Pulsed discharge emission detector: an element-selective detector for gas chromatography

An element-specific pulsed discharge emission detector (PDED) has been coupled directly with a vacuum UV monochromator so that vacuum UV atomic emissions from Cl, Br, I and S can be observed. The observed sensitivities for the elements are in the range of mid to high pg/s, but can be lowered by direct absorption of the radiation using a vacuum UV radiation photomultiplier tube. A helium pulsed discharge photoionization detector (He-PDPID) was run simultaneously in parallel with the PDED. The chromatograms recorded with the two detectors had similar peak shapes, suggesting that there is no peak tailing in the PDED. The ratio of the detector responses PDED/He-PDPID can be used for qualitative identification of the Cl-, Br-, I- or S-containing compounds.     

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.     

Universal and discriminative detection using a miniaturized pulsed discharge detector in comprehensive two-dimensional GC

A miniaturized pulsed discharge detector (Mini-PDD) has been successfully demonstrated for comprehensive 2-D GC (GC x GC) analysis of pyrolysis gasoline and the pyrolysis GC x GC analysis of a polyethylene copolymer. The detector cell volume of the Mini-PDD is reduced to 25% of the Valco plug-in PDD D-3. An n-C11 peak width at base is 96 ms for the Mini-PDD, about 23% larger than a peak width of 78 ms detected by a flame ionization detector (FID). The Mini-PDD has sufficient response time for most GC x GC applications. When Mini-PDD is operated in helium photoionization mode (Mini He-PDD), it is a universal detector for both inorganic and organic compounds. This is especially useful when detection of water is needed in GC x GC applications. When krypton is doped in the helium discharge gas (Mini Kr-PDD), it can suppress signals of compounds having higher ionization potentials and enhance relative signal intensities of aromatic compounds. The determination of aliphatic to aromatic hydrocarbon ratios is essential to the operation of petroleum crackers. Comparison of the signal from two modes of the Mini-PDD is a simple and fast way to verify the location of aromatics in comprehensive 2-D gas chromatograms.     

Detection of organotin,organomercury, and organolead compounds with a pulsed discharge detector (PDD)

The response of a pulsed discharge detector (PDD) to organometallic compounds in the helium ionization detection (HID) mode was dependant on the number of C atoms in the tested analytes with the limits of detection ranging from 0.7 pg (tetraethyllead (Et(4)Pb)) to 1.2 pg di- n-propyl mercury (Pr(2)Hg)). Response linearity was excellent over three orders of magnitude. Selectivity in the HID mode was enhanced by doping the He discharge gas with argon, although sensitivity dropped threefold. In electron capture detection (ECD) mode, only organolead was detected with a limit of 0.1 pg.     

Pulsed discharge helium ionization detector

Summary A pulsed discharge helium ionization detector (PDHID) (patent pending) for gas chromatography has been developed. This detector uses a non-radioactive pulsed high voltage discharge source for generation of electrons and pulsed collection of these electrons. We have evaluated this detector for the analysis of a wide range of chemical compounds. In this paper the analytes are passed through the discharge since the permanent gases are difficult to ionize. The initial results for the permanent gases indicate that the PDHID can be used as a universal detector of contaminant traces at detection levels on the order of 1–20 pg. The response in this mode of operation is linear over four orders of magnitude.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

Characterization of chlorinated compounds using a dual chlorine-selective pulsed discharge emission detector-helium-pulsed discharge photoionization detector system

The Cl-selective pulsed discharge emission detector (Cl-PDED) response is dependent only upon the Cl content, irrespective of the molecular structures of the compounds. This provides a simple, fast quantitative method of analysis for chlorinated compounds. The response of the helium-pulsed discharge photoionization detector (He-PDPID) is a function of the molecular structure and the number of photoionizable electrons using the He2 band at 13.5-17.5 eV. The ratio of the responses of the two detectors is independent of concentration and can be used to characterize the Cl-containing compounds along with the retention time, or the ratio can be used as evidence for coelution. The dual Cl-PDED-He-PDPID detector system is a useful tool for peak identification. The effect of coeluting hydrocarbons on the Cl-PDED response was evaluated by spiking a gasoline sample with US Environmental Protection Agency mixture 502. All Cl-PDED responses were greater than 90% of the response in the absence of the hydrocarbons.     

