Gas chromatographic determination of organolead compounds with an alternating current plasma detector

The performance of the gas chromatography/alternating current plasma detector as a selective detector for organolead compounds is investigated. The helium make-up flow rate and the spatial position from which the lead emission is viewed, have an effect on the detector response. The detection limit for tetrabutyl lead was established as 130 pg/s and the lead selectivity ratio was found to exceed 13,800. Some applications of organolead determination in complex matrices were also studied in order to demonstrate the selectivity and sensitivity of the alternating current plasma detector.     

Multi-element selective radio frequency plasma detector for capillary gas chromatography

A radio frequency plasma detector for element specific detection in gas chromatography is described. The detector is comprised of a radio frequency (300 kHz) discharge between electrodes in helium, and utilizes a low-resolution emission spectrometer to monitor selected spectral emission lines produced when the helium discharge decomposes and excites the atomic constituents in the chromatographic column effluent. The spectrometer is tuned to an atomic emission line in the near-infrared portion of the spectrum, and the emission intensity from the discharge region of a selected line is used to monitor the concentration of the element producing that line. Acceptable detector sensitivity was achieved by the use of a high-throughput optical system. Selectivity was achieved by a combination of correct line selection, plasma and carrier gas purification, and plasma gas doping.     

Pulsed discharge emission detector — Application to analytical spectroscopy of permanent gases

Summary This publication contains our initial development of a pulsed discharge emission detector (PDED) (patent pending). It uses a pulsed high voltage discharge in helium, which provides a stable source for atomic and polyatomic emission spectroscopy. We have evaluated this detector for both quantitative and qualitative analysis of a range of chemical compounds. Emission spectra observed from the pulsed high voltage discharge are valuable for spectral analysis. The results obtained for selected permanent gases in the ultraviolet, visible and infrared regions of the optical spectrum indicate that these spectra can be used for compound identification after a chromatographic separation. The data are unique in our opinion and serve as a basis for the future development and investigation of the analytical significance of this detection method.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

等离子体发射检测器在检测高纯氦气中微量氖气的应用

采用等离子发射检测器(PED)和氦离子放电检测器(DID)对重量法制备的氦气中微量氖气进行了检测,对比了微量氖气在两种检测器上的灵敏度和重复性。结果显示,PED对氖气的检测灵敏度较高,氖气含量在0.03~0.3μmol/mol范围与响应值呈良好的线性关系,r2=1.000,检测限小于1 nmol/mol,测定结果的相对偏差小于2%(n=6)。利用大气压离子质谱仪对检测限测试结果进行了验证。采用等离子发射检测器检测氦气中微量氖气的方法,可以降低微量氖气标准物质的定值不确定度,为研制高准确度微量氖气标准物质奠定基础。     

Characteristic responses of an atmospheric pressure DC micro-plasma detector for gas chromatography to organic functional groups

A gas chromatographic detector using direct current micro-plasma discharged a distance of less than 50 μm under helium at atmospheric pressure is described. The micro-plasma device was assembled on glass substrates; the volume of the plasma region was only 0.58 nL. Very low power consumption (15 mW) and only carrier helium flow were needed to maintain micro-plasma stability. Organic compounds with various functional groups were chromatographically separated and fed into the micro-plasma. Fluctuations in plasma current were detected as the sample passed through the micro-plasma. All non-halogen organics showed positive peaks, while simple alkyl halides showed negative peaks. Compounds with both aromatic and halogen groups exhibited hybrid peak shapes, consisting of both positive and negative peaks. The detection limits (3σ) ranged from 24.5 pg for m-xylene to 756 pg for 1,2-dichloroethane, depending on differences in ionization and electron-capture efficiency.     

New studies of the plasma emission detector

Being an element-selective detector, the plasma emission detector was used to determine carbon in organic compounds. Experiments were carried out with the aid of osculating interference filters and lock-in amplifiers. The obtained signals were processed by a fast-Fourier-transform analyzer to study their frequency spectra. Results are given for the detection of carbon. Furthermore studies on the influence of angle-adjustment, microwave power, photomultiplier voltage and oscillation frequency on the determination of fluorine in organic compounds were carried out and results for detection limits and dynamic range of this method are presented.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Adirectly Coupled Microwave-Induced Plasma Atomic Emission Liquid Chromatograpy Detector for Nonmetals: Preliminary Characterization with Halides and Oxohalogen Salts

Abstract

A liquid chromatography system is directly coupled to a moderate power helium microwave induced plasma for the selective determination of no metals in aqueous solutions. The detector is a large volume helium microwave-induced plasma operated at 500 watts with a helium support gas flow of 21L/min. A sample set of halides and oxohalgen salts are separated by ion exchange chromatography and introduced into the plasma as mist generated with an ultrasonic nebulizer. Detection limits range from 1.5 to 6 μg. Calibration plots are presented. Selectivity is observed when monitoring the elemental signals of co-eluting peaks.     

