Pulsed discharge detector: theory and applications

The pulsed discharge detector (PDD) is a significant advancement in gas chromatography (GC) detector design which can be operated in three different modes: pulsed discharge helium ionization (He-PDPID), pulsed discharge electron capture (PDECD) and helium ionization emission (PDED). The He-PDPID can detect permanent gases, volatile inorganics and other compounds which give little or no response with the flame ionization detector (FID) and has significantly better limits of detection (minimum detectable quantities (MDQs) in low picogram range) than can be achieved with a thermal conductivity detector (typically not lower than 1 ng). The PDECD has similar or better sensitivity (MDQs of 10(-15) to 10(-12) g) than radioactive source ECD but does not require licensing, wipe tests and other administrative or safety requirements which have increased over security concerns. The PDED shows promise as an extremely selective and sensitive elemental detector but a commercial unit is not presently available. In this report, the theory of operation, applications of the PDD and the practical aspects of using this novel detector are presented.     

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.     

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.     

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.     

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%.     

Applications using the chlorine-selective pulsed discharge emission detector

The use of the chlorine-selective pulsed discharge emission detector (Cl-PDED) for the GC analyses of EPA mixtures 502, 612, 624, organochlorine pesticides, and polychlorinated biphenyls has been demonstrated. The Cl-PDED is the most sensitive chlorine-selective detector with a minimum detectability of 50 fg Cl/s. A constant response/pg Cl was observed for these mixtures regardless of the number of Cl atoms/molecule and structure of the compound to which the Cl atoms are attached. The analysis of standard samples of polychlorinated biphenyls using the Cl-PDED have sensitivities comparable to those of the electron-capture detector; however, the predictable response/pg Cl from the Cl-PDED is preferred over the extremely variable response from the electron capture detector.     

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.     

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.     

A new photoionization detector for gas chromatography

Summary A new photoionization detector for gas chromatography is discribed. The source of vacuum ultra-violet (VUV) radiation is separated from the ionization chamber by a window and thus the ionization chamber may be run at atmospheric pressure using an intense source of ionizing radiation. The operation consequently is improved and considerably simplified. Except for a ten times reduction in linearity, the performance characteristics of the detector are comparable to those of the flame ionization detector. Filtration of the VUV radiation allows the selectivity to be varied without affecting the dynamic properties of the detector.Z. ternberg, N. Ostoji, Yug. Pat. Appl.     

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.     

Analysis of small droplets with a new detector for liquid chromatography based on laser-induced breakdown spectroscopy

The miniaturization of analytical techniques is a general trend in speciation analytics. We have developed a new analytical technique combining high pressure liquid chromatography (HPLC) with laser-induced breakdown spectroscopy (LIBS). This enables a molecule-specific separation followed by an element-specific analysis of smallest amounts of complex samples. The liquid flow coming from a HPLC pump is transformed into a continuous stream of small droplets (diameter 50–100 μm, volume 65–500 pl) using a piezoelectric pulsed nozzle. After the detection of single droplets with a droplet detector, a Q-switched Nd:YAG Laser is triggered to emit a synchronized laser pulse that irradiates a single droplet. The droplets are evaporated and transformed to the plasma state. The spectrum emitted from the plasma is collected by a spherical mirror and directed through the entrance slit of a Paschen–Runge spectrometer equipped with channel photomultipliers. The spectrometer detects 31 elements simultaneously covering a spectral range from 120 to 589 nm. Purging the measurement chamber with argon enables the detection of vacuum–UV lines. Since the sample is transferred to the plasma state without dilution, very low flow rates in the sub-μl/min range can be realised.     

Application of radiochromic gel detector (FXG) for UVA dose measurements

Tissue equivalent radiochromic gel material containing ferrous ions, xylenol-orange ion indicator and gelatin as gelling agent (FXG) is known to be sensitive to γ- and X-rays; hence it has been used for ionizing radiation dosimetry. Changes in optical absorbance properties of FXG material over a wide region in the visible spectrum were found to be proportional to the radiation absorbed dose. An earlier study demonstrated the sensitivity of FXG gel detector to ultraviolet radiation and therefore that could give quantitative measure for UV exposure. This study focuses on the detection of UVA radiation (315–400 nm), which forms an important part (～97%) of the natural solar UV radiation reaching the earth surface. A solar UV simulator device was used to deliver UVA radiation to FXG samples. The beam was optically modified to irradiate gel samples at an exposure level about 58 W/m², which is comparable to the summer natural UVA radiation measured outside the laboratory building at midday (～60 W/m²). Experimental results were used to generate mathematical second order formulas that give the relationship between UVA dose and optical absorbance changes observed at two wavelengths in the visible region of the spectrum—430 and 560 nm.     

A NEW DOSIMETER FOR ULTRAVIOLET-B RADIATION

Abstract— A type of polycarbonate plastic was found to be sensitive to ultraviolet (UV) radiation. The damage to the material due to UV exposure was revealed by etching in a strong alkaline solution. The latent effect can be retained in the material for a period of at least 30 days. The material was tested for use as a detector of ultraviolet-B (UV-B 280–320 nm) radiation.
The response of the detector in the wavelength region between 254 and 365 nm was determined using a set of narrow-band filters and a 200 W UV xenon-mercury lamp. The maximum UV effect in the detector was observed at a wavelength of 290 nm. The spectral response curve was found to be similar to the human erythema action spectrum.
The detector may be miniaturized for dosimetric applications. The dose response curve is linear in the region up to an erythemal dose of 300 mJcm⁻². Laboratory and field tests showed that the dosimeter response to UV exposure was additive and was independent of dose rate. Further experiments suggested that the dosimeter was stable against changes in temperature and humidity.     

