Adaptation of an echelle spectrograph to a large CCD detector

A broad range echelle spectrograph with a CCD matrix detector is developed for different applications in atomic spectroscopy. The compact optical design in combination with a dispersive entrance slit illumination offers a low stray light level and high throughput in the UV spectral region comparable only with spectrographs of higher focal length. Ray tracing calculations for typical wavelengths and the multi-line spectrum of an iron arc show the excellent overall spectrum quality. The subtraction of two partial spectra of different steel alloys demonstrates the spectra evaluation possibilities of the CCD spectrograph.     

Arc atomic emission determination of noble metals in mineral raw materials and products of their processing

A procedure has been developed for the direct atomic emission determination of medium concentrations of noble metals in mineral raw materials and products of their processing. The procedure is based on the application of a spectral complex, consisting of an arc source of spectrum excitation, a DFS-8 spectrograph, a receiver of spectrum emission with CCD structures, and a registration system including software. The detection limits are n × 10^?5% for a number of noble metals and n × 10^?7% for Ag with RSD of 7?C14%.     

Dispersed fluorescence spectroscopy of jet-cooled HCF and DCF: Vibrational structure of the X 1A' state

We recorded dispersed fluorescence (DF) spectra following excitation of the pure bending levels 2(0) (n) and the combination states 1(0) (1)2(0) (n) and 2(0) (n)3(0) (1) in the A 1A"<--X 1A' system of HCF and DCF. Spectra were measured with a 0.3 m spectrograph equipped with a gated intensified charge coupled device (CCD) detector and obtained under jet-cooled conditions using a pulsed discharge source. The DF spectra reveal rich detail concerning the vibrational structure of the X state up to 10 000 cm(-1). For HCF, resonances among the nearly degenerate levels 1(1)2n, 2n+13(1), and 2n+2 produce a polyadlike structure in the spectrum, and the usual effective spectroscopic Hamiltonian (Dunham expansion) poorly reproduces the experimental term energies. In contrast, this Hamiltonian works well for the term energies of DCF. Density functional calculations of the ground state vibrational frequencies were performed; the results are in excellent agreement with the experimentally derived vibrational parameters. The search for perturbations involving the low-lying a 3A" state is described.     

Spectroscopic diagnostics on CW-laser welding plasmas of aluminum alloys

In-process diagnostics intended to correlate spectrometric measurements to the occurrence of laser welding defects such as notches and blowholes have been carried out. The plasma light emitted during high-power CO₂ laser welding of a 6013 aluminum alloy was guided to an imaging spectrograph and the dispersed light was detected with a CCD system. A transient recorder was used to record the signal from a fast laser-power monitor and the sync signals from the CCD and a fast speed video camera. Accuracy of the measurements are discussed in relation to the low and fast acquisition rate approaches (58 spectra s⁻¹ and 4×10³ spectra s⁻¹, respectively) used in the experiments. Spectroscopic measurements at fast acquisition rates showed both an increase in the intensity of the overall spectral emission and the growth of lines corresponding to ionic aluminum species taking place right before the occurrence of weld defects.     

Investigation of the electronic structure of paradichlorobenzene using x-ray emission spectroscopy

The Cl Kβ emission spectra from disordered and ordered molecules of paradichlorobenzene were recorded using a high-resolution curved crystal spectrograph. It was possible to separate the component polarized perpendicularly to the molecular plane from the in-plane polarized radiation. Thus information is obtained about the molecular π orbitals. By comparison with the photoelectron spectrum a partial assignment of the structural features of the spectra to the molecular orbitals is achieved.     

Echelle-spectrograph as a tool for studies of structured background in flame atomic absorption spectrometry

An echelle-spectrograph with solid-state image detector and active wavelength stabilization was developed. It is used as a tool for investigations of structured background in flame atomic absorption spectrometry (flame-AAS). The simultaneously recordable spectral range of the spectrograph extends from 200 to 465 nm. Its pixel-based bandwidth is λ/80 000. The wavelength stabilization was developed for suppressing spurious structures in the calculated ratios of sample and blank spectra. Such structures arise in case of wavelength shifting during recording of the spectra. The stabilization compensates for spectrum displacements with respect to the pixel matrix of the detector by correction of both position and dispersion of the spectrum. The achievable precision is 1% of the pixel width. By averaging a multitude of measurements, transmittance spectra with high signal-to-noise ratios are obtained. Using an air-acetylene flame, alternate measurement of 50 spectra of both sample and blank results in a transmittance spectrum with a noise level of less than 5×10⁻⁴ (rms). The spectra of highly concentrated samples of H₃PO₄, Fe, and Cu exemplary show the appearance of broad range, narrow structure background phenomena.     

