Rare earth elements (REEs, ‘lanthanides’) constitute a vital commodity for technological applications. Although these elements occur at trace levels in many minerals, they can comprise major constituents of low abundance phosphate, carbonate, silicate and oxide minerals, some of which form during granite weathering. REE-phosphate phases can be a source of phosphorus for essential biomolecules and certain REEs are required by some bacterial enzymes involved in the oxidation of methanol, an important compound in the global biogeochemical carbon cycle. The mechanisms that promote the dissolution of lanthanide phosphate minerals are largely unknown, but probably vary with the lanthanide phosphate mineralogy of weathered rock and soil. Here, we studied weathering of five I-type, three S-type and one A-type granite to determine the extent of weathering of primary REE- and/or P-bearing minerals apatite, allanite and monazite, and the formation of secondary REE/P-bearing minerals. We found evidence for greater mobilisation of REE and P in weathered I-type and A-type granites than in S-types, reflecting the higher solubility of apatite and allanite relative to monazite. Although monazite persisted in highly weathered S-type granites, some alteration was detected. Secondary REE/P-bearing minerals were not detected in two S-type profiles, while spherical secondary REE/P-bearing mineral aggregates were abundant throughout the third S-type profile. Secondary euhedral REE/P-bearing crystals were abundant even in the slightly weathered I-type and A-type granite material, yet they were not detected in the highly weathered material, indicating that these minerals had dissolved. Our findings indicate that mineralogy constrains substantially, but does not control completely, lanthanide availability as a function of degree of weathering. These results have implications for predicting REE and phosphate bioavailability in soils derived from granitic rock types and suggest that highly weathered I-type granites may provide inocula for bioleaching experiments.

The free energies of formation of the minerals libethenite, Cu2PO4OH, pseudomalachite, Cu5(PO4)2(OH)4, cornetite, Cu3PO4(OH)3, tarbuttite, Zn2PO4OH, spencerite, Zn2PO4OH · 1.5H2O, and scholzite, CaZn2(PO4)2 · 2H2O, have been determined at 298.2 K using solution techniques. The values of ΔfG° (298.2 K) for the above minerals are, respectively, −1228.8±3.0, −2840.3±4.2, −1600.9±5.9, −1632.1±4.0, −1982.4±3.1, and −3556.7±7.6 kJ mol−1. These results, together with others from the literature concerning hopeite, Zn3(PO4)2·4H2O, hydroxyapatite, Ca5(PO4)3(OH), and the synthetic salt Cu3(PO4)2 · 2H2O have been used to construct a model for the formation of suites of Zn(II) and Cu(II) phosphate minerals found in the oxidation zone of base metal orebodies. The distributions and modes of occurrence of many natural assemblages of these minerals are readily explained by the model. Particular attention has been focused on deposits at Broken Hill, Zambia, and Saginaw Hill, Arizona, USA.

A survey of the surface-area-normalized dissolution rates of major phosphate bearing minerals shows these rates to vary by >8 orders of magnitude with a general dissolution-rate trend sturvite > britholite ∼ fluoroapatite > variscite > monazite ∼ rhabdophane. This trend reflects the relative strength of the metal-oxygen bonds holding together the phosphate tetrahedra in the mineral structure. Due to the high surface-area-normalized reactivity of fluoroapatite, and the high surface area of natural variscite and rhabdophane, it seems likely that these minerals buffer the concentration of P and the rare-earth elements in many natural waters. As such, the solubility of these minerals plays a significant role in the global phosphorus cycle, and may potentially provide clues for future sustainable phosphorus use.

Spheniscidite is a new phosphate mineral occurring in a soil profile in an area of nesting penguins on Elephant Island. It is the NH4-dominant analogue of leucophosphite and has the formula (NH4,K)(Fe3+,Al)2 (PO4)2(OH) · 2H2O. It is monoclinic, P21/n with unit cell parameters a = 9.75, b = 9.63, c = 9.70 Å, β = 102° 34′, and Z = 4. The strongest X-ray lines are 6.79(100), 5.99(90), 3.05(45), 7.62(40) Å. Spheniscidite is thought to have formed by the interaction of ammonium phosphate solutions from penguin guano with micaceous and chloritic minerals in the soil. The name is for Sphenisciformes, the order name for penguins, and has been approved by the IMA Commission on New Minerals and Mineral Names.

For complex rocks in which the structure of minerals, rather than their chemical composition, changes with progressive evolution of the system, it makes sense to try and monitor such an evolving system through the progressive change in the crystal structures of the constituent phases. In effect, the paragenetic sequences of minerals in such complex environments should be related to the crystal structures of the constituent minerals. In order to consider variations in structure topology, we need to organize crystal structures into hierarchical schemes, using the hypothesis that structures may be hierarchically ordered according to the polymerization of the coordination polyhedra with higher bondstrengths. Structural units are organized according to the mode of polymerization: unconnected polyhedra, clusters, chains, sheets and frameworks.

The bond-valence structure of (OH) and (H2O) shows that on one side, (OH) and H2O are strong Lewis bases; on the other side, they are weak Lewis acids. As a result, a very important role of both (OH) and (H2O) is to prevent polymerization of the structural unit in specific directions. Thus, the dimensionality of the structural unit is controlled primarily by the amount and role of hydrogen in the structure. The way in which we have formulated these ideas also allows development of a predictive framework within which specific aspects of the chemistry and structure of phosphates can be considered.

This approach to mineral structure, applied via the idea of a structural unit, can play a major role in developing structural hierarchies in order to bring about some sort of order to the plethora of hydroxyhydrated-phosphate structures. Furthermore, by combining the idea of binary structural representation with bond-valence theory, we see the eventual possibility of predicting stoichiometry and structural characteristics of these minerals, particularly those in complex low-temperature hydrothermal environments

The crystal structure and the chemical composition of a paravauxite from the Siglo Veinte Mine, Llallagua, Bustillo Province, Potosi Department, Bolivia [Fe (Fe0.916 2+Mn0.016 2+Mg0.064Ca0.002)∑0.998Al(1)Al(2)Al2.005P (P1.998Si0.002)∑2O8(OH)2·8H2O, a = 5.242(1) Å, b = 10.569(2) Å, c = 6.970(2) Å, α = 106.78(3)°, β = 110.81(2)° and γ = 72.29(2)°, space group P ], was investigated by single-crystal neutron diffraction and electron microprobe analysis in wavelength-dispersive mode. Neutron-intensity data were collected at 293 K and anisotropic structure refinement was performed. At the end of the refinement no peak larger than ±1.3 fm/Å3 was present in the final difference-Fourier map of the nuclear density. The final statistical index was R 1 = 0.0495 for 194 refined parameters and 1678 unique reflections with F o > 4σ(F o). Eleven independent H sites (i.e. H(1), H(2), H(3), H(4A), H(4B), H(5), H(6), H(7), H(8), H(9A) and H(9B)), all at ∼1 Å from the respective O sites, were located successfully. H(4A) and H(4B) and H(9A) and H(9B) are two mutually exclusive subsite couples only 0.4−0.6 Å apart. The complex H-bonding scheme in the paravauxite structure is now well defined and 12 independent H bonds, with an energetically favourable bonding configuration, are described. A comparison between the previous experimental findings based on Raman and infrared spectroscopy and those obtained in this present study is carried out. Paravauxite provides the rare opportunity to investigate the H-bond configuration of coexisting hydroxyl groups and H2O molecules in minerals by single-crystal neutron diffraction. H2O is present as zeolitic (i.e. lying in the cavities) and non-zeolitic H2O (i.e. bonded to Al or Fe to form Al or Fe octahedra).