An application of the zeeman effect to analytical atomic spectroscopy-II Background correction

A double-beam atomic-absorption spectrometer is described in which sample and reference beams are generated by Zeeman splitting of the source emission-line. The instrument was found to give satisfactory correction for lamp drift and for background scatter signals. The main advantage of the technique is the simplicity of the optical system used. Analytical sensitivity is found to be generally poorer than that given by single-beam measurements, largely because of the poor spectral characteristics of the lamps used here in comparison to their modern commercial hollow-cathode counterparts.     

分光光度计波长校准用低压汞灯的研制

基于辉光放电原理,采用小功率点光源及高频开关电源设计分光光度计波长校准用WSHg-B型低压汞灯,并提出汞灯辐射光谱波长不确定度的分析方法。实验结果表明,WSHg-B型低压汞灯在200～700nm波长范围内,具有分布均匀的线光谱,相对强度稳定,适用于各类通用紫外可见分光光度计的波长校准,还可用于分辨率及光谱带宽的测试。     

Photodegradation of polyimides. III. The effect of chemical composition,radiation source,atmosphere, and processing

Polymide films made from diarylanhydrides with oxygen, carbonyl, and hexafluoroisopropylidene 6F bridging groups are photolabile when irradiated with unfiltered light from a medium-pressure mercury lamp. The presence of oxygen is necessary to the photolytic degradation process, which results in the ultimate oxidative ablation of thin polyimide films. Films based on the 6F dianhydride containing a hexafluoroisopropylidene hinge group are the most unstable. However, photolysis of 6F dianhydride based polyimides in an inert atmosphere with either the unfiltered medium pressure mercury lamp or an electron beam results in no detectable changes even after long exposure times.     

Analytical characteristics of a continuum-source tungsten coil atomic absorption spectrometer.

A continuum-source tungsten coil electrothermal atomic absorption spectrometer has been assembled, evaluated, and employed in four different applications. The instrument consists of a xenon arc lamp light source, a tungsten coil atomizer, a Czerny-Turner high resolution monochromator, and a linear photodiode array detector. This instrument provides simultaneous multi-element analyses across a 4 nm spectral window with a resolution of 0.024 nm. Such a device might be useful in many different types of analyses. To demonstrate this broad appeal, four very different applications have been evaluated. First of all, the temperature of the gas phase was measured during the atomization cycle of the tungsten coil, using tin as a thermometric element. Secondly, a summation approach for two absorption lines for aluminum falling within the same spectral window (305.5-309.5 nm) was evaluated. This approach improves the sensitivity without requiring any additional preconcentration steps. The third application describes a background subtraction technique, as it is applied to the analysis of an oil emulsion sample. Finally, interference effects caused by Na on the atomization of Pb were studied. The simultaneous measurements of Pb and Na suggests that negative interference arises at least partially from competition between Pb and Na atoms for H2 in the gas phase.     

Application of a modulated Grimm-type glow discharge plasma as primary light source for simultaneous reading atomic absorption spectrometry

Summary The Grimm-type glow discharge lamp (GDL) working in a modulated way can be used as primary light source for atomic absorption measurements. The number of element radiations is given by the composition of the target (sample on GDL) which becomes sputtered. Its composition can be adopted to the analytical problem to be solved. It is easy to change the target.The glow discharge source generated at relatively low power (10–24 W) is burning stable for >20 min on the same spot. This is time enough to operate atomic absorption measurements of 10 samples simultaneously, for example, by using the normal flame technique or the graphite tube furnace or the atomsource sputter method to generate atoms of the sample material. The monochromator device of an AA spectrometer has to be replaced by a polychromator one.The spectral behaviour of the glow discharge source compared to that of the hollow cathode lamps of the elements studied is described here by using a double beam two channel AA spectrometer for simultaneous reading of both the signals. In most cases the glow discharge source is the better one. Home-made targets are used to measure first analytical results.

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Einsatz einer modulierten Glimmentladungslampe als Primärlichtquelle zur simultan messenden Atomabsorptionsspektrometrie

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We have to thank the Spectruma company and Bernhard Bogdain especially for supporting this work.     