Determination of phosphorus, sulfur and the halogens using high-temperature molecular absorption spectrometry in flames and furnaces—A review

The literature about the investigation of molecular spectra of phosphorus, sulfur and the halogens in flames and furnaces, and the use of these spectra for the determination of these non-metals has been reviewed. Most of the investigations were carried out using conventional atomic absorption spectrometers, and there were in essence two different approaches. In the first one, dual-channel spectrometers with a hydrogen or deuterium lamp were used, applying the two-line method for background correction; in the second one, a line source was used that emitted an atomic line, which overlapped with the molecular spectrum. The first approach had the advantage that any spectral interval could be accessed, but it was susceptible to spectral interference; the second one had the advantage that the conventional background correction systems could be used to minimize spectral interferences, but had the problem that an atomic line had to be found, which was overlapping sufficiently well with the maximum of the molecular absorption spectrum. More recently a variety of molecular absorption spectra were investigated using a low-resolution polychromator with a CCD array detector, but no attempt was made to use this approach for quantitative determination of non-metals. The recent introduction and commercial availability of high-resolution continuum source atomic absorption spectrometers is offering completely new possibilities for molecular absorption spectrometry and its use for the determination of non-metals. The use of a high-intensity continuum source together with a high-resolution spectrometer and a CCD array detector makes possible selecting the optimum wavelength for the determination and to exclude most spectral interferences.     

Intracavity laser spectroscopy of the HfCl molecule. Analysis of rotational structure of new bands of the 2Δ-X2Δ electronic transition

Electron absorption spectrum of the HfCl molecule was studied in the 550–800 nm region using intracavity laser spectroscopy. HfCl molecules were obtained using the passage of an impulse electric discharge through a mixture of HfCl₄ and He vapors. A cuvette with the mixture of gases was placed in a dyelaser resonator cavity. The spectra were registered using diffraction spectrograph (resolution capability 240000). The high sensitivity of the intracavity method made it possible to detect in the HfCl spectrum new bands with a resolved rotational structure. Rotational analyses of the given bands were performed and the molecular constants were determined.     

High resolution spectrum of the xenon molecule in the vacuum ultraviolet region (1150–1300 Å)

The absorption spectrum of the Van der Waals dimer Xe₂ has been photographed in the region 1150–1130 Å with a ten-metre spectrograph. The vibronic analysis of twelve molecular systems provides information on the ground state and on several excited molecular states. Some of the numerous bands appearing in the Xe-rare-gas mixture spectra are examined and compared to those of Xe₂.     

Spectrum shift fitting technique for atomic emission spectrometry

The use of the principle of additivity for the atomic emission spectra registered by a multi-element solid-state detector (SSD) requires to take into account the possible non-controlled spectrum shift. The method of solution for the problem, based on the construction of parabolic model of signal change on pixels under the spectrum shift with respect to detector, is suggested. The algorithm of the model construction depends neither on the spectral line shape nor on the spectrometer apparatus function. The method can be applied with equal success both for the short spectral regions (10–20 pixels) and for the long regions (10 000 and more pixels). The values of relative spectrum shifts can lie in a continuous range from 0.05 to 100 and more pixels. The advantages of this method are shown on the examples of subtraction of spectra in the process of registration on diffraction spectrograph PGS-2 (Carl Zeiss, Jena) with the help of a linear solid state detector (MAES-10, VMK-Optoelectronika, Russia, Novosibirsk).     

