Optimal conditions are determined for laser-induced breakdown spectroscopy in liquid jets by investigating laser de-focusing and laser energy variation in aqueous liquid jets containing dilute levels of calcium chloride. It has been found that the atomic emission shows a strong correlation with both laser pulse energy and focal position. The data cannot be rationalized on the basis of electron density or ionization temperature changes alone, but rather it requires the additional consideration of the volume of the liquid sample interacting with the laser and that portion of the volume which is above the threshold energy for plasma formation. A moving breakdown model has been applied to the plasma formation in the jet to calculate the amount of sample ablated with sufficient energy for plasma formation, which models well the observed results and allows prediction of optimal focusing conditions for a given laser energy.

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