The atomic structure of ammoniojarosite,[(NH4)Fe3(SO4)2(OH)6], a = 7.3177(3) Å, c = 17.534(1) Å, space group Rm, Z = 3, has been solved using single-crystal X-ray diffraction (XRD) to wR 3.64% and R 1.4%. The atomic coordinates of the hydrogen atoms of the NH4 group were located and it was found that the ammonium group has two different orientations with equal probability. Hydronium commonly substitutes into jarosite group mineral structures and samples in the ammoniojarosite–hydronium jarosite solid-solution series were synthesized and analysed using powder XRD and Rietveld refinement. Changes in unit-cell dimensions and bond lengths are noted across the solidsolution series. The end-member ammoniojarosite synthesized in this study has no hydronium substitution in the A site and the unit-cell dimensions determined have a smaller a dimension and larger c dimension than previous studies. Two natural ammoniojarosite samples were analysed and shown to have similar unit-cell dimensions to the synthetic samples. Short-wave infrared and Fourier transform infrared spectra were collected for samples from the NH4–H3O jarosite solid-solution series and the differences between the end-members were significant. Both are useful tools for determining NH4 content in jarosite group minerals.

Micas incorporate a wide variety of elements in their crystal structures. Elements occurring in significant concentrations in micas include: Si, IVAl, IVFe3+, B and Be in the tetrahedral sheet; Ti, VIAl, VIFe3+, Mn3+, Cr, V, Fe2+, Mn2+, Mg and Li in the octahedral sheet; K, Na, Rb, Cs, NH4, Ca and Ba in the interlayer; and O, OH, F, Cl and S as anions. Extensive substitutions within these groups of elements form compositionally varied micas as members of different solid-solution series. The most common true K micas (94% of almost 6750 mica analyses) belong to three dominant solid-solution series (phlogopite–annite, siderophyllite–polylithionite and muscovite–celadonite). Theirclassification parameters include: Mg/(Mg+Fetot) [=Mg#] formicas with VIR >2.5 a.p.f.u. and VIAl <0.5 a.p.f.u.; Fetot/(Fetot+Li) [=Fe#] formicas with VIR >2.5 a.p.f.u. and VIAl >0.5 a.p.f.u.; and VIAl/(VIAl+Fetot+Mg) [=Al#] formicas with VIR <2.5 a.p.f.u. The common true K micas plot predominantly within and between these series and have Mg6Li <0.3 a.p.f.u. Tainiolite is a mica with Mg6Li >0.7 a.p.f.u., or, fortr ansitional stages, 0.3–0.7 a.p.f.u. Some true K mica end-members, especially phlogopite, annite and muscovite, form binary solid solutions with non-K true micas and with brittle micas (6% of the micas studied). Graphical presentation of true K micas using the coordinates Mg minus Li (= mgli) and VIFetot+Mn+Ti minus VIAl (= feal) depends on theirclassification according to VIR and VIAl, complemented with the 50/50 rule.

Hundholmenite-(Y) occurs as pale brown, subhedral crystals up to 1 mm across, embedded in REE–bearing fluorite, in a granitic pegmatite at Hundholmen, Tysfjord, Nordland County, north Norway. Two other occurrences in the same area are the granitic pegmatites at Stetind and Lagmannsvik. The simplified formula, obtained from wavelength-dispersive EMP analyses and boron determination by ICP-AES, is (Y,REE,Ca,Na)15(Al,Fe3+)CaxAs1–x3+ (Si,As5+)Si6B3(O,F)48 (x = 0.78). The mineral is trigonal, R3m, with a = 10.675(6), c = 27.02(2) Å , V = 2667(5) Å 3, Z = 3. The crystal structure was refined to R1 = 0.037 for 1720 observed reflections. Hundholmenite-(Y) is isostructural with okanoganite-(Y) and vicanite-(Ce), and the differences in site populations are discussed. The strongest seven reflections of the X-ray powder-diffraction pattern [dobs in Å , (I) (hkl)] are: 4.38 (33) (202), 3.114 (43) (214), 2.972 (100) (027), 2.947 (76) (125), 2.924 (66) (303, 033), 2.681 (36) (220) and 1.978 (37) (235). The mineral is optically uniaxial (–) with o 1.7578(5) and e 1.7487(5). The Mohs hardness is ~5–6; Dcalc = 5.206(9) g/cm3.

