Combining μX-ray fluorescence, μXANES and μXRD to shed light on Zn2+ cations in cartilage and meniscus calcifications

We aimed to examine the presence of Zn, a trace element, in osteoarthritis (OA) cartilage and meniscus from patients undergoing total knee joint replacement for primary OA. We mapped Ca2+ and Zn2+ at the mesoscopic scale by X-ray fluorescence microanalysis (μX-ray) to determine the spatial distribution of the 2 elements in cartilage, μX-ray absorption near edge structure spectroscopy to identify the Zn species, and μX-ray diffraction to determine the chemical nature of the calcification. Fourier transform infrared spectroscopy was used to determine the chemical composition of cartilage and meniscus. Ca2+ showed a heterogeneous spatial distribution corresponding to the calcifications within cartilage (or meniscus) or at their surface. At least 2 Zn2+ species were present: the first may correspond to Zn embedded in protein (different Zn metalloproteins are known to prevent calcification in biological tissues), and the second may be associated with a Zn trap in or at the surface of the calcification. Calcification present in OA cartilage may significantly modify the spatial distribution of Zn; part of the Zn may be trapped in the calcification and may alter the associated biological function of Zn metalloproteins.