vaporization of volatile coordination compounds with organic ligands

We present results of the experimental study and numerical simulation of radiation-convective heat and mass transfer during the sublimation of spherical particles of metal β-diketonates in a high-temperature inert gas flow (argon or helium). The sublimation process is visualized, and experimental data on the temperature variation dynamics and particle size are obtained. It is shown that at stable transfer of the compound from the particle surface the sublimation proceeds with the formation of large pores in its structure. The effect of inert gas properties on the kinetics of the vaporization process of precursor particles with various initial diameters is analyzed in the temperature range from 200 °C to 330 °C. Due to a higher thermal conductivity and heat capacity of helium as compared with argon, the choice of helium as carrier gas causes an increase in the sublimation intensity.     

分子筛对微量二氧化碳的吸附

本文研究了分子筛对氦气中微量二氧化碳的静态吸附和对氩气中微量二氧化碳的连续动态吸附，及格连续流动法测定了载气氩和氦对分子筛吸附微量二氧化碳的影响。     

Development of soft plasma ionization (SPI) source for analysis of organic compounds

We present a newly designed soft plasma ionization (SPI) source developed for mass spectrometric study of organic compounds in this study. The SPI cell having a relatively small size consists of a hollow anode and a hollow mesh cathode. The voltage–current characteristic depending on the pressure was investigated, indicating that it has similar characteristics to conventional hollow cathode glow discharges. To investigate the emission characteristics of the SPI source, some molecular band emission spectra (N₂, N₂⁺ and OH⁺) were measured by using argon and helium discharge gases. The SPI source was installed to a commercially used quadrupole mass analyzer for analyzing organic compounds. To demonstrate the SPI source, the mass spectra of some organic compounds (methylene chloride, toluene, benzene, cyclohexane and chloroform) were measured. The organic compounds were ionized with good stability in the plasma, and the fragmentation depended on the applied current. When helium and argon gases were used as the discharge gas, the helium plasma was more suitable for SPI-MS rather than argon because the argon plasma not only suffers from spectral interference but also has lower sensitivity.     

Comparison of helium and argon as collision gases in the high energy collision-induced decomposition of MH+ ions of peptides

Collision-induced decompositions (CID) of protonated peptides were studied using a four-sector mass spectrometer. The collision gases employed were helium and argon. The CID spectra of several peptides covering the molecular mass region of 905–2465 u were recorded. These investigations established several previously unrecognized differences between the CID spectra obtained with helium and argon as collision gases. These can be summarized as follows: (1) Structurally significant and specific side chain fragmentations (d_n ^f, w_n ^f and v_n, ion types) are greatly reduced or completely missing in the CID spectra obtained with helium as a collision gas compared to those obtained with argon. (2) As the peptide molecular mass increases, argon, which is heavier than helium, is increasingly more efficient than helium for generating fragment ions.     

Investigation of condensed products of graphite evaporation in an electric arc in argon and helium atmosphere

The composition of products formed in the discharge chamber at the synthesis of nanostructures by arc discharge was investigated. The fullerene soot obtained in an argon atmosphere was shown to contain at least three structural phases: amorphous carbon, fullerenes, and graphitized particles. In the process of thermal desorption, the water and oxygen adsorbed from the atmosphere, as well as carbon oxides generated at the oxidation evolve from the argon soot. By the reactivity, the fullerene black obtained in different buffer gases form a series: special helium, argon, usual helium. The cathode deposit of the arc discharge in argon, as in helium, contains multiwall nanotubes in its soft parts.     

Electronic spectroscopy of benzo[g,h,i]perylene and coronene inside helium nanodroplets

We have recorded the electronic spectra of benzo[g,h,i]perylene and coronene and their van der Waals complexes with argon and oxygen with a helium-nanodroplet depletion spectrometer. These molecules differ by the addition of one and two fused benzene rings to perylene, which was previously studied in helium. The coronene spectrum is similar to a previously reported jet-cooled laser-induced fluorescence (LIF) spectrum. The van der Waals complexes with argon and oxygen show different complexation sites and maximum number of adsorbants. We report a vibronically resolved benzo[g,h,i]perylene S(1) <-- S(0) spectrum. The spectral lines are split in a similar way to that of several molecules studied before. However, surprisingly, while the van der Waals complexes with argon are free of the splitting, the complexes with oxygen retain the splitting, with increased linewidth and splitting. We could also observe the S(2) <-- S(0) origin transition of benzo[g,h,i]perylene which was previously observed by cavity ring down spectroscopy. While in general the two spectra are quite similar, the relative intensities and spectral shifts of several lines are different.     

A continuous flow mass spectrometry technique of argon isotope measurement for K/Ar geochronology

A new method for the measurement of argon isotope composition in a continuous flow of helium for potassium/argon geochronology is described. Extraction of argon from geological samples in multiple‐sample holders was carried out in a chamber by heating with a continuous Nd‐YAG laser. The extracted and pre‐concentrated argon is passed through a chromatographic capillary column in a flow of helium. Argon is separated from possible contaminants in the column and is injected through an open split into the ion source of an isotope ratio mass spectrometer. Measurement of the ³⁶Ar, ³⁸Ar and ⁴⁰Ar isotopes was carried out in dynamic mode, using a triple‐collector ion detector. These experiments have shown that continuous flow mass spectrometry can be used for the analysis of radiogenic argon in picogram quantities with an accuracy that is satisfactory for the solution of many geochronological problems. The method of argon isotope measurement in a continuous flow of helium is an alternative to the measurement of argon isotopes in the static mode. The sensitivity and accuracy of argon measurement by this method are comparable with those provided by the classical static method. The measurement of argon isotopes in a continuous flow of helium is simpler and more reliable than measurement in the static mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Comparative study of microwave-induced plasma atomic emission spectrometry and atomic fluorescence spectrometry as gas-chromatographic detectors for the determination of methylmercury in biological samples

