Fiber Laser Induced Breakdown Spectroscopy Combined with Surface Enhancement and Spark Discharge for Sensitive Detection of Heavy Metals in Hair Dye Creams

The unauthorized addition of silver nitrate and excessive heavy metals in hair dye creams poses serious health risks, creating an urgent need for rapid and sensitive detection methods. In this study, a spark discharge-enhanced fiber laser-induced breakdown spectroscopy (SD-LIBS) system was developed for the simultaneous detection of five heavy metal ions (Ag, Pb, Cd, As, Hg) in hair dye creams. The system combines three signal enhancement strategies: high-voltage spark discharge, Au nanoparticle-assisted enhancement, and analyte enrichment on a superhydrophobic–hydrophilic patterned graphite substrate. Hydrophilic micro-pits were fabricated by laser scanning on the superhydrophobic graphite surface to confine and concentrate analyte residues upon droplet drying. Under optimized discharge conditions of 22 nF and 2000 V, the spark discharge achieved a signal-to-noise ratio enhancement of approximately 12 times. Au nanoparticle enhancement further increased the signal intensity by 49.3%. The optimal pit diameter and sample loading volume were 0.1 mm and 30 μL, respectively. The calibration curves for all five elements showed good linearity with R2 values close to 0.99, and the lowest detection limits reached 1.9 μg/L for Ag. The average spiked recovery was 82.07%. The method was applied to four commercial hair dye cream samples, and the Ag detection results agreed well with ICP-OES reference values with an average error of 16.41%. This work demonstrates that the proposed SD-LIBS system offers a low-cost, rapid, and sensitive approach for on-site screening of heavy metals in cosmetics and other consumer products.