Direct determination of Ti content in sunscreens with laser-induced breakdown spectroscopy: Line selection method for high TiO2 nanoparticle concentration

• Direct determination of titanium content in sunscreen with LIBS
• Behavior of titanium lines for concentration prediction as a function of their intensity
• Efficient and practical procedure for optimizing line selection in LIBS analysis

Sunscreen represents a large variety of creams which, in the analytical point of view, exhibit a similar matrix. Such matrix corresponds to a semi-solid emulsion of mixture of oil and water. The formulation of a cream can include metal and nonmetal elements in different contents in order to realize specific pharmaceutical or cosmetic functions designed for the product. The complex matrix of these materials makes their analysis challenging for classical elemental analytical techniques with specific and complicated sample pretreatment procedures needed for reliable quantification. In this work we demonstrate and assess direct determination, without any pretreatment, of elemental content, especially for metallic element such as titanium, in a sunscreen using laser-induced breakdown spectroscopy (LIBS). The used configuration corresponds to that of indirect ablation of a thin film of cream applied on the surface of a pure aluminum target. We especially focused, in this work, on the case of high concentration of TiO2 nanoparticle in cream. Such choice was justified first by the fact that such concentration level is usually found in commercial sunscreens. On the other hand, titanium presents a large number of lines, neutral as well as singly ionized, in the spectral range from the near UV to the near IR. It provides therefore an ideal case to study line selection method to manage the effect of self-absorption, which becomes unavoidable at high concentration level, and to optimize measurement precision. Through such study, we try to deduce a quantifiable and generalizable line selection method for high performance LIBS measurements. More specifically, calibration curves were first established using 6 laboratory-prepared samples. The quadratic term of the curves was then studied as a function of the intensity of the used lines and their type (neutral or ion, resonant or non-resonant). The prediction performance of the lines was assessed with 2 validation samples with relatively low Ti content for one and higher Ti content for the second. The titanium content of 4 unknown samples was finally determined using a set of different selected lines.