Sub-picogram detection of lead by non-flame atomic fluorescence spectrometry with dye laser excitation

The frequency-doubled radiation of flashlamp-pumped dye laser has been compared with the radiation of an eleotrodeless discharge lamp (EDL) and a hollow cathode lamp (HCL) as excitation light sources in non-flame atomic fluorescence spectrometric (AFS) measurements. Detection limits and linear ranges of the analytical working curves have been studied. The aqueous Pb sample solutions used in this study were atomized in an electrically heated graphite rod. Direct line fluorescence at 405.8 nm has been observed. The limit of detection obtained with the laser as excitation source is about one order of magnitude lower than the detection limits obtained with the EDL and HCL. The absolute limit of detection of 0.2 pg is the lowest reported value to date attained in any atomic spectrometric method. The ultraviolet laser irradiance was found to be high enough to approach saturation conditions. As a result selfabsorption of the exciting laser beam is reduced and the linear range of the analytical working curve is extended to higher analyte concentrations.     

High-accuracy measurement of specular spectral reflectance and transmittance

The realization of spectrophotometric quantities at the Helsinki University of Technology is based on our reference spectrometer. The reference spectrometer is a high-accuracy instrument developed for measuring spectral specular transmittance and reflectance in a wavelength range extending from ultraviolet to near-infrared. The relative uncertainty estimates for transmittance measurements of neutral-density filters are ca. 0.05%. For spectral reflectance the estimated uncertainties are between 0.14% and 0.34% depending on the sample reflectance and the measurement geometry. We have derived and verified equations that enable both the reflectance and transmittance of various samples to be predicted. Utilizing these equations, the reflectance and transmittance can be accurately calculated for samples with known refractive index. For precise calculations, the characteristics of the measurement beam must be taken into account.     

Studies in atomic-fluorescence spectroscopy--VIII. Atomic fluorescence and atomic absorption of thallium and mercury with electrodeless discharge tubes as sources

Atomic-fluorescence measurements, with microwave-excited electrodeless discharge tubes as sources of excitation, are described for thallium and mercury. The limits of detection by atomic fluorescence are 0.12 ppm for thallium and 0.08 ppm for mercury; the corresponding limits by atomic absorption (using the same instrument and source) are 6 and 10 times as great. The preparation, operation and spectral characteristics of thallium and mercury discharge tubes are described and comparisons are made with a thallium hollow cathode lamp and thallium and mercury spectral discharge lamps.     

Oxygen-flask combustion with light beam ignition.

A robust oxygen-flask combustion system was developed using light beam ignition. An appropriate amount of environmental sample was wrapped with a small piece of filter paper and held in a basket made of platinum-zirconium spiral. After the sample was inserted into an oxygen-filled flask containing an acid mixture, the light beam from an overhead projector lamp was focused to ignite the sample. The combusted products were absorbed into the acid mixture by shaking the flask and then used for the ICP-AES measurement of metals. The proposed method was successfully applied to the determination of metals in Environmental Standard Reference Materials and Artemia salina. The present method is also applicable to ion chromatographic measurements of chlorine in polyvinyl chloride wall paper by using hydrogen peroxide as absorbent.     

MgZnO/ZnO p–n junction UV photodetector fabricated on sapphire substrate by plasma-assisted molecular beam epitaxy

We have investigated the spectral response of back- and front-surface-illumination MgZnO/ZnO p–n ultraviolet photodetector fabricated by plasma-assisted molecular beam epitaxy on sapphire substrate. The current–voltage measurements show that the device has a rectifying behavior with a turn-on voltage of 4.5 V. The detector exhibits a broad spectral response which covers the visible and UV spectra regions (from 275 to 375 nm) and has a maximum peak response at the wavelength of 330 nm. At a reverse bias of 5 V, the visible rejection (R330 nm/R500 nm) was more than two orders of magnitude. The peak responsivity at 330 nm for the device under back-illumination is about four times larger than that of the device under front-illumination under the same reverse bias. The response mechanisms of the device under back- and front-illumination are discussed.     

Significant improvement of signal-to-noise ratio in capillary electrophoresis through optimization of aperture width for UV absorption detection.