Operating the pulsed discharged detector in both the electron-capture and photoionization modes within the same GC analysis

Summary Since the electron-capture detector (ECD) is highly selective, it is imperative to use a more universal ionization detector in conjunction with the ECD in order to detect non-capturing or weakly capturing compounds. Also in an EC study of weakly or moderately strong electron-capturing compounds, it is necessary to identify the EC peak of the compound by identifying the major component with an ionization detector. In this paper we have shown that the pulsed discharge detector can be interchanged between the EC and the helium ionization modes within 4–6 s. The application of this procedure has been illustrated with a mixture of alkane/alkene chlorocompounds. The interchange between EC and argon photoionization modes has also been investigated. The change from EC to argon photoionization also occurs in 4–6 s but the reverse process requires 9 s.     

Determination of percent composition of a mixture analyzed by gas chromatography. Comparison of a helium pulsed-discharge photoionization detector with a flame ionization detector

We present the results of a study of percent composition for a mixture which has been separated by gas chromatography and analyzed using helium pulsed-discharge photoionization detection (He-PDPID) and flame ionization detection (FID). FID has long been the means by which the percent composition of a hydrocarbon mixture has been determined since it has been previously established as a "carbon counting device". However, in this study we present results which show that He-PDPID is more accurate in determining the percent composition of a hydrocarbon mixture and, because it is a universal detection method and can detect compounds that FID cannot, it is also more effective for determining the percent composition of mixtures containing organic compounds with a variety of other functional groups.     

Development and characterization of chlorine-selective pulsed discharge emission detector for gas chromatography

A novel chlorine-selective pulsed discharge emission detector (Cl-PDED) for gas chromatography has been developed based on a reaction of krypton with chlorine and a unique design of the detector. A krypton ion produced in the krypton-doped helium pulsed discharge reacts with chlorinated compounds within the pulsed discharge to produce an excited species of KrCl* which emits at 221-222 nm. The reaction has the following advantages in respect to the detection of chlorinated compounds: (1) the reaction is an ion-molecule reaction that is 100-1000 times faster than a reaction of neutrals, which greatly enhances the sensitivity; (2) the KrCl* emission wavelength is far separated from interfering C emissions at 193. and 247.3 nm; (3) the KrCl* emission is transparent to air and can be recorded without a helium purge of the monochromator. The detector itself has been designed to have the following features: (1) the detector has a microvolume of the pulsed discharge region, ca. 0.35 microl, which increases the discharge power density to enhance the sensitivity; (2) this microvolume detector allows the use of a low flow-rate of approximately 5 ml/min, which enhances the sensitivity by the lower dilution of the column effluent; (3) the pulsed discharge is sufficiently narrow to replace the monochromator entrance slit, which gives much greater light gathering power; (4) the discharge electrodes are protected with a helium purge to prevent carbon deposition on the electrodes. This new Cl-PDED is the most sensitive chlorine-selective detector with a minimum detectability of approximately 50 fg Cl/s. The selectivity to carbon is 1000. There are no significant carbon emission lines in the KrCl* emission wavelength region, but the carbon continuum interference (stray light) limits the selectivity. The selectivity could be increased if a double monochromator were used to diminish the stray light. The detector linear range is over three orders of magnitude from 40 fg Cl to approximately 130 pg Cl, and the dynamic range is approximately 4 orders of magnitude. The relative standard deviation of the elemental response to chlorinated compounds is about 5%.     

