Published electron microprobe analyses of mattheddleite, a lead sulpho-silicate apatite from Leadhills, Scotland, have 9–13% IV site deficiencies. However, galena was used as a standard for S, which suggested that low S resulted from a shift in the S-Kα peak. Wavelength scans with a PET crystal show that the S-Kα peak is shifted down by 0.0026 Å for sulphates relative to sulphides. Quantitative analyses show a ~30% increase of S in mattheddleite using a celestite standard, which fills the IV site, but with Si > S, on average Pb5S1.2Si1.8O11.7Cl0.6(OH)0.4. Direct analysis of oxygen with the electron microprobe implies that the charge imbalance engendered from the inequality of Si and S is compensated with substitution of a vacancy (□), as in Pb5S1.2Si1.8[O11.70.3][Cl0.6(OH)0.4] or Pb5S1.2Si1.8[O11.7(Cl,OH)0.3][Cl,OH)0.70.3]. Calculation of OH as 1–Cl suggests the presence of both OH- and Cl-dominant mattheddleite at Leadhills, but direct analysis of H is needed to confirm the dominance of OH in the channel site. Wavelength-dispersive analyses of S in apatite and other sulphates must be undertaken with sulphate standards: use of sulphide standards yields a negative error on the order of 10–20% in the resultant S concentration. Reactions of mattheddleite with other Pb minerals at Leadhills show that their stability depends on fluid composition as well as pressure and temperature. An X-ray map of Cl shows complex zoning between Cl-poor and Cl-rich mattheddleite, recording rapid changes in the fluid chemistry during late-stage hydrothermal processes at Leadhills.

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