In capillary electrophoresis (CE), light flux passes through a capillary cell and is in most cases detected photometrically. Due to the thinness of the cell, a part of the light passes through the wall and misses hitting the sample. In most CE apparatuses, incident light is focused by converging lenses in order to condense light beams passing through the capillary. Considering the aberration of lenses and lens effects of capillary, we assumed that light beams inside were approximately parallel. Although the path lengths of light beams vary depending on their tracks, we could estimate the virtual light path length, L, by measuring absorbance when concentration and molar absorptivity of the sample solution were known. A light-restricting device consisting of narrow slits makes effectively L longer and signal intensity higher. On the other hand, noise increases as light width narrows. The signal-to-noise ratio showed a maximum at 68 microm of light width for a capillary with diameter of 75 microm. The optimized L was evaluated by the simulation. The experimental data verified it even in indirect UV detection. Our approach could help to design the optics of CE apparatuses.     

Spectral Interference in Antimony Analysis with High Temperature Furnace Atomic Absorption

Abstract

Background correction in atomic absorption spectrophotometry using a high temperature furnace has a close relation to the chemical treatment and the detection limit. Conventionally used for this correction is the D₂ lamp method, but spectral interference is inevitable in this method because the spectral bandwidth of the light from the D₂ lamp after passing through a monochromator is as wide as 0.1 to 5 nm. In the analysis of Sb in lead alloy or in steel, there is spectral interference due to high concentration of elements such as Pb, Cu or Fe, in the matrix, so accurate measurement is impossible unless these elements are removed at the pretreatment stage.

In polarized analyte Zeeman atomic absorption spectrophotometry developed by the authors, the wavelength of the measuring beam is the same as that of the reference and they are identical in spectral line profile as well as in geometrical shape. They differ only in the direction of polarization. For these reasons, we found that there is no spectral interference like that recognized in the D₂ lamp correction technique. As a result, a direct analysis was done simply by dissolving gunmetal or steel in acid without removing the matrix elements Pb, Cu or Fe.     

A LABORATORY INVESTIGATION OF TWO ULTRAVIOLET SPECTRORADIOMETERS

Abstract— Spectral measurements of the solar UV irradiance at the earth's surface depend critically on the characteristics of the spectroradiometers and the procedures used in their calibration. Two UV spectroradiometers were subjected to a series of laboratory tests to investigate which factors were most significant in limiting the reliability of the absolute irradiance measurements. Three independent standards of spectral irradiance were scanned by both instruments under a range of bench conditions. The results were consistent to within about 3%, most of the uncertainty being due to scattered light in the laboratory. An UV laser was used to determine the slit function of each spectrometer and the influence of internal stray light. Significant departures from the ideal cosine and azimuth responses were measured by a xenon lamp. Both spectroradiometers were kept indoors throughout the experiments. The relevance of these laboratory results is discussed with respect to the task of measuring solar UV radiation in the field.     

Dermatological Risk of Indoor Ultraviolet Exposure from Contemporary Lighting Sources¶†‡§

Discussions of risks and implications of cutaneous exposure to indoor lighting, including hypothetical contribution to causality of melanoma, have mainly concentrated on ultraviolet (UV) A and B (UVA, UVB) spectral emissions from fluorescent bulbs. Only studies of quartz halogen lamps have suggested that users might sustain UVC‐induced injury. Examination of light sources in the home and school of a child with xeroderma pigmentosum revealed that several different types emitted surprising levels of UV. Our purpose was to assess the extent of UV emissions from a variety of commonly used light sources to identify potential dermatological risks. UV and visible spectral emissions of commercially obtained lamps of several types were measured using a calibrated spectral radiometer traceable to the National Institute of Standards and Technology. Indoor light sources including fluorescent, quartz halogen and even tungsten filament incandescent lamps provided UVA, UVB and sometimes UVC emissions. Intensities of some emissions were of similar magnitude to those in sunlight. Chronic exposure to indoor lighting may deliver unexpected cumulative UV exposure to the skin and eyes. Patients with UV‐exacerbated dermatoses should be cautioned about potential adverse reactions from indoor lighting.     

A simple,low cost,multielement atomic absorption spectrometer with a tungsten coil atomizer

An inexpensive, multielement atomic absorption spectrometer utilizing a tungsten coil atomizer has been developed. The novel optical arrangement employs three 60° beam combiners to blend the spectral output from four light sources such as electrodeless discharge lamps, or hollow cathode lamps, and then direct that output over an atomizer. This instrument uses an inexpensive tungsten coil atomizer that is extracted from a standard 150 W projector bulb. The temperature of the coil is computer-controlled by changing the voltage across the coil. A low voltage is first used to dry the sample then a higher voltage is used to atomize the sample. Simultaneous detection of the analyte absorption signals is accomplished using a charge-coupled device. The elements of interest in this study were Cd, Pb, and Cu. Near-line background correction was used to correct for nonspecific analyte absorption.     

