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On-line nickel and vanadium determination in oil samples was proposed using laser induced breakdown spectroscopy to reach low mg kg−1 concentrations. Both 266 nm and 532 nm emissions of a neodymium YAG laser were evaluated and the visible wavelength gave better results. An original optimization strategy employing a Doelhert design and full quadratic model was carried out. The number of laser shots, the delay time, the integration time gate and the laser energy were selected as factors. Measurements were compared under static and dynamic conditions (i.e. the sample being moved at a cc h−1 flow rate as it is under the process conditions), and no significant difference in terms of sensitivity and detection limits was observed due to the viscous nature of oil samples. Detection limits achieved for vanadium were 7 mg kg−1 and 31 mg kg−1 for nickel. In view of on-line measurements a Czerny Turner spectrometer equipped with a photomultiplier was evaluated. Then, the LIBS method developed enabled the plot of linear calibration curves for Ni and V with a sensitivity in agreement with the need of the petroleum industry for on-line determination. [ABSTRACT FROM AUTHOR]

Laser ablation coupled to inductively coupled plasma optical emission spectrometry (LA-ICP-OES) and laser-induced breakdown spectroscopy (LIBS) were investigated for the determination of Ca, Mg, Zn and Na in milk samples. The accuracy of both methods was evaluated by comparison of the concentration found using LA-ICP-OES and LIBS with classical wet digestion associated with ICP-OES determination. The results were not fully acceptable, with biases from less than 1% to more than 60%. Matrix effects were also investigated. The sample matrix can influence the temperature, electron number density ( n) and other excitation characteristics in the ICP. These ICP characteristics were studied and evaluated during ablation of eight milk samples. Differences in n (from 8.9 to 13.8 × 10 cm) and rotational temperature (ranging from 3,400 to 4,400 K) occurred with no correlation with trueness. LIBS results obtained after classical external calibration procedure gave degraded accuracy, indicating a strong matrix effect. The LIBS measurements clearly showed that the major problem in LA-ICP was related to the ablation process and that LIBS spectroscopy is an excellent diagnostic tool for LA-ICP techniques. [ABSTRACT FROM AUTHOR]

Abstract: Fundamental understanding of aerosol formation during laser ablation is important for the development of LA-ICP analysis of complex samples. Using a Lina Spark Atomizer™, the application of this technique to the field of heterogeneous catalysis gave an accuracy of 5–15% while extreme values of +100% could be obtained in some cases. To improve understanding of laser ablation processes, particles generated during ablation of alumina based catalysts were collected and analysed using different microscopy and surface analysis techniques. Morphological study by scanning electron microscopy showed that most of the particles leaving the ablation cell were nanoparticle aggregates generated from vapor condensation. An XRD study of these aerosols revealed that the condensation converge on the formation of a spinel structure with large coherence domains. Elemental composition of the aerosol was also followed and exhibited differences between a catalyst containing large Mo concentration or low Pt concentration. [Copyright &y& Elsevier]

The retention of organic selenium compounds on a porous graphitic carbon stationary phase was investigated. Different acids were studied as mobile phases to elute selenocystamine, selenoethionine, selenomethionine and selenocystine. Detection was achieved using inductively coupled plasma-atomic emission spectrometry to provide selenium-specific and sensitive detection. The separation of the four species was carried out using methanoic acid. An important on-column preconcentration was obtained when solutes were injected in nitric acid or trifluoroacetic acid (TFA) media. The large injection volume employed (2,500 µL) allowed us to reach low relative detection limits (2–6 µg/L). The method, employing TFA as injection solvent and methanoic acid as the eluent was found to be robust with respect to different matrices spiked with selenocompounds. [ABSTRACT FROM AUTHOR]

Determination of sulfur in petroleum products is described using Laser Induced breakdown spectroscopy (LIBS). A study of buffer gases employed to improve sulfur IR line detection is presented. Optimisation of the flow rate led to a 1.4 L/min optimal helium flow rate. An adaptation between a typical laboratory setup to a compact system allowed to obtain detection limits in the 0.2% w /w range. Calibration is made under the process conditions (70 °C) and at room temperature. Normalization with a helium emission line compensates for liquid level variations and for the temperature variations. The analysis of a sample over the course of 2 days under the conditions of the industrial process was tested and gave a good repeatability. [ABSTRACT FROM AUTHOR]

Abstract: Pollution of water is a matter of concern all over the earth. Particles are known to play an important role in the transportation of pollutants in this medium. In addition, the emergence of new materials such as NOAA (Nano-Objects, their Aggregates and their Agglomerates) emphasizes the need to develop adapted instruments for their detection. Surveillance of pollutants in particulate form in waste waters in industries involved in nanoparticle manufacturing and processing is a telling example of possible applications of such instrumental development. The LIBS (laser-induced breakdown spectroscopy) technique coupled with the liquid jet as sampling mode for suspensions was deemed as a potential candidate for on-line and real time monitoring. With the final aim in view to obtain the best detection limits, the interaction of nanosecond laser pulses with the liquid jet was examined. The evolution of the volume sampled by laser pulses was estimated as a function of the laser energy applying conditional analysis when analyzing a suspension of micrometric-sized particles of borosilicate glass. An estimation of the sampled depth was made. Along with the estimation of the sampled volume, the evolution of the SNR (signal to noise ratio) as a function of the laser energy was investigated as well. Eventually, the laser energy and the corresponding fluence optimizing both the sampling volume and the SNR were determined. The obtained results highlight intrinsic limitations of the liquid jet sampling mode when using 532nm nanosecond laser pulses with suspensions. [Copyright &y& Elsevier]