The pearceite-polybasite group of minerals, general formula [M6T2S7][Ag9CuS4] with M = Ag, Cu; and T = As, Sb, show a crystal structure which can be described as the succession, along the c axis, of two pseudo-layer modules: a [M6T2S7]2–A module layer and a [Ag9CuS4]2+B module layer. Copper is present in one structural position of the B module layer and replaces Ag in the only fully occupied M position of the A module layer. When the Cu content is >4.00 a.p.f.u., the structural position of the A module layer becomes Cu-dominant and, consequently, the mineral deserves its own name. In this paper we report the crystal-chemical characterization of two Cu-rich members exhibiting the 111 unitcell type (corresponding to the Tac polytype). One sample (space group (P)m1, a 7.3218(8), c 11.8877(13) Å, V 551.90(10) Å3, Z = 1) having As >Sb and with the structural position of the A module layer dominated by Cu, has been named cupropearceite and the other sample (space group (P3̄)m1, a 7.3277(3), c 11.7752(6) Å, V 547.56(8) Å3, Z = 1) having Sb >As has been named cupropolybasite.

Both the new minerals and mineral names have been approved by the IMA-CNMNC.

Geochemical processes and mineralogical transformations in the spontaneously combusting coal waste pile of the Kukla mine in Oslavany, Czech Republic, were investigated. The aims of the study were: (1) the characterization of secondary minerals; and (2) determination of processes which influence the mobility of elements in the pile. The pile burned from the late 19th century until the 1990s and has acquired a zoned nature, with original black material in the core of the pile, red material produced by burning close to the pile slopes and grey and white efflorescent salts precipitated on the pile top and slopes. Several mineral assemblages have been identified including (1) primary minerals in the black material including bituminous coal to anthracite, micas, pyrite and goethite; (2) hematite, spinels and corundum in the red materialproduced by pyrometamorphism; and (3) hydrated sulphates of magnesium including hexahydrite, konyaite and picromerite in efflorescent precipitates on the slopes of the pile. A conceptual model of geochemical processes in the pile includes seasonal changes with mineral dissolution during the wet season and precipitation of efflorescent salt minerals during the dry season. Formation of secondary minerals such as hematite, which is resistant to weathering and immobilizes hydrolysable Fe, may have a positive environmental impact in the long term.

Small (m-scale) peridotite enclaves at Planany (central Czech Republic) are separated from their gneissic host rocks by a narrow (cm-scale) reaction rim comprising an inner, tremolite + phlogopite zone and an outer, essentially monomineralic phlogopite zone. Both retain an Mg# very similar to that of the peridotite (Mg# = 81), but relative to this reference frame, show large increases in LILE (K, Rb, Ba) and radionuclides (U, Th). On a smaller scale, however, there has been a mineralogically-controlled decoupling of various components, particularly among the HFSE and REE, the former favouring the phlogopite-rich outer layer of the reaction rim, the latter the amphibole-rich inner zone. Taken together, however, the reaction zones preserve key compositional features of their inferred protolith.

One metamorphic and four magmatic aegirines, together with two end-member aegirines synthesized at atmospheric pressure and different temperatures, were investigated by single-crystal X-ray diffraction. The limited compositional differences allow the polyhedral volumes to be almost constant in all the aegirines investigated( VM1 ≈ 11.0 Å3; VM2 ≈ 26.3 Å3; VT ≈ 2.21 Å3). However, differences in polyhedral distortions are responsible for the cell-volume variations, reflected mainly in the change of a and β cell parameters. Cell volume is only partly related to the composition of these aegirines: with increasing formation temperature, an increase in the unit-cell volume of ~1.2 Å3 is observed, while a significant contraction of the cell volume occurs during high-pressure formation. As the difference in cell volume between the two synthetic aegirines is ascribed to the different conditions of synthesis temperature, the same interpretation could be adopted for the differences observed in natural aegirines.