脉冲放电氦光离子化检测器分析有机化合物的性能研究

研究本实验室组装的脉冲放电氦光离子化检测系统上PDPID的性能、各种操作参数对信号的影响、操作最佳化及信号线性。用该系统分析了汽油、酮醇混合物和痕量挥发性有机化合物等样品,它们的色谱图可以同FID相比。     

二维气相色谱法分析天然气水合物区沉积物间隙水中示踪气体的浓度

利用微流路控制技术中心切割装置(Deans Switch)、两根色谱柱(PoraPLOT Q和Molsieve 5A)和3个检测器(脉冲氦离子化检测器、火焰光度检测器、热导检测器),建立了一种二维气相色谱分析系统,实现了海洋中多种示踪气体组分(氢气、甲烷、二氧化碳、硫化氢)的同时分析和精确测定。氢气、甲烷、二氧化碳、硫化氢的含量分别在2～1030、0.6～501、120～10500和0.2～49.1 μmol/mol范围内的校正曲线线性关系良好,检出限分别为0.51、0.17、82和0.08 μmol/mol,10次重复测定含量的相对标准偏差均小于10%。通过对南海天然气水合物区沉积物间隙水顶空气的测定,表明该方法方便、灵敏、可靠,易于实现海上现场测定;与以往采用多种分析方法分别测定示踪气体相比,大大节省了样品量。该方法适用于海洋天然气水合物、海底热液等资源的调查和海洋溶解态气体的研究等。     

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。     

Helium Droplets: An Apparatus to Study Ultra Cold Chemistry

A new pulsed helium nano droplets machine has been constructed. The droplets were gener-ated by expansion of the pure helium through the cryogenic valve attached to a closed-cycle cryostat. The mean size of helium droplets can be controlled between 103 and 105 helium atoms by tuning the backing pressure (10-40 bar) and temperature (10-30 K). Compared with the continuous-flow beam source, the density of droplet is at least one order of magni-tude higher, which offers the opportunity to combine the system with the commercial pulsed laser to study chemical reactions inside of the superfluid helium at ultra-low temperature. The performance for the system has been checked by studying the photodissociation of CH₃I doped droplets at 252 nm with the velocity map imaging technique. The photofragments, CH₃, were detected by (2+1) resonance enhanced multiphoton ionization. The speed and angular distributions derived from resulting images show clear evidence of the relaxation effect by the surrounding helium atoms. The pulsed helium droplets depletion spectroscopy was also demonstrated. The depletion spectrum of benzene doped helium droplets indicatesthat less than 3% depletion can be observed with the newly constructed apparatus.     

Pulsed discharge photoionization detector: Application to analysis of chloro alkanes/alkenes

A windowless pulsed discharge photoionization detector (PDPID) is described which uses the emission spectra from the discharge in helium and Ar/Kr doped helium. The emission from helium is a continuum ranging from 13.5–17.7 eV which ionizes all compounds except neon. The emission from 5.4% Ar/He ranges from 9.3–11.8 eV and ionizes most organic compounds and many inorganic compounds. The emission from 1.36% Kr/He consists principally of the resonance lines at 10.6 and 10.1 eV. These PDPIDs are used to analyze a 12 component mixture containing principally chloro alkane/alkene. The relative responses of the PDPID combined with the relative retention time can be used to qualitatively identify the chloro compounds.     

高灵敏度的脉冲氦离子化检测器分析混合气体中的Kr、Xe

使用高灵敏度的脉冲氦离子化检测器（PDHID）气相色谱法对Kr、Xe浓度进行定量分析,并通过采用反应床除去杂质气体或与Kr、Xe难以分离的干扰组分N2、CH4和CO等,可使最低检测限达到Kr为7．931×10^-8、Xe为7．186×10^-8．对Kr的测量相对偏差在2％以内,对Xe的测量相对偏差在6％以内．     

Analysis of low levels of oxygen, carbon monoxide, and carbon dioxide in polyolefin feed streams using a pulsed discharge detector and two PLOT columns

