Plasma produced by a 355 nm pulsed Nd:YAG laser with a pulse duration of 6 ns focussed onto a copper solid sample in air at atmospheric pressure is studied spectroscopically. The temperature and electron density characterizing the plasma are measured by time-resolved spectroscopy of neutral atom and ion line emissions in the time window of 300-2000 ns. An echelle spectrograph coupled with a gated intensified charge coupled detector is used to record the plasma emissions. The temperature is obtained using the Boltzmann plot method and the electron density is determined using the SahaBoltzmann equation method. Both parameters are studied as a function of delay time with respect to the onset of the laser pulse. The results are discussed. The time window where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the laser-induced breakdown spectroscopy (LIBS) analysis of samples, is deduced from the temporal evolution of the intensity ratio of two Cu I lines. It is found to be 700-1000 ns.

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Laser-Induced Breakdown Spectroscopy (LIBS) is well recognized as a promising tool for in situ/remote elemental analysis of environmental, archeological, clinical, and hazardous samples. With the aim of quantifying trace elements in such samples, using LIBS technique, an echelle spectrograph-ICCD system with high sensitivity and good resolution has been assembled. Various important parameters of this system were studied and optimized. Conditions for getting good quality LIBS spectra and signal for multielemental analysis have been achieved, and these are discussed and illustrated in this paper.

Direct spectro-chemical analysis of trace elements in complex matrices like minerals and soil is usually difficult because of possible interference from the intense background spectrum of the major components generated in the plasma. Optimization of the Laser Induced Breakdown Spectroscopy (LIBS) technique is essential for routine analysis of such samples. In the present work, we have shown that low detection limits can be achieved for trace elements like copper, zinc, and calcium in soil samples by using high resolution echelle spectrographs coupled to the LIBS system, and eliminating the background by subtraction of a suitable matrix "blank" spectrum. It is also shown that the LOD (limits of detection) can be further reduced by suitable data processing techniques like signal addition from multiple lines provided by the wide-range echelle system and use of correlation function calculation with a pure element spectrum. The validity of our LIBS technique was confirmed by conventional Atomic Absorption Spectroscopy (AAS) analysis for the same analyte after pre-concentration.

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