New compact Echelle spectrographs with multichannel time-resolved recording capabilities

The paper describes a new type of Echelle spectrograph system that utilises a gated interline CCD camera. The system, that contains no moving parts, records simultaneously 6000 time-resolved spectral channels in the range 200–1100 nm with a lowest gate time of 100 ns and with a constant spectral resolution. Results from time-resolved recordings made both from a Xe-flash source and from laser induced breakdown, are presented. It is concluded that the gated CCD sensors are of great interest for applications in spectroscopy. They are of special interest for the application with Echelle spectrographs. The high resolution of the gatable CCD with 6.7×6.7 μm² surpasses that of any ICCD today and in the foreseeable future. The gated CCD also opens the NIR wavelength region for time-resolved multichannel spectroscopy.     

Characterization of jewellery products by laser-induced breakdown spectroscopy

The suitability of laser-induced breakdown spectroscopy (LIBS) for the characterization of jewellery products is demonstrated by the development of a method based on the use of an Nd-YAG laser (operating at 532 nm) which induces ablation of the material and the production of a plasma whose emission reaches 1/8 m spectrograph (connected to a coupled charge detector (CCD)) through an optic fiber. The treatment of the instrumental signal provides enough analytical information, both for identifying and quantifying the major metals present in this type of material. The method proposed has been developed both by multivariate optimization and calibration procedures with application of the appropriate quality criteria. The chemometric analysis of the data and the use of PLS regression for calibration guarantee the ruggedness of the proposed method. The study of the emission spectra allows characterization of the most common noble metals (gold and silver) as well as other metals present in jewellery pieces.     

Analysis of laser-induced breakdown spectroscopy spectra: The case for extreme value statistics

In most instances, laser-induced breakdown spectroscopy (LIBS) spectra are obtained through analog accumulation of multiple shots in the spectrometer CCD. The average acquired in the CCD at a given wavelength is assumed to be a good representation of the population mean, which in turn is implicitly regarded to be the best estimator for the central value of the distribution of the spectrum at the same wavelength. Multiple analog accumulated spectra are taken and then in turn averaged wavelength-by-wavelength to represent the final spectrum. In this paper, the statistics of single-shot and analog accumulated LIBS spectra of both solids and liquids were examined to evaluate whether the spectrum averaging approach is statistically defensible. At a given wavelength, LIBS spectra are typically drawn from a Frechet extreme value distribution, and hence the mean of an ensemble of LIBS spectra is not necessarily an optimal summary statistic. Under circumstances that are broadly general, the sample mean for LIBS data is statistically inconsistent and the central limit theorem does not apply. This result appears to be due to very high shot-to-shot plasma variability in which a very small number of spectra are high in intensity while the majority are very weak, yielding the extreme value form of the distribution. The extreme value behavior persists when individual shots are analog accumulated. An optimal estimator in a well-defined sense for the spectral average at a given wavelength follows from the maximum likelihood method for the extreme value distribution. Example spectra taken with both an Echelle and a Czerny–Turner spectrometer are processed with this scheme to create smooth, high signal-to-noise summary spectra. Plasma imaging was used in an attempt to visually understand the observed variability and to validate the use of extreme value statistics. The data processing approach presented in this paper is statistically reliable and should be used for accurate comparisons of LIBS spectra instead of arithmetic averaging on either complete or censored data sets.     

Lamp‐based wavelength‐resolved fluorescence detection for protein capillary electrophoresis: Setup and detector performance

A lamp‐based fluorescence detection (Flu) system for CE was extended with a wavelength‐resolved (WR) detector to allow recording of full protein emission spectra. WRFlu was achieved using a fluorescence cell that employs optical fibres to lead excitation light from a Xe‐Hg lamp to the capillary window and protein fluorescence emission to a spectrograph equipped with a CCD. A 280 nm band pass filter etc. together with a 300 nm short pass cut‐off filter was used for excitation. A capillary cartridge was modified to hold the detection cell in a commercial CE instrument enabling WRFlu in routine CE. The performance of the WRFlu detection was evaluated and optimised using lysozyme as model protein. Based on reference spectral data, a signal‐intensity adjustment was introduced to correct for transmission losses in the detector optics that occurred for lower protein emission wavelengths. CE‐WRFlu of lysozyme was performed using BGEs of 50 mM sodium phosphate (pH 6.5 or 3.0) and a charged‐polymer coated capillary. Using the 3‐D data set, signal averaging over time and emission‐wavelength intervals was carried out to improve the S/N of emission spectra and electropherograms. The detection limit for lysozyme was 21 nM, providing sufficient sensitivity to obtain spectral information on protein impurities.     

