Validation of X-ray Fluorescence Measurements of Metals in Toenail Clippings Against Inductively Coupled Plasma Mass Spectrometry in a Nigerian Population<sup/>

Objective: Metal exposures have been linked with many adverse health outcomes affecting nearly every system in the body. Exposure to metals has been tracked primarily using blood. Blood metal concentrations have drawbacks as biomarkers stemming from the metals' short biologic half-lives, shipping and storage requirements, and invasive collection procedures. Toenails, which capture a longer exposure period, can be collected non-invasively and stored at room temperature, and can be more feasible and cost-effective for large-scale population studies.

Approach: Inductively coupled plasma mass spectrometry (ICP-MS) has been used for analysis of toenail metal concentrations, but x-ray fluorescence (XRF) has many advantages in versatility and cost effectiveness over these analyses. This study compared toenail concentrations of manganese (Mn) and lead (Pb) measured with XRF against ICP-MS, in samples collected from 20 adults in Nigeria. To do this we developed a novel calibration method that corrects XRF measurements for toenail weight and thickness to reduce the variability in XRF measurements of toenail clippings.

Main Results: We found a high correlation (R  =  0.91) between toenail manganese metal measurements made with XRF and ICP-MS and a correlation of (R  =  0.32) between toenail lead XRF and ICP-MS with over half of the lead results below the detection limit of the instrumentation.

Significance: XRF can be used effectively to quantify metals at the part per million level or lower depending on the XRF equipment used in the measurements.