气相色谱-微波等离子体炬双检测器及其气相色谱的响应特性

提出并建立了气相色谱-微波等离子体炬(MPT)原子发射光谱和离子化双检测器系统. 以Ar气作为等离子体工作气体, O2气作为等离子体屏蔽气体, 同时获得了被测组分的原子发射和离子化信息, 并对不同种类有机化合物的相对响应系数及检出限进行了测定.     

On-line microwave-induced helium plasma atomic emission detection for capillary zone electrophoresis

We report a feasibility study on using a microwave-induced helium plasma atomic emission detector (MIP-AED) as an on-line detector in capillary zone electrophoresis (CZE). To couple CZE to MIP-AED, we used an ion exchange membrane capillary to connect the separation capillary to the interfacing capillary. The outlet end of the interfacing capillary was placed directly in the discharge tube of the MIP-AED system. The electroosmotic flow generated in the separation capillary carried the analytes and the electrolyte buffer solution through the interfacing capillary into the MIP-AED discharge tube where the analytes were detected. The performance of the CZE/MIP-AED system was evaluated with trimethyltin chloride, dimethyltin dichloride, n-propanol, and 2-butanone. The preliminary results indicate that the MIP-AED can be used in CZE to provide element-specific detection for target analytes.     

直流等离子体离子化检测器的研究：管道煤气中可燃气体的测定

本文提出一种改进的直流等离子体离子化检测器（ＤＣＰＩＤ），用于管道煤气中可燃气体Ｈ２、ＣＨ４和ＣＯ的测定。采用氢气作工作气体，对该检测器的工作参数和响应特性进行了优化。本法结果与微波诱导等离子体离子化检测器（ＭＩＰＩＤ）的结果作了比较，结果满意。     

Determination of Xenon in Air by a Pulse-discharge Helium Ionization Detector

A pulse-discharge helium ionization detector(Valco, PD-D3-I) was used to measure xenon concentration in air. The dependences of the detector relative response on various gas chromatograph parameters were investigated. Based on the well prepared gas connections for the detector system and optimized gas chromatography(GC) working conditions, the atmospheric xenon concentration could be measured by the cheap GC method with a detection level of 0.7?0^-9(parts by volume). Moreover, the xenon concentration in the ground level air around our laboratory was measured with the result of 0.085?0^-6(parts by volume) and RSD of 0.91%.     

The Use of the Helium Ionization Detector for Gas Chromatographic Monitoring of Trace Atmospheric Components

Two different gas chromatographic detectors, the helium ionization detector (HID) and the more commonly used flame ionization detector (FID), were used in parallel to compare their responses to a number of organic compounds. Atmospherically important oxygenated species were analyzed, as well as hydrocarbons and chlorinated and sulfur containing organics. The HID exhibited the better response to all compounds investigated, most notably to formaldehyde and higher oxygenates. A gas chromatographic system was developed to trap and analyze atmospheric organic compounds with HID detection. This required careful choice of the adsorbent material and removal of inorganic components (namely nitrogen and oxygen) before analysis. Real air samples were then taken and analyzed qualitatively for a range of olefinic and aromatic compounds.     

Correlation Between the Electrical and Optical Properties of an Atmospheric Pressure Plasma During Siloxane Coating Deposition

The effect of varying process parameters on atmospheric plasma characteristics and properties of nanometre thick siloxane coatings is investigated in a reel-to-reel deposition process. Varying plasma operation modes were observed with increasing applied power for helium and helium/oxygen plasmas. The electrical and optical behaviour of the dielectric barrier discharge were determined from current/voltage, emission spectroscopy and time resolved light emission measurements. As applied power increased, multiple discharge events occurred, producing a uniform multi-peak pseudoglow discharge, resulting in an increase in the discharge gas temperature. The effects of different operating modes on coating oxidation and growth rates were examined by injecting hexamethyldisiloxane liquid precursor into the chamber under varying operating conditions. A quenching effect on the plasma was observed, causing a decrease in plasma input power and emission intensity. Siloxane coatings deposited in helium plasmas had a higher organic component and higher growth rates than those deposited in helium/oxygen plasmas.     

Investigations on laser ablation–microwave induced plasma–atomic emission spectrometry using polymer samples

The potential of laser ablation–microwave induced plasma–atomic emission spectrometry (LA–MIP–AES) for the analysis of plastic materials has been investigated. A Nd/YAG laser, operated in its fundamental mode at 1064 nm, was used to ablate small amounts of various plastics. The sample atoms were transported and excited in a closely neighbored continuously running microwave induced plasma (MIP) operated in argon or helium at reduced pressure. A 0.5-m échelle spectrometer, equipped with an intensified charge coupled device (ICCD) as a detector was used for recording the spectra. The amount of ablated material was found to be strongly dependent on the matrix (10–190 ng/shot). Signals for some metals often used as additives in polymers (Al, Ca, Cu, Sb, Ti) and for the elements F, Cl, Br, J, and P in various polymers were recorded in the spectral range 250–840 nm. The estimated detection limits were found to be in the range 0.001–0.08% for metals and 0.05–0.7% for non-metals. Spectral lines of fluorine and iodine could only be measured in the helium MIP. For high concentrations of chlorine and carbon in the samples (polyvinylchloride), a memory effect was observed.     