单个蓝藻细胞的光谱

利用共焦显微和光栅光谱技术，得到了蓝藻Anabaena strain PCC 7120完整藻丝体中的单细胞吸收和荧光发射光谱.发现了前人未观察到的不同异形胞之间有显著光谱差异的现象，该现象可能与异形胞不同发育阶段的藻胆体和光系统的演化相关联.     

Ultraviolet absorption spectrum of chlorine peroxide, ClOOCl

The photolysis of chlorine peroxide (ClOOCl) is understood to be a key step in the destruction of polar stratospheric ozone. This study generated and purified ClOOCl in a novel fashion, which resulted in spectra with low impurity levels and high peak absorbances. The ClOOCl was generated by laser photolysis of Cl2 in the presence of ozone, or by photolysis of ozone in the presence of CF2Cl2. The product ClOOCl was collected, along with small amounts of impurities, in a trap at about -125 degrees C. Gas-phase ultraviolet spectra were recorded using a long path cell and spectrograph/diode array detector as the trap was slowly warmed. The spectrum of ClOOCl could be fit with two Gaussian-like expressions, corresponding to two different electronic transitions, having similar energies but different widths. The energies and band strengths of these two transitions compare favorably with previous ab initio calculations. The cross sections of ClOOCl at wavelengths longer than 300 nm are significantly lower than all previous measurements or estimates. These low cross sections in the photolytically active region of the solar spectrum result in a rate of photolysis of ClOOCl in the stratosphere that is much lower than currently recommended. For conditions representative of the polar vortex (solar zenith angle of 86 degrees, 20 km altitude, and O3 and temperature profiles measured in March 2000) calculated photolysis rates are a factor of 6 lower than the current JPL/NASA recommendation. This large discrepancy calls into question the completeness of present atmospheric models of polar ozone depletion.     

The third and fourth spectra of gallium: Ga III and Ga IV

The third and fourth spectra of gallium have been photographed in the region 6000–400 Å by using a 3-m normal-incidence, vacuum spectrograph and a 3.5-m Ebert spectrograph. A three-electrode vacuum spark and a spark in helium were used as sources. New measurements for the wavelengths have confirmed earlier work and provided material to extend the analysis of Ga III and Ga IV.     

Spatially-resolved observation of glow discharge plasma for atomic emission spectrometry.

An imaging spectrograph equipped with a CCD detector was employed to measure two-dimensional emission images from a glow discharge plasma in atomic emission spectrometry. The emission images at Zn I 334.50 nm for a zinc sample and at Cu I 324.75 nm for a copper sample could be obtained. Their emission intensities were not uniform in the radial direction of the plasma region but became weaker at larger distance from the central zone. The two-dimensional distribution would result from a spatial variation in the excitation efficiency of the plasma and thus provide useful information for understanding the excitation processes occurring in the plasma.     

Aperiodic x-ray multilayer mirrors and their application in plasma spectroscopy

We discuss the potentialities of aperiodic multilayer structures for the reflection of XUV radiation, including attooptical applications. Pilot samples of aperiodic normal-incidence broadband focusing multilayer mirrors are employed in a stigmatic transmission grating spectrograph with an operating range of 12.5–30 nm.This spectrograph was used to study (i) the XUV spectra arising from the charge exchange of laser-produced plasma ions with rare-gas (Xe, Kr, He) jet atoms, (ii) a debris-free Xe-jet plasma XUV source driven by Nd-laser pulses.     

Raman spectra of dipicolinic acid in crystalline and liquid environments

Raman spectra of dipicolinic acid (DPA) are important for detection of bacterial spores, since DPA and its salts present one of their major components. The implementation of a deeply cooled CCD camera in combination with pulsed excitation at 532 nm allowed measuring well-resolved Raman spectra of the DPA in different forms. Powder preparations, crystals grown from saturated solutions and aqueous solutions of the DPA were studied. The spectral features in different environments and comparison with the spectra obtained by other methods are discussed.