Olmiite, ideally CaMn[SiO3(OH)](OH), is a newly identified mineral from the N’Chwaning II mine of the Kalahari manganese fields (Republic of South Africa), which occurs as a product of hydrothermal alteration associated with poldervaartite, celestine, sturmanite, bultfonteinite and hematite. The mineral occurs as wheat-sheaf aggregates consisting of pale to intense reddish pink minute crystals. Olmiite is transparent with vitreous lustre, and exhibits deep-red fluorescence under short-wave UV-light. The mineral is brittle, with irregular fracture. Streak is white and Mohs hardness is 5–51/2. No cleavage was observed. The measured density (pycnometer method) is 3.05(3) g/cm3. The calculated density is 3.102 g/cm3 or 3.109 g/cm3 using the unit-cell volume from single-crystal or powder data, respectively. Olmiite is biaxial positive, with refractive indices α = 1.663(1), β = 1.672(1), γ = 1.694(1) (589 nm), 2Vmeas = 71.8(1)º, 2Vcalc = 66(8)º. The optical orientation is X = a, Y = c, Z = b and dispersion: r > v, distinct. Pleochroism is not observed. Chemical analysis by electron microprobe yielded the chemical formula (Ca2–xMnxFey)[SiO3(OH)](OH), with 0.84 ≤ x ≤ 0.86, and y ≤ 0.01. Olmiite is orthorhombic, space group Pbca, with a = 9.249(3), b = 9.076(9), c = 10.342(9) Å , V = 868(1) Å 3 and Z = 8. The strongest five powder-diffraction lines [d in Å , (I/Io), hkl] are: 4.14, (45), 021; 3.19, (100), 122; 2.807, (35), 311; 2.545 (35), 312; 2.361, (40), 223. Single-crystal structure refinement (R1 = 2.74% for 1012 observed reflections) showed that the atomic arrangement of olmiite is similar to that of poldervaartite, with all Mnordered onthe M2 site. Significant variations in bond distances and angles are related to the pronounced difference in the Mn content. Olmiite, therefore, is the Mn-dominant analogue of poldervaartite. The name poldervaartite should be reserved for samples having Ca dominant at the M2 site.

The crystal structures of a suite of amphiboles from the Kola Superdeep Borehole, Russia, have been refined to R values of ∼3% using single-crystal Mo-Kα X-ray diffraction data. The same crystals used in the collection of the intensity data were subsequently analysed by electron microprobe (EMP) and milliprobe Mössbauer spectroscopy. Site populations were assigned from the results of site-scattering refinement and stereochemical analysis, taking into account the unit formula determined for each crystal. The Fe3+/(Fe2++Fe3+) values were derived (1) by least-squares refinement of the Mössbauer spectra, and (2) SREF (Structure REFinement) by careful analysis of the mean bond lengths at the M(2) site using two possible models for the behaviour of Ti4+: (i) Ti4+ at M(2); and (ii) Ti4+ at M(1). The agreement between the SREF and Mössbauer/EMP values for Fe3+ is very close for Ti4+ assigned to M(2). This result indicates that the calculation of Fe3+ contents in amphiboles from refined site populations and <M(2)–O> distances are accurate. This paper presents the first confirmation of this result.

Strontium and Mg in calcite and aragonite are widely used as proxies of temperature in palaeoenvironmental reconstructions. We use X-ray absorption fine structure (XAFS) to examine Sr and Mg substitution in calcite and aragonite. We have measured the K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of Mg and Sr-bearing calcite and aragonite, plus the carbonates: strontianite, hydromagnesite, magnesite, dolomite and a suite of calcites with differing amounts of Mg. The Sr substitutes ideally for Ca in aragonite but causes a small (2%) dilation of the site. Strontium substitutes for octahedral Ca in calcite but with a 6.5% dilation and distortion. Magnesium in the calcites studied provides a variable XANES indicating that the Mg structural state in calcite is variable. Refinement of EXAFS gives Mg–O bond distances of ∼2.12 Å, which are much smaller than the Ca–O bond distance of 2.35 Å but consistent with published amounts of relaxation of the calcite structure. The XANES and EXAFS are consistent with a model whereby some calcites contain nanodomains, e.g. of dolomite and/or huntite structures. The variability in the XANES can be explained by domains of different types and/or sizes. Substitution of Mg into aragonite has 9-fold coordination but relatively short bond distances (2.08 Å) demonstrating either: (1) substantial distortion of the site; or (2) that Mg is accommodated in nanodomains of an unknown phase. Variability in the Mg structural state in calcite may be linked to the variety of temperature dependences observed, e.g. in foraminiferal calcite

