It is found in this work that variation of laser power density in low-pressure plasma spectrochemical analysis of hydrogen affects sensitively the hydrogen emission intensity from the unwanted and yet ubiquitous presence of ambient water. A special experimental setup has been devised to allow the simple condition of focusing/defocusing the laser beam on the sample surface. When applied to zircaloy-4 samples prepared with various hydrogen impurity concentrations using low-pressure helium surrounding gas, good-quality hydrogen emission lines of very high signal to background ratios were obtained with high reproducibility under weakly focused or largely defocused laser irradiation. These measurements resulted in a linear calibration line with nonzero intercept representing the residual contribution from the recalcitrant water molecules. It was further shown that this can be evaluated and taken into account by means of the measured intensity ratio between the oxygen and zirconium emission lines. We have demonstrated the applicability of this experimental approach for quantitative determination of hydrogen impurity concentrations in the samples considered.

A novel method for the direct and sensitive analysis of powder samples has been developed by utilizing the characteristics of a transversely excited atmospheric (TEA) CO(2) laser. In this study, a powder sample was placed in a container and covered by a metal mesh; the metal mesh functions to control the blowing-off of the powder. The container was then perpendicularly attached on a metal surface. When a TEA CO(2) laser (1.5 J, 200 ns) was focused on the metal surface, a large hemispherical gas plasma (radius of around 8 mm) with long emission lifetime (several tens of microseconds) was produced without ablating the metal surface. The high-speed expansion force of the gas plasma samples the powder covered by the metal mesh and fine powder particles are sent into the gas plasma region to be dissociated and excited. Sensitive semi-quantitative analysis was made on organic powder samples such as powdered rice, starch, seaweed (agar), and supplements. The detection limit of heavy metals of Cr in powdered mineral supplement was approximately 0.55 mg/kg.

A crucial safety measure to be strictly observed in the operation of heavy-water nuclear power plants is the mandatory regular inspection of the concentration of deuterium penetrated into the zircaloy fuel vessels. The existing standard method requires a tedious, destructive, and costly sample preparation process involving the removal of the remaining fuel in the vessel and melting away part of the zircaloy pipe. An alternative method of orthogonal dual-pulse laser-induced breakdown spectrometry (LIBS) is proposed by employing flowing atmospheric helium gas without the use of a sample chamber. The special setup of ps and ns laser systems, operated for the separate ablation of the sample target and the generation of helium gas plasma, respectively, with properly controlled relative timing, has succeeded in producing the desired sharp D I 656.10 nm emission line with effective suppression of the interfering H I 656.28 nm emission by operating the ps ablation laser at very low output energy of 26 mJ and 1 μs ahead of the helium plasma generation. Under this optimal experimental condition, a linear calibration line is attained with practically zero intercept and a 20 μg/g detection limit for D analysis of zircaloy sample while creating a crater only 10 μm in diameter. Therefore, this method promises its potential application for the practical, in situ, and virtually nondestructive quantitative microarea analysis of D, thereby supporting the more-efficient operation and maintenance of heavy-water nuclear power plants. Furthermore, it will also meet the anticipated needs of future nuclear fusion power plants, as well as other important fields of application in the foreseeable future.

The crystal structure of the room temperature phase (RTP) of the title compound was determined at 297 K (monoclinic, space group C2/c, a = 1384.2(2), b = 1377.8(3), c = 755.5(2) pm, ß = 121.58(1)°). A complicated disorder was found for the cation. A phase transition from the lowtemperature phase (LTP) to the RTP was found at (224 ±1) K (T c ). The 'H NMR spectra showed a sharp motional narrowing at ca. T=T C , indicating the occurrence of a reorientational motion of the cation in the RTP in accord with the disorder. It was found that another reorientational motion is excited in the LTP.

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A series of measurements have been performed on the time dependences of the intensities of helium, hydrogen, and deuterium emission lines from the corresponding laser-induced helium plasma at atmospheric pressure for two different He flow rates. The prolonged H ␣ and H ␤ emissions along with their constant intensity ratio over a relatively extended period indicate the need to provide an alternative excitation mechanism other than the well-known thermal excitation process in a hot plasma. This additional excitation mechanism is also related to the metastable excited state of a He atom as indicated by the similar characteristics of the observed time dependence of the emission intensities. The enhanced intensity and lifetime of He emission at a high He flow rate was explained in terms of the collision-induced increase in the number of He atoms excited to above the 2 1 S 0 metastable state, which was also responsible for the delayed excitation of H and D atoms via an energy transfer mechanism involving a Penning-like chemi-ionization process. Finally, the benefits of He-assisted delayed excitation of H and D atoms and the aforementioned enhanced intensity and lifetime at a high He flow rate were demonstrated by the achievement of clearly resolved H ␣ and D ␣ emission lines.

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