In order to attain a lower detection limit with the HS GC MIP analytical method (Head-Space Gas Chromatography with Microwave-Induced Plasma detection) recently developed for the analysis of methylmercury in biological samples, the quarter-wave Evenson-type cavity used until now was replaced by a TM₀₁₀ Beenakker-type cavity, which was used with both argon and helium as carrier gas. With an argon plasma, an eightfold increase in detection limit was gained compared with the argon plasma sustained by the Evenson cavity, while only a four-fold increase was gained with the helium plasma. In a second step of the study, the MIP detector was replaced by an AFS (atomic fluorescence) detector (CVAFS Model-2, Brooks Rand Ltd, Seattle, USA). With this AFS detector a detection limit of 1 ng methyl mercury per g biological tissue could be reached; i.e. measurements were 40 times more sensitive than those using the Evenson cavity. This detector has some other advantages compared with MIP detection: it is less expensive and easier to manipulate, while the same precision and accuracy are obtained. The use of AFS as detector in the headspace gas chromatographic system is therefore an important improvement for the analysis of methyl-mercury in biological samples.     

Optimization of matrix-assisted laser desorption/ionization time-of-flight collision-induced dissociation using poly(ethylene glycol)

Details of the optimization of the collision-induced dissociation (CID) process, using a collision cell on a matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometer, are described using poly(ethylene glycol) 1000 (PEG 1000) as a model analyte. The effects of collision gas identity (helium, air, and argon), as well as collision gas pressure, on the resulting MS/MS data were investigated. With PEG 1000, helium was found to give the best results with respect to signal-to-noise (S/N) ratio. The optimum pressure for each gas was found to be in the range where the precursor ion signal was attenuated to approximately 30-50% for helium and 40-60% for argon. The effect of cation choice (Li, Na, and K) on the CID of PEG was also studied. CID spectra were produced for each, but PEG cationized with lithium was found to produce the spectra with the highest S/N ratio. The MALDI-TOF CID spectra that were generated for PEG were compared with the high-energy and low-energy MS/MS spectra obtained from a sector mass spectrometer and from a triple quadrupole mass spectrometer, respectively. The results observed for PEG confirm that CID on a MALDI-TOF mass spectrometer is a high-energy MS/MS technique.     

Thermodynamic and transport properties of argon/carbon and helium/carbon mixtures in fullerene synthesis

The equilibrium composition and thermodynamic and transport properties of argon; carbon and helium/carbon mixtures are calculated in the temperature range 300–20,000 K. The curves for the composition of mixtures of 50%, carbon in argon or helium are shown fir a pressure of 1.33 × 10⁴ Pa. The calculations for the heat capacity at constant pressure (C_p) and transport coefficients are validated with other studies, for the cases or pure argon and pure helium at a pressure of 10⁵ Pa. The properties of mixtures with various proportions of carbon in argon and helium are calculated. Results are presented at pressures of 105 and 1.33 × 10⁴ Pa, typical of reactors for the synthesis of fullerenes and nanotubes. It is observed that the properties of carbon and mixtures of carbon with a buffer gas (argon or helium) are very different from those of the buffer gas, thus the need to consider this effect in simulations. In general, the mixtures follow trends intermediate to those of the pure gases from which they are composed except for the thermal conductivity which shows a deviation from this tendency in the region between 11,500 and 19,000 K for argon/carbon mixtures and between 8,000 and 12,000 K for helium/carbon mixtures. Also, the electrical conductivity of mixtures of low carbon concentration is very close to that ofpure carbon. A datafile containing the transport properties of mixtures for pressures between 10⁴ and 10⁵ Pa is available free of charge from the authors.     

The Effects of Added Hydrogen on Noble Gas Discharges Used as Ambient Desorption/Ionization Sources for Mass Spectrometry

We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H₂/Ar and 2 using H₂/He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

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Excitation Temperature and Constituent Concentration Profiles of the Plasma Jet Under Plasma Spray-PVD Conditions

Plasma spray-physical vapor deposition (PS-PVD) is a promising technology to produce columnar structured thermal barrier coatings with excellent cyclic lifetime. The characteristics of plasma jets generated by standard plasma gases in the PS-PVD process, argon and helium, have been studied by optical emission spectroscopy. Abel inversion was introduced to reconstruct the spatial characteristics. In the central area of the plasma jet, the ionization of argon was found to be one of the reasons for low emission of atomic argon. Another reason could be the demixing so that helium prevails around the central axis of the plasma jet. The excitation temperature of argon was calculated by the Boltzmann plot method. Its values decreased from the center to the edge of the plasma jet. Applying the same method, a spurious high excitation temperature of helium was obtained, which could be caused by the strong deviation from local thermal equilibrium of helium. The addition of hydrogen into plasma gases leads to a lower excitation temperature, however a higher substrate temperature due to the high thermal conductivity induced by the dissociation of hydrogen. A loading effect is exerted by the feedstock powder on the plasma jet, which was found to reduce the average excitation temperature considerably by more than 700 K in the Ar/He jet.