Copiapite is a mineral of iron- and sulphate-rich acidic environments and has a general formula AFe3+4 (SO4)6(OH)2(H2O)20, where A = Fe2+, 2/3Fe3+, 2/3Al3+, Mg, Zn. The structure is built by infinite tetrahedral-octahedral chains and isolated octahedrally coordinated A sites. Our synthetic and natural copiapite samples can be divided into two large groups based on the orientation of the structural fragments. One group comprises copiapite phases where A = Al3+, Fe2+ or Fe3+ and we designate it as the structural type AL. The other group consists of copiapite with A = Mg2+, Zn2+ or Ni2+ and this is the structural type MG. The solid-solution series between Fe3+ and Al3+ copiapite is continuous. The series between Mg2+-Al3+, Mg2+-Fe3+ and Mg2+-Al3+-Fe3+ copiapite are not continuous; the samples with intermediate compositions contain two copiapite phases, one of the type AL and one of the type MG. The series between Mg2+ and Zn2+ copiapite is continuous only at 25°C. At 75°C, the Zn-rich portion of this systemcrystallizes a copiapite-like phase whose structure may be a superstructure of copiapite. The series between Al-Fe2+ and Mg-Fe2+ copiapite are not continuous and show complex behaviour of the intermediate compositions.

A multi-methodological study, based on electron microprobe analysis (in wavelength dispersive mode), single-crystal X-ray diffraction (XRD), transmission electron microscopy and single-crystal Fourier transform infrared spectroscopy was performed in order to describe the crystal chemistry of four leucite samples from different localities of the Roman Comagmatic Province (central Italy). All the crystals examined were found to be tetragonal (space group I41/a with a = 13.076–13.103 Å and c = 13.744–13.784 Å) and characterized by a complex twinning (merohedric twins: on the tetragonal planes (110) and (1̄10) with the two individuals having parallel crystallographic axes with a and b interchanged; pseudo-merohedric twins: on the tetragonal planes (101), (011), (1̄01), (01̄ 1), with the two individuals having parallel a (or b) axes and the remaining two axes not parallel). The chemical analyses show that all the samples contain minor Na and Fe. Infrared spectroscopy shows that all samples contain structurally bound water molecules, up to unexpectedly large amounts (~0.4 wt.%) for a nominally anhydrous mineral, suggesting that ‘analcime-like’ substitution (K to Na + H2O) occurs in the leucite samples investigated here. The detection limits of the ‘analcime-like’ substitution by singlecrystal XRD are also discussed.

The Takab meta-ultramafic rocks of northwestern Iran crop out in association with a variety of metamorphic rocks and they can be divided into three types on the basis of dominant mineral assemblage and degree of serpentinization: metaperidotites, talc-serpentine rocks and serpentinites. The peridotite protoliths were mainly spinel-harzburgites and -dunites. The talc-serpentine rocks formed under low-grade conditions and their dominant mineral assemblage is lizardite/chrysotile + talc + calcite/dolomite. Pseudomorphic textures after olivine and pyroxene are typical. Later, lower amphibolite-facies metamorphism produced antigorite, clinochlore and tremolite. Late alteration, assisted by local shearing, produced more antigorite and late lizardite in the metaperidotites. The mineral chemistry of the serpentine polymorphs is variable. Compositions of coexisting spinel and olivine point to an ophiolitic origin. Thermometric estimates from co-existing relict olivine, pyroxenes and spinel are in the range 1000–1200ºC; clinopyroxene barometry yields a pressure of 24± 2.7 kbar for the mantle conditions. Exhumation and hydration followed, and the stability of lizardite/chrysotile constrains the T and XCO2 to <280ºC and <0.002, respectively. Subsequent prograde regional metamorphism took place in an orogenic setting, reaching peak temperatures in the range 410–540ºC at XCO2 >0.1. A Neoproterozoic–Early Cambrian age for the Takab protoliths is suggested on the basis of correlations with the Central Iran Zone. The strips of ultramafic rock in the Takab complex can be attributed to lithospheric remnants of the Proto-Tethyan ocean which closed during the Pan-African orogeny.

