Determination of the Crystal Structure and Redefinition of Tsugaruite, Pb28As15S50Cl, the First Lead-Arsenic Chloro-Sulfosalt

Author:

Biagioni Cristian1,Bindi Luca2,Momma Koichi3,Miyawaki Ritsuro3,Matsushita Yoshitaka4,Më Yves5

Affiliation:

1. Dipartimento di Scienze della Terra, Università di Pisa, Via Santa Maria 53, I-56126 Pisa, Italy

2. Dipartimento di Scienze della Terra, Università di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy

3. Department of Geology and Paleontology, Division of Mineral Sciences, National Museum of Nature and Science, 4-1-1 Amakubo, Tsukuba, Ibaraki, 305-0005 Japan

4. Research Network and Facility Services Division (RFNS), National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki, 305-0047, Japan

5. Université de Nantes, CNRS, Institut des Matériaux Jean Rouxel, IMN, F-44000 Nantes, France

Abstract

Abstract Tsugaruite was originally defined as a lead-arsenic sulfosalt from the Yunosawa mine, Aomori Prefecture, Japan. Until recently its crystal structure remained unsolved and its actual classification in the sulfosalt realm was unknown. Here the refinement of the crystal structure of tsugaruite using single-crystal X-ray diffraction data is reported. The mineral is orthorhombic, space group P2nn, with unit-cell parameters a = 8.0774(10), b = 15.1772(16), c = 38.129(4) Å, V = 4674.3(9) Å3, in agreement with previous studies. The solution of the crystal structure of this mineral revealed Cl occupying a specific position. Chlorine was thus sought and found using the electron microprobe; the average of six spot analyses gave (in wt.%): Pb 68.04, As 12.83, S 18.29, Cl 0.63, total 99.80. The empirical formula, calculated on the basis of Pb + As = 43 atoms per formula unit, is Pb28.26As14.74S49.08Cl1.52. Tsugaruite is an N = 4 plesiotypic derivative of the homologous series of Pb-Sb chloro-sulfosalts having the general formula Pb(2+2N)(Sb,Pb)(2+2N)S(2+2N)(S,Cl)(4+2N)ClN. It has a Cl/(Cl + S) atomic ratio close to that of other known Pb-Sb chloro-sulfosalts (pillaite, pellouxite) and slightly higher than that of dadsonite.

Publisher

Mineralogical Association of Canada

Subject

Geochemistry and Petrology

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