Double beam nanosecond laser flash photolysis for precise measurement of small absorbances in transient spectroscopy: Observation of decay profile of the excited triplet state of tetraphenylporphyrinatoantimony(V) with absorbance smaller than 0.01

Double beam laser flash photolysis has been newly developed for precise measurement of small absorbances in transient spectroscopy. The monitoring light beam was divided into two parts; one beam for monitoring the sample and a reference one. The two beams were simultaneously monitored by two similar independent photomultipliers and recorded on a two channel digital storage oscilloscope. The method enabled observation of signals within the full range of the pulse width of Xe lamp around 100 μs. Even a decay profile with extremely small absorbance around 0.01 of transient such as the excited triplet state of metalloporphyrins was precisely observed by the double beam method.     

The determination of carbon,phosphorus and sulphur in steel and cast iron with a glow-discharge emission source and an atomic fluorimeter as spectral line isolator

The atomic fluorimeter, an instrument using an atomic vapour generated by cathodic sputtering for isolating resonance spectral lines emitted by an emission source, was used for detecting the vacuum ultraviolet emission lines of carbon, phosphorous and sulphur. A glow-discharge lamp was used as emission source. Detection limits of 0.012, 0.004 and 0.002% were obtained for carbon, phosphorus and sulphur respectively in cast iron and steel. A narrow-band interference filter through which the matrix emission was measured directly by a photomultiplier tube, was used in an effort to correct for varying sputtering rates from different kinds of samples. This monitoring channel proved to be efficient for the determination of phosphorus and carbon in high alloy steels, but was not necessary for sulphur since in this case working curves of the different types of steels coincided.     

Application of Dielectric Barrier Discharge Reactor Immersed in Wastewater to the Oxidative Degradation of Organic Contaminant

Dielectric barrier discharge (DBD) is an effective method available for the production of ozone and ultraviolet light. The wastewater treatment system of this study was designed to utilize both ozone and ultraviolet light produced in the DBD reactor for the degradation of organic contaminant. The DBD reactor consisted of a quartz cylinder and a coaxial ceramic tube inside of which a steel rod was placed. The DBD reactor was immersed in the wastewater that was grounded. In this case, the wastewater acted not only as an electrode but also as the cooling medium for the DBD reactor. An azo dye, Acid Red 27, was used as the organic contaminant. In this system, the organic contaminant was degraded by two oxidation pathways induced by ozone and ultraviolet light. The concentration of ozone, the ultraviolet radiation intensity and the degradation efficiency of the organic contaminant were measured by varying the discharge. The results showed that the present system was very effective for the degradation of the organic contaminant. The energy requirement for the degradation was found to be 0.654 kJ/mg, which is much smaller value than those obtained with an ultraviolet/photocatalytic process.     

Perturbative theory and modeling of electronic-resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy of nitric oxide

A theory is developed for three-laser electronic-resonance-enhanced (ERE) coherent anti-Stokes Raman scattering (CARS) spectroscopy of nitric oxide (NO). A vibrational Q-branch Raman polarization is excited in the NO molecule by the frequency difference between visible Raman pump and Stokes beams. An ultraviolet probe beam is scattered from the induced Raman polarization to produce an ultraviolet ERE-CARS signal. The frequency of the ultraviolet probe beam is selected to be in electronic resonance with rotational transitions in the A (2)Sigma(+)<--X (2)Pi (1,0) band of NO. This choice results in a resonance between the frequency of the ERE-CARS signal and transitions in the (0,0) band. The theoretical model for ERE-CARS NO spectra has been developed in the perturbative limit. Comparisons to experimental spectra are presented where either the probe laser was scanned with fixed Stokes frequency or the Stokes laser was scanned with fixed probe frequency. At atmospheric pressure and an NO concentration of 100 ppm, good agreement is found between theoretical and experimental spectral peak locations and relative intensities for both types of spectra. Factors relating to saturation in the experiments are discussed, including implications for the theoretical predictions.