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Five samples of voltaite-group minerals from post-volcanic occurrences (geothermal fields and solfatara at pyroclastic flow) and from pseudofumaroles born by coal fires are characterized by single-crystal X-ray diffraction, scanning electron microscopy and electron microprobe analysis. The studied minerals include ammoniomagnesiovoltaite, ammoniovoltaite, voltaite and magnesiovoltaite. The quadrilateral of chemical compositions is determined by monovalent cations such as (NH4)+ and K+ and divalent cations such as Fe2+ and Mg2+. Minor Al can occur in the Fe3+ site. Minor amounts of P, V can occur in the S site. Ammonium members are described from geothermal fields, expanding the mineral potential of this type of geological environment. All minerals are cubic, space group Fd-3c, a = 27.18–27.29 Å, V = 20079–20331 Å3, Z = 16. No clear evidence of symmetry lowering (suggested for synthetic voltaites) is observed despite the chemical variation in the studied samples. Ammonium species tend to have a larger a lattice parameter than potassium ones due to longer distances (A = N or K). The systematically shorter obs (Me2+ = Fe, Mg; ϕ = O, H2O) in comparison to calc bond lengths can be explained as a consequence of mean bond length variation due to significant bond length distortion in Me2+ϕ6 octahedra Me2–O2—2.039–2.055 Å; Me2–O4—2.085–2.115 Å; and Me2–Ow5—2.046–2.061 Å, with bond length distortion estimated as from 0.008 to 0.014 for different samples.

A new mineral, hanauerite, ideally AgHgSI, was found in the oxidation zone of Ag- and Hg-bearing ores at two old, abandoned mines in Rhineland-Palatinate, Germany. In a holotype specimen originating from the Schöne Aussicht Mine, Dernbach, Westerwald, it is associated with plumbogummite–hinsdalite series of minerals and goethite. In cotype from the Friedrichssegen Mine, Bad Ems, it is associated with perroudite, goethite, and quartz. At both localities, hanauerite occurs as a prismatic crystal up to 0.15 mm long and up to 0.02 mm thick. The mineral is yellow, transparent, with an adamantine lustre. It is brittle, and cleavage was not observed. The calculated density values are 6.671 and 6.575 g cm−3 for holotype and cotype, respectively. The empirical formulae calculated (from electron microprobe data) based on the sum of all atoms = 4 apfu are Ag0.95Hg1.00S1.01(I0.83Br0.19Cl0.03)Σ1.05 for holotype and Ag0.97Hg0.97S1.05(I0.76Br0.25)Σ1.01 for cotype. Hanauerite is orthorhombic, space group Pmma; the unit cell parameters (from single-crystal X-ray diffraction data; holotype/cotype) are: a = 9.932(2)/9.9256(8), b = 4.6219(19)/4.6209(2), c = 9.891(4)/9.9006(4) Å, V = 454.0(3)/454.19(5) Å3, and Z = 4. The crystal structure was studied on single crystals extracted from both holotype and cotype specimens; R1 = 0.0416 (holotype) and =0.0544 (cotype). In hanauerite, Hg2+ cations centre strongly distorted octahedra with two short Hg–S bonds (Hg and S atoms build “crankshaft-type” chains) and four strongly elongated Hg–I bonds. The Hg-centred octahedra are connected via common edges and faces to form corrugated layers; Ag+ cations are located between these layers. Hanauerite is named in honour of the German mineral collector Dr. Alfred Hanauer (1912–1988). The common crystal chemical features of mercury sulphohalide minerals are discussed.

Crystals of the natural zeolite amicite, ideally K4Na4(Al8Si8O32)·10H2O, were ion-exchanged in the reactions with 0.1 N aqueous solutions of AgNO3, RbNO3, CsNO3 and Pb(NO3)2 at 363 K for 24 h. Under these conditions, Cs+ substitutes K+ whereas the most part of Na+ remains unexchanged; Rb+ partly substitutes both Na+ and K+; Pb2+ and Ag+ completely substitute Na+ and K+. All the compounds are monoclinic. The Cs- and Rb-substituted samples have unit-cell parameters close to those of initial amicite. The exchange of Na+ and K+ for Ag+ is accompanied by a significant decrease of the unit-cell volume. The unit-cell parameter c of Pb-amicite is nearly threefold larger than the c parameter of initial amicite. Infrared spectra show that framework topology is preserved during the ion exchange. The crystal structures of initial and Cs-exchanged amicites have been solved by direct methods.

