Development and validation of a laser-induced breakdown spectroscopic method for ultra-trace determination of Cu, Mn, Cd and Pb metals in aqueous droplets after drying

• A laser induced breakdown method on direct analysis of dried droplets is described.
• 300 nm thick oxide coated silicon wafer (Si+SiO2) was used as a substrate.
• Energetic laser pulses are focused onto the droplets, at the out of focus condition.
• Measurements indicate 7 times enhancement in S/N for Cu(I) line at 324.75 nm.
• Technique can identify pg amounts of toxic elements in aqueous environments.

The present study reports a fast and accurate methodology for laser-induced breakdown spectroscopic, LIBS, analysis of aqueous samples for environmental monitoring purposes. This methodology has two important attributes: one is the use of a 300 nm oxide coated silicon wafer substrate (Si+SiO2) for the first time for manual injection of 0.5 microliter aqueous metal solutions, and two is the use of high energy laser pulses focused outside the minimum focus position of a plano convex lens at which relatively large laser beam spot covers the entire droplet area for plasma formation. Optimization of instrumental LIBS parameters like detector delay time, gate width and laser energy has been performed to maximize atomic emission signal of target analytes; Cu, Mn, Cd and Pb. Under the optimal conditions, calibration curves were constructed and enhancements in the LIBS emission signal were obtained compared to the results of similar studies given in the literature. The analytical capability of the LIBS technique in liquid analysis has been improved. Absolute detection limits of 1.3 pg Cu, 3.3 pg Mn, 79 pg Cd and 48 pg Pb in 0.5 microliter volume of droplets were obtained from single shot analysis of five sequential droplets. The applicability of the proposed methodology to real water samples was tested on the Certified Reference Material, Trace Metals in Drinking Water, CRM-TMDW and on ICP multi-element standard samples. The accuracy of the method was found at a level of minimum 92% with relative standard deviations of at most 20%. Results suggest that 300 nm oxide coated silicon wafer has an excellent potential to be used as a substrate for direct analysis of contaminants in water supplies by LIBS and further research, development and engineering will increase the performance and applicability of the methodology.

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