Hydrogen analysis in solid samples by utilizing He metastable atoms induced by TEA CO2 laser plasma in He gas at 1 atm

A TEA CO₂ laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO₂ laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO₂ laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO₂ laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens.     

Evaluation of a radio frequency plasma for oxygen-selective detection in capillary gas chromatography

A radio frequency plasma detector for capillary GC has been modified for oxygen-selective detection. Purification of the plasma gas and purging of both ends of the discharge region with helium were crucial to minimizing oxygen background emission from impurities in the plasma. With a pure helium plasma, eluting hydrocarbons released oxygen from the discharge region resulting in interfering signals on the oxygen channel. These interfering signals were efficiently reduced by using a methane-doped (0. 15%) low power RF plasma (15 W) sustained in a high make-up flow (150 mL/min). With this plasma, a 10³:1 oxygen-to-carbon selectivity and a 100 pg oxygen/s detection limit were obtained. The detector was linear over three orders of magnitude. The detection system has been used to screen for oxygenated compounds in two environmental samples.     

A comparative study of two cavities for generating a microwave induced plasma in helium or argon as a detector in gas chromatography

In the microwave induced plasma (MIP) detector both $\text{1}\text{4}$λ-Evenson and Beenakker cavities are used. The last one also operates at atmospheric pressure. Both cavities are investigated with some simple alkanes. In the gas chromatographical system helium and argon are used as carrier gas. Measuring the C emission line, the Beenakker cavity with argon shows the greatest sensitivity, the best detection limit (0.2 ng C/s) and a good linear dynamic range (> 800). The best detection limit for H emission is found at use of the Beenakker cavity with helium (0.13 ng $\text{H}\text{s}$). The results of measuring the H emission line using the Beenakker cavity with argon are poor. It was further shown that, although it is in principle possible to determine a ratio formula or molecular formula with the aid of a reference compound, the results are inadequate for ‘unknown’ compounds.     

Analytical Potentials and Features of Atomic Emission Analysis Using Electron-Impact Excitation of Atoms in Helium under Atmospheric Pressure

A device is described for the atomic emission analysis of vaporous samples using electron-impact excitation in helium under atmospheric pressure. The device consists of a cathode atomizer with a test sample applied onto it and the anode located at 1–3 mm from the cathode. The electrons emitted by the cathode upon heating are accelerated by applying a constant voltage to the electrodes. The mechanism for the formation of a non-self-sustained gas discharge between the cathode and anode is considered and the properties of the discharge are compared to those of the known discharges used in atomic emission spectrometry. The influence of atomization temperature and helium pressure on the analytical and background signals was studied. It is shown that, under certain conditions, the analytical signal increases with helium pressure. The relative detection limits attained for a number of elements are from tenths to dozens of nanogram per liter; this is two or three orders of magnitude lower than those in inductively coupled plasma atomic emission spectrometry and of the same order of magnitude as detection limits in inductively coupled plasma mass spectrometry.     

Relative Responses of Noble Gases Using a Pulsed Discharge Helium Photoionization Detector:Theoretical Calculation and Experimental Determination

The relative response factors（RRFs） for noble gas（Ng） were determined on a pulsed discharge helium photoionization detector. Using ab initio method, the atomic orbitals of noble gas were calculated and used to determine the number of ionizable electrons on the basis of the continuous emission of He2. The molar responses of noble gases is well correlated with the number of ionizable electrons.     

Determination of non-metallic elements by capacitively coupled helium microwave plasma atomic emission spectrometry with capillary gas chromatography

A capacitively coupled microwave helium plasma with a tubular tantalum electrode was evaluated as an element selective detector for gas chromatography (GC). The end of a 10-m bonded fused capillary column was directly inserted into the tubular electrode without any switching system. A heated copper tube was used to house the part of the GC column that protruded from the oven. The optimisation of operating parameters, line selection, background emission and horizontal and vertical observation position is described. Analytical figures of merit including sensitivity, reproducibility, signal to background ratio, selectivity, dynamic range and limit of detection (LOD), were evaluated for carbon, hydrogen, chlorine and bromine emission. Limits of detection in the low ng range (20 pmol) were obtained for halogenated compounds using carbon emission, whereas LODs in the 0.1 micrograms range (2 nmol) were obtained using chlorine or bromine emission lines.