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.     

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.     

Si drift detector in comparison to Si(Li) detector for total reflection X-ray fluorescence analysis applications

TXRF is routinely used and suited to inspect Si wafer surfaces for possible impurities of metallic elements at the level of pg and below. Lightweight, compact sized, high-resolution Silicon drift detectors (FWHM=148 eV at 5.9 keV) electically cooled and with high throughput are ideally as the new spectrometer and for clean room application. A KETEK 5 mm² Si drift detector was compared with a NORAN 80 mm² SiLi in a previously commercially available ATOMIKA 8010 wafer analyzer. Results are presented and show that almost the same detection limits for both detector types were achieved analyzing a droplet sample containing 1 ng Ni on a Si wafer. Also, the performance to detect low Z elements like Na, excited with monochromatic Cr K radiation in a vacuum chamber was tested and detection limits of 600 pg obtained.     

Dual wavelength excitation fluorescence detector for capillary electrophoresis using a pulsed bi-colour light emitting diode

A simple and novel two-colour fluorescence detector for capillary electrophoresis was created using a single bi-colour light emitting diode (LED), multi-band pass excitation and emission filters and a single detector. Excitation light from a blue/red (470/635 nm) bi-colour LED was filtered through a 390/482/563/640 nm multi-band bandpass filter, with emitted light filtered through a 446/523/600/677 nm multi-band bandpass filter before being detected using a photon counting detector. Sequential pulsing of the blue/red LED and deconvolution of the collected fluorescence data allowed extracted electropherograms to be obtained corresponding to excitation with the blue and red LEDs. Optimisation of the pulsed LED conditions revealed an optimum LED on-time of 50 ms, off-time of 30 ms with a pulsed current of 40 mA, giving an effective data acquisition rate of 6.25 Hz. The characteristics of this system were validated by the simultaneous separation and determination of six fluorescent dyes: fluorescein, FITC, coumarin 334, dibromo(R)fluorescein (Ex/Em 470/525 nm), and Cy 5 and the Agilent Bioanalyser DNA dye (Ex/Em 635/670 nm). Under optimum conditions, the detection limits for FITC, fluorescein and Cy 5 were 69 nM, 42 nM and 289 nM (S/N = 3), respectively. These were lower than those obtained with continuous operation of the individual wavelengths at a constant current of 20 mA, but were slightly higher than those obtained using dedicated single wavelength filter combinations designed specifically for use with these fluorophores. The intraday repeatability (n = 6) of migration times was less than 1.0% and less than 3.4% for peak areas, while interday (n = 3) migration time and peak area reproducibility were less than 0.9% and 3.6%, respectively. This simple detector is capable of performing quantitative two-wavelength excitation without the need for complex optics and light source configurations.     

Capillary electrophoretic system incorporating an UV/CL dual detector

We developed a capillary electrophoretic system incorporating an ultra-violet absorption (UV)/chemiluminescence (CL) dual detector, taking advantage of the CL reaction of luminol-hydrogen peroxide and the batch-type CL detection cell. UV detection was carried out using the on-capillary method while CL detection was performed using the end-capillary method. Examination of isoluminol isothiocyanate (ILITC) as a model sample revealed two main peaks with UV detection and one main peak with CL detection. The first peak in the UV detection data corresponded to the main peak in the CL detection data. We then determined that the ILITC sample included natural ILITC as well as an impurity that had absorption behavior but did not have CL properties and labeling ability. Furthermore, the components of a mixture containing glycine, glycylglycine and glycylglycylglycine, all labeled with ILITC, were well separated and detected using the present system. The present system easily, rapidly, and simultaneously produces useful information due to the presence of both UV and CL detectors.     

Determination of ethanol in alcoholic beverages by liquid chromatography using the UV detector

Ethanol in certain beverages and in similar solutions may be determined by reversed-phase liquid chromatography (LC) using the UV detector. The mobile phase in this indirect photometric detection technique contains a low concentration of a UV-absorbing compound, such as acetone, that coelutes with the ethanol peak. Several variables such as the choice and concentration of the UV-detection agent are examined regarding their effects on the retention time, magnitude and linearity of peak area, and other aspects of quantitation. Except for filtering to remove particulate matter, samples can be injected without pretreatment. The concentration of ethanol in several types of beverages can be determined with 2% relative standard deviation, calibration is linear to 40% ethanol, and the minimum detectable concentration is 0.1%.     

Improved dual photometric-contactless conductometric detector for capillary electrophoresis

A new design of a dual, UV photometric - contactless conductometric detector is described. The separation capillary with an optical window created is pressed onto two semitubular electrodes, 3 mm wide and 2 mm apart. The electrodes form the detection cell of the contactless conductometric detector. An optical fiber, placed in the gap between the conductometric electrodes, brings radiation from the source. The radiation that passes through the separation capillary is recorded by a large-area photodiode. The optical fiber and the photodiode operate the photometric cell which is between the conductometric electrodes. The detector thus permits simultaneous photometric and conductometric detection in the same place of the capillary, while exchanging of the separation capillary is easy and without effect on the detector geometry and performance.