First finding of tiemannite, HgSe, in human bladder stones: An electron microprobe study.

Human bladder stones, surgically removed from a 4 years old boy, were studied by X-ray diffraction (XRD) and by electron microprobe analyses (EPMA). XRD data show that the bladder stones are mainly composed of struvite with minor apatite. Tiny particles, <10 µm in size, composed of mercury (Hg) and selenium (Se) were found using scanning electron microscopy (SEM) and quantitative analysis by wave-length dispersive system (WDS). On the basis of their composition, the particles consist of tiemannite, a rare mineral with the ideal formula HgSe. The young patient was not exposed to relevant mercury contamination and has no teeth fillings of amalgam. Although this observation is not conclusive, we suggest that Hg was introduced as methylmercury by food. The discovered tiemannite can be classified as endogenous mineral, i.e., directly precipitated from the same fluids that formed the host bladder stones. This assumption is supported by the fact that tiemannite and struvite can crystallize at the same temperature and pH values. As proposed for the formation of tiemannite previously reported in the liver of cetaceans, we suggest that the tiemannite in the human body represents a probable product of demethylation of Hg. In this contribution, we suggest that Hg and Se were initially collected by urine in the human body and finally precipitated to form tiemannite under appropriate chemical-physical conditions together with the formation of the host bladder stone. This observation suggests that the precipitation and accumulation of metals, including Hg and Se, in the human body can be considered a physiological response to eliminate part of these trace elements, thus enabling detoxification.

Metals in Human Gall, Bladder, and Kidney Stones Based on an Electron Microprobe Investigation.

Several particles of copper accompanied by a few particles of nickel, lead, and a compound composed of selenium containing minor Ni, Si, Cu, and Co were found in human gall, kidney, and bladder stones. The investigated particles occur as tiny grains, <10 µm in size, that are irregularly dispersed in the stones. Therefore, they were studied by scanning electron microscopy and qualitatively analyzed by energy dispersive system. One grain of copper contained a small amount of Ni and Zn, and some grains of nickel proved to contain Cr as trace element. Most of the discovered metals formed a single-phase grain. However, a few grains found in two gallstones were associated with inclusions of calcium and apatite. Based on the results presented in this contribution, we argue that most of the studied metals can be classified as endogenous particles, i.e., directly precipitated from the same fluids that formed their host human stones. This observation suggests that the precipitation and accumulation of metals in some human stones can be considered an efficient way to eliminate them from the human body.

Electron Microprobe and Raman Spectroscopy Investigation of an Oxygen-Bearing Pt-Fe-Pd-Ni-Cu Compound from Nurali Chromitite (Southern Urals, Russia).

One grain, about 100×80 µm in size, occurring in chromitite associated with the layered sequence of the Nurali mafic-ultramafic complex (Southern Urals, Russia) was investigated by electron-microprobe analyses and Raman spectroscopy. The grain is characterized by a spotty, rugged appearance and chemical zoning from which two compositions were calculated: (Pt(0.35)Pd(0.26)Fe(0.22)Cu(0.01)Ni(0.05))(0.98)O(1.02) and (Fe(0.90)Pt(0.58)Ni(0.28)Pd(0.13)Cu(0.08)Rh(0.01))(1.98)O(1.02). In the lack of X-ray data, Raman spectroscopy established the presence of a diffuse 500-700 band and a sharp peak at 657 cm⁻¹ of relative wavenumber that strongly resemble the Raman spectra of synthetic PtO and PdO (palladinite). It is concluded that the Nurali grain probably represents a platinum group element (PGE) oxide, and does not consist of a mixture of PGE alloys with Fe oxide or hydroxide as reported for other natural PGE-O compounds.