A gas chromatography (GC) method is developed for rapid analysis of polyolefin feed streams for the catalyst poisons CO, CO(2), and O(2). The method uses an HP MoleSieve column in parallel with a CP-PoraPLOT Q column and a pulsed discharge detector (PDD). Detection limits for each of the potential poisons are between 50 and 250 ppb. For a 10-ppm standard, the precision of the method was +/- 4.2% for oxygen, +/- 7.8% for carbon dioxide, and +/- 2.0% for carbon monoxide. In addition to the polyolefin feed stream, nitrogen and hydrogen feed streams are also analyzed. In each case, sampling is observed to be a critical issue, with air contamination of the sample cylinder often the limiting step in determining the true level of oxygen. It is also noted that large amounts of argon are present in the standards when nitrogen is used as a balance gas. Because the trace oxygen peak partly coelutes with the larger argon peak, it is suggested that helium be used as the balance gas for all standards. This general experimental arrangement should be effective when applied to feed streams for other polymers as well.     

Evaluation of a pulse-discharge helium ionisation detector for the determination of neon concentrations by gas chromatography

A pulse-discharge helium ionisation detector, PDHID (Valco, PD-D2-I) with sample introduced to the discharge zone is shown to be applicable for reliable determinations of neon by gas chromatography. The detection level of 80 pg was obtained, but the dependence between detector response and neon mass was non-linear. However, for the discharge gas doped with 33 ppm of neon, a linear response to the neon mass up to 10(-5) g and the detection level of 0.5 ng were obtained. The method can be used for measuring neon concentrations in groundwater systems for hydrogeological purposes.     

A high speed micro vacuum-fusion apparatus

A micro vacuum-fusion apparatus capable of extracting, collecting and examining volumes of gas of no more than 2 x 10(-3) cm(3) at N.T.P. from metal samples is described. The resulting gas mixture is analysed by gas chromatography with helium as the carrier gas and with a highly sensitive ionization detector.     

Development of ambient sampling chemi/chemical ion source with dielectric barrier discharge

The development of a new configuration of chemical ionization (CI)‐based ion source is presented. The ambient air containing the gaseous sample is sniffed into an enclosed ionization chamber which is of sub‐ambient pressure, and is subsequently mixed with metastable species in front of the ion inlet of the mass spectrometer. Metastable helium atoms (He*) are used in this study as the primary ionizing agents and are generated from a dielectric barrier discharge (DBD) source. The DBD is powered by an AC high‐voltage supply and the configuration of the electrodes is in such a way that the generated plasma is confined within the discharge tube and is not extended into the ionization chamber. The construction of the ion source is simple, and volatile compounds released from the bulky sample can also be analyzed directly by approaching the sample to the sampling nozzle. When combined with heated nitrogen or other desorption methods, its application can also be extended to non‐volatile compounds, and the consumption for helium can be kept minimum solely for maintaining the stable discharge and gas phase ionization. Applications to non‐proximate sample analysis, direct determination of active ingredients in drug tablets and the detection of trace explosive such as hexamethylene triperoxide diamine are demonstrated. Copyright © 2010 John Wiley & Sons, Ltd.     

Indirect hydrogen analysis by gas chromatography coupled to mass spectrometry (GC–MS)

Gas chromatography (GC) is an analytical tool very useful to investigate the composition of gaseous mixtures. The different gases are separated by specific columns but, if hydrogen (H₂) is present in the sample, its detection can be performed by a thermal conductivity detector or a helium ionization detector. Indeed, coupled to GC, no other detector can perform this detection except the expensive atomic emission detector. Based on the detection and analysis of H₂ isotopes by low‐pressure chemical ionization mass spectrometry (MS), a new method for H₂ detection by GC coupled to MS with an electron ionization ion source and a quadrupole analyser is presented. The presence of H₂ in a gaseous mixture could easily be put in evidence by the monitoring of the molecular ion of the protonated carrier gas. Copyright © 2013 John Wiley & Sons, Ltd.