The Tertiary volcano-sedimentary sequence of the Feres basin (Thrace, NE Greece), includes lavas of andesitic–rhyolitic composition as well as volcaniclastic rocks, pyroclastic flows and pyroclastic fall deposits principally of dacitic–rhyodacitic composition. The pyroclastic flow deposits frequently show intense devitrification, vapour-phase crystallization and evidence of fumarolic activity, which involves deposition of scapolite in pore spaces. The Feres basin can be subdivided on the basis of mineral alteration assemblages: (1) the Pefka region; characterized by intense hydrothermal alteration of the volcanic rocks and mineral zoning(silicic, argillic, sericitic and propylitic zones) with polymetallic mineralization, and (2) the remainder of the basin; where the volcaniclastic rocks are characterized by the alteration of volcanic glass to zeolites (clinoptilolite, heulandite, mordenite, analcime), clay minerals (smectite, illite, celadonite, chlorite), SiO2 polymorphs (cristobalite, opal-CT, quartz), K-feldspar and calcite. Laumontite is also present as an alteration product of plagioclase, with stilbite sporadically occurringin veinlets. Locally, rhyolites are also altered to zeolites (clinoptilolite and/or mordenite). The zeolitization process has occurred rapidly with the depositional environment, temperature, rate of cooling(of the volcanic rocks), nature and temperature of the mineral-forming fluids and composition of the parent material controllingthe formation of zeolites.

Agates from a 430 Ma host at Stockdale Beck, Cumbria, England have been characterized. The crystallite size of the Stockdale Beck agates was found to be ~60% greater than any other agates from five regions aged 400–1100 Ma. Raman spectroscopy identified moganite in all agates tested except those from Stockdale Beck. Infrared spectroscopy showed that the silanol content of the Stockdale Beck agates was near zero. The properties of agates from Stockdale Beck and the 1.84–3.48 Ga metamorphosed hosts found in Western Australia were similar but different from agates found in other hosts aged 400–1100 Ma. Cathodoluminescence demonstrates further differences between agates from hosts aged 13–1100 Ma and those from Stockdale Beck and Western Australia. Agates from the latter areas have a lower proportion of defects causing a red emission band (~660 nm) but an increased proportion of defects causing blue (~470 nm) and orange (~640 nm) emission bands. Agates found in hosts aged 13–1100 Ma are also differentiated from the Stockdale Beck and Western Australian agates in a ternary plot of the relative intensities of violet to blue to orange emission bands. Single scans producing this combination of colours are only found in the Stockdale Beck and Western Australian agates. The properties shown by the Stockdale Beck and Western Australian agates demonstrate that an agate or chalcedony infill can be used to identify post-deposition palaeoheating within a host rock.

Three natural amphibole samples collected from the former vermiculite mine near Libby, Montana. USA, have been analysed by Rietveld X-ray powder diffraction (XRPD) refinement and Fourier transform infrared spectroscopy (FTIR) in the OH-stretching region. The same materials have been analysed previously by electron microprobe analysis (EMPA), Mössbauer spectroscopy and structure refinement (SREF) single crystal X-ray diffraction (SC-XRD), which revealed that these amphiboles have a crystal chemical formula very close to an intermediate composition between winchite and richterite, i.e. AA0.5BNaCaCMg4.5M3+T0.5Si8O22(OH)2 (A = Na and/or K; M3+ = Fe3+ and/or Al). The Rietveld analysis showed the powder samples used for the experiments here to be composed only of amphibole. This in turn allowed us to use FTIR OH-stretching data to derive cation ordering on these powder samples. The three FTIR spectra are quite similar and up to four components can be fitted to the patterns. The two lower-frequency components (labelled A and B) can be attributed to a local O(3)-H dipole surrounded by M(1)M(3)Mg3 and M(1)M(3)Mg2Fe2+; (respectively), an empty A site and rSi8 environments; on the contrary, the higher-frequency C and D bands indicate the presence of an occupied A site. The FTIR OH-stretching data alone allow us to calculate the site occupancy of the A, M(1)–M(3) and T sites with confidence, as compared with previously published data. By contrast M(4)- and M(2)-site occupancies are more difficult to evaluate. This study takes advantage of the large database of well characterized synthetic amphiboles, built over the last two decades. The comparison of vibrational spectroscopy data with micro-chemical and crystallographic data reported in this study demonstrate that the FTIR OH-stretching method alone is a valuable and rapid method to derive or at least sensibly constrain site occupancy for natural amphiboles. A much more detailed cation site occupancy can be obtained by combining micro-chemical and FTIR OH-stretching data.

