Toxic metals in medicinal herbs are potentially harmful for people taking herbal medicines. In this work, laser-induced breakdown spectroscopy–laser-induced fluorescence (LIBS-LIF) spectroscopy was first applied to carry out rapid and sensitive trace lead analysis in medicinal herb samples. To overcome the problem of diversity on the sample size, shape, and density for different samples, original samples were pulverized to powder and then pressed into pellets for spectral analysis. A series of standard samples were self-made for building a calibration curve. As an exemplary study, lead in Rheum officinale was analyzed with LIBS-LIF spectroscopy with significantly improved analytical sensitivity. The R2 of the build linear calibration curve was 0.996 and the detection limit of lead in R. officinale was determined to be 0.13 ppm. The enhancement factor on the signal-to-background ratio was >100 under low lead concentrations if compared with LIBS analysis. The lead concentrations in several original R. officinale samples were quantitatively determined. This work demonstrated that LIBS-LIF can be successfully applied to carry out rapid, sensitive, and quantitative trace lead analysis for medicinal herbs.
