ABSTRACT:We describe and illustrate a three-step dataprocessing approach that enables individual congener groups of chlorinated paraffins (CPs) to be resolved in mass spectra obtained from either of two soft ionization methods: electron capture negative ionization mass spectrometry (ECNI-MS) or atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In the first step, general fragmentation pathways of CPs are deduced from analysis of mass spectra of individual CP congeners. In the second step, all possible fragment ions in the general fragmentation pathways of CPs with 10 to 20 carbon atoms are enumerated and compared to mass spectra of CP mixture standards, and a deconvolution algorithm is applied to identify fragment ions that are actually observed. In the third step, isotope permutations of the observed fragment ions are calculated and used to identify isobaric overlaps, so that mass intensities of individual CP congener groups can be deconvolved from the unresolved isobaric ion signal intensities in mass spectra. For a specific instrument, the three steps only need to be done once to enable deconvolution of CPs in unknown samples. This approach enables congener group-level resolution of CP mixtures in environmental samples, and it opens up the possibility for quantification of congener groups.

A flat-field extreme ultraviolet (EUV) spectrometer working in the 20-500 Å wavelength range with fast time response has been newly developed to measure line emissions from highly ionized tungsten in the Experimental Advanced Superconducting Tokamak (EAST) with a tungsten divertor, while the monitoring of light and medium impurities is also an aim in the present development. A flat-field focal plane for spectral image detection is made by a laminar-type varied-line-spacing concave holographic grating with an angle of incidence of 87°. A back-illuminated charge-coupled device (CCD) with a total size of 26.6 × 6.6 mm(2) and pixel numbers of 1024 × 255 (26 × 26 μm(2)/pixel) is used for recording the focal image of spectral lines. An excellent spectral resolution of Δλ0 = 3-4 pixels, where Δλ0 is defined as full width at the foot position of a spectral line, is obtained at the 80-400 Å wavelength range after careful adjustment of the grating and CCD positions. The high signal readout rate of the CCD can improve the temporal resolution of time-resolved spectra when the CCD is operated in the full vertical binning mode. It is usually operated at 5 ms per frame. If the vertical size of the CCD is reduced with a narrow slit, the time response becomes faster. The high-time response in the spectral measurement therefore makes possible a variety of spectroscopic studies, e.g., impurity behavior in long pulse discharges with edge-localized mode bursts. An absolute intensity calibration of the EUV spectrometer is also carried out with a technique using the EUV bremsstrahlung continuum at 20-150 Å for quantitative data analysis. Thus, the high-time resolution tungsten spectra have been successfully observed with good spectral resolution using the present EUV spectrometer system. Typical tungsten spectra in the EUV wavelength range observed from EAST discharges are presented with absolute intensity and spectral identification.

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We study the core effect of nonhydrogenic alkaline-earth-metal barium in its diamagnetic spectrum by one photon transition from the ground state 6s 2 1 S 0 experimentally and theoretically. The non-Coulombic potential of the ion core introduces an extra energy shift compared with hydrogen and a level anticrossing between different n manifolds, characterized by the quantum defect of the concerned angular momentum states. With a complex rotation coordinate technique and a B-spline expansion method, we develop a matrix-form Hamiltonian based on an effective potential incorporating the angular-dependent quantum defect into the angular rotation term. The nonhydrogen core effects are investigated by sweeping the quantum defects of different channels in the calculation. Results show that quantum defects of p and f states have a undeniable effect on the intensities and positions of the spectral lines, although barium is closely hydrogenlike in the energy range examined. The anticrossing spectral lines are also identified with the aid of theoretical calculations. The calculations are in good agreement with the experimental observations.

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