The high-pressure behaviour of manganese carbonate was investigated by in situ synchrotron X-ray powder diffraction up to 54 GPa with a laser-heated diamond anvil cell. A phase transition from rhodochrosite to a new structure form was observed at 50 GPa after laser heating. The diffraction pattern of the new high-pressure form was reasonably indexed with an orthorhombic unit-cell with a = 5.361 A, b = 8.591 A and c = 9.743 Å. The pressure-induced phase transition implies a unit-cell volume reduction of ∼5%. This result does not support the direct formation of diamond by dissociation of solid state MnCO3 reported in a previous study. Fitting the compression data of rhodochrosite to a second-order Birch-Murnaghan equation of state (Ko’ = 4) gives K0 = 126(±10) GPa. The c axis of the unit-cell parameter was more compressive than the a axis.

The Bafq mining district is in the Early Cambrian Kashmar-Kerman volcano-plutonic arc in Central Iran and hosts important ‘Kiruna-type’ magnetite-apatite deposits. The hydrothermal magnetite-apatite mineralization occurs mostly as massive orebodies, metasomatic replacements, veins and stockworks. Apatite (low-Sr fluorapatite containing small amounts of hydroxyl) has undergone a partial hydrothermal overprint which involved leaching of Na, Cl and REE. The REE were remobilized into monazite (and minor allanite, parisite and xenotime) which nucleated as inclusions within apatite or as individual crystals. The monazites have very small ThO2 contents (usually <1 wt.%), but they occasionally show an inner core of high-Th monazite, with low-Th overgrowth rims. The chemical Th-U-total Pb dating of the high-Th monazites by electron microprobe analysis yields an isochron age of 515±21 Ma (initial PbO intercept = 68 ppm), or 529±21 Ma (forced initial PbO = 0), which is contemporaneous with the emplacement of the volcano-plutonic host rocks of the magnetite-apatite mineralization, as well as with widespread sedimentation of Late Proterozoic to Cambrian evaporitic rocks in Central Iran. The monazite age and the mineralogical and geochemical data suggest that the magnetite-apatite deposits are probably related to large-scale brine circulation induced by felsic magmatism during the Cambrian.

The literature contains considerable disagreements on the relative stabilities of the members of the copper hydroxyl sulphate family. Titration of copper sulphate with sodium hydroxide is claimed by some to produce only brochantite, while other reports indicate that antlerite and a dihydrate of antlerite are produced in the titration. Most stability field diagrams show that antlerite is the more stable stoichiomer at pH 4 and sulphate activity of 0.05–1. We have reexamined this stoichiometric family by titration of aqueous copper sulphate with sodiumhydroxide and sodium carbonate, reverse titration of sodiumhydroxide with copper sulphate and simultaneous addition of copper sulphate and sodium hydroxide at a variety of mole ratios, concentrations, temperatures and reaction times. We have also explored the reaction of copper hydroxide with copper sulphate and the reaction of weak bases, such as sodiumacetate, sodiumcarbonate and urea, with copper sulphate. Our work indicates that: (1) antlerite is not formed in reactions of 0.05 to 1.2 M CuSO4 with 0.05–1.0 M NaOH or Na2CO3 at room temperature; (2) antlerite is formed in the addition of small concentrations of base (≤0.01 M) to 1 M CuSO4 at 80°C, but not at roomtem perature or with 0.01 M CuSO4 at 80°C; (3) the formation of Cu5(SO4)2(OH)6·4H2O occurs at large Cu2+ to base mole ratios; (4) the compound described in the literature as antlerite dihydrate is actually Cu5(SO4)2(OH)6.4H2O; (5) at mole ratios of Cu2+ to OH– ranging from 2:1 to 1:2 the predominant product is brochantite; and (6) brochantite and Cu5(SO4)2(OH)6.4H2O are converted to antlerite in the presence of 1 M CuSO4 (the latter requires temperatures of 80°C or greater).

The Ksp (ion activity product) values of antlerite and brochantite were determined to be 2.53 (0.01)⨯10−48 and 1.01 (0.01)⨯10−69, respectively, using atomic absorption spectroscopy and Visual MINTEQ after equilibration in solutions of varying ionic strength and pH for six days. These values are in good agreement with those from the literature. However, after 6 months, antlerite in contact with solution is partially converted to brochantite and hence is metastable with a relatively low conversion rate. The Ksp value for antlerite must therefore be considered approximate. The relative stabilities of the copper hydroxyl sulphates are rationalized using appropriate equations and Gibbs energy calculations. A Gibbs free energy of formation for Cu5(SO4)2(OH)6.4H2O of –3442 kJ/mol was obtained from the simple salt approximation.