Technogenic steklite, KAl(SO4)2, and unnamed mineral phase (K,Na)3Na3(Fe,Al)2(SO4)6 from burnt dumps of the Chelyabinsk Coal Basin have been investigated by single-crystal X-ray diffraction and electron microprobe analysis. Steklite is trigonal, space group P3¯, a = 4.7277(3), c = 7.9871(5) Å, V = 154.60(2) Å3. The crystal structure was refined to R1 = 0.026 (wR2 = 0.068). It is based upon the [Al(SO4)2]− layers formed by corner sharing of SO4 tetrahedra and AlO6 polyhedra. The anionic [Al(SO4)2]− layers are parallel to the (001) plane and linked via interlayer K+ ions. The regular octahedral coordination of Al is observed that distinguishes technogenic steklite from that found in Tolbachik fumaroles. The (K,Na)3Na3(Fe,Al)2(SO4)6 phase is trigonal, space group R3¯, a = 13.932(2), c = 17.992(2) Å, V = 3024.4(7) Å3, R1 = 0.073 (wR2 = 0.108). The crystal structure is based upon the anionic chains [(Fe,Al)(SO4)3]3− running parallel to the c axis and interconnected via K+ and Na+ ions. There are no known minerals or synthetic compounds isotypic to (K,Na)3Na3(Fe,Al)2(SO4)6, due to the presence of separate K and Na sites in its structure.

A new mineral, krasnoshteinite (Al8[B2O4(OH)2](OH)16Cl4⋅7H2O), was found in the Verkhnekamskoe potassium salt deposit, Perm Krai, Western Urals, Russia. It occurs as transparent colourless tabular to lamellar crystals embedded up to 0.06 x 0.25 x 0.3 mm in halite-carnallite rock and is associated with dritsite, dolomite, magnesite, quartz, baryte, kaolinite, potassic feldspar, congolite, members of the goyazite–woodhouseite series, fluorite, hematite, and anatase. Dmeas = 2.11 (1) and Dcalc = 2.115 g/cm3. Krasnoshteinite is optically biaxial (+), α = 1.563 (2), β = 1.565 (2), γ = 1.574 (2), and 2Vmeas = 50 (10)°. The chemical composition (wt.%; by combination of electron microprobe and ICP-MS; H2O calculated from structure data) is: B2O3 8.15, Al2O3 46.27, SiO2 0.06, Cl 15.48, H2Ocalc. 33.74, –O=Cl –3.50, totalling 100.20. The empirical formula calculated based on O + Cl = 33 apfu is (Al7.87Si0.01)Σ7.88[B2.03O4(OH)2][(OH)15.74(H2O)0.26]Σ16[(Cl3.79(OH)0.21]Σ4⋅7H2O. The mineral is monoclinic, P21, a = 8.73980 (19), b = 14.4129 (3), c = 11.3060 (3) Å, β = 106.665 (2)°, V = 1364.35 (5) Å3, and Z = 2. The crystal structure of krasnoshteinite (solved using single-crystal data, R1 = 0.0557) is unique. It is based upon corrugated layers of Al-centered octahedra connected via common vertices. BO3 triangles and BO2(OH)2 tetrahedra share a common vertex, forming insular [B2O4(OH)2]4− groups (this is a novel borate polyanion) which are connected with Al-centered octahedra via common vertices to form the aluminoborate pseudo-framework. The structure is microporous, zeolite-like, with a three-dimensional system of wide channels containing Cl- anions and weakly bonded H2O molecules. The mineral is named in honour of the Russian mining engineer and scientist Arkadiy Evgenievich Krasnoshtein (1937–2009). The differences in crystal chemistry and properties between high-temperature and low-temperature natural Al borates are discussed.

New data are obtained for minerals from metasomatic rocks of the orogenetic zone related to the “Mixed series” metamorphic complex situated in the Pelagonian massif near the Nežilovo village, about 40 km SW of Veles, Republic of Macedonia. A specific feature of these rocks is the concentration of chalcophile elements (S, As, Sb, Zn, Pb) mainly in the form of oxides and oxysalts, whereas sulfides and sulfosalts are present only in trace amounts. Rock-forming and accessory minerals have been characterized by electron microscopy, electron mictoprobe analyses and in part by X-ray diffraction and IR spectroscopic data. Some of described minerals (Sb-rich analogue of zincohögbomite-2N6S, hydroxyplumbobetafite, Fe3+-analogue of coronadite) are potentially new mineral species. Some genetic aspects of the formation of oxidized As-Sb-Zn-Pb-rich rocks are discussed.

The reviewed monograph is the first extended work in which data on the minerals of the Republic of Macedonia have been described. This book is written in English to make the information on the mineralogy of the Republic of Macedonia accessible to a worldwide audience. The monograph contains a general introduction to mineralogy, which makes it useful for people starting their education in this science, i.e. students of geology, amateur mineralogists and mineral collectors in the Republic of Macedonia. Thus, the monograph is a dual-purpose book.