The sulphide ores from the Julcani mining district (Peru) display many retrograde reactions that may be attributed to solid-state processes accompanying cooling. Fahlores [˜(Cu,Ag)10(Zn,Fe)2(Sb,As)4S13] from the Herminia mine exhibit pronounced downstream enrichments in molar Ag/(Ag+Cu) ratios that are strongly correlated with the abundance of PbS-AgSbS2-AgBiS2 phases. These correlations, discontinuous core to rim Sb/(Sb+As) enrichments in bournonites, and prominent reaction textures involving fahlores, bournonites and galenas provide strong evidence that the fahlores in these ores have been enriched in Ag by the Ag–Cu exchange reaction

which occurred during cooling following mineralization of a PbS-AgSbS2-AgBiS2 galena and has been documented elsewhere. Secondary PbS-AgSbS2-AgBiS2 minerals aramayoite, bismuthian diaphorite [Pb2Ag3(Bi,Sb)3S8], and diaphorite were produced from primary galenas with cooling of ores with high Pb/Cu and Bi/Sb; pyrargyrite formed from the breakdown of the Ag10Zn2Sb4S13 component in the most Ag-rich fahlores, as an exsolution product of galena, and from replacement of aramayoite and galena with the evolution of semimetal sulphides. Based on mineral compositions, phase equilibria, a thermochemical database for sulphides and sulphosalts, and the reintegrated composition for primary grains of Ag-rich PbS-AgSbS2-AgBiS2 phases, we estimate that the primary temperature of hydrothermal mineralization was >320±10°C, that these reactions ceased to affect fahlore Ag/(Ag+Cu) ratios and Bi/(Bi+Sb) ratios of aramayoite and miargyrite after cooling through 220±10°C. Galenas, however, appear to have continued to adjust their compositions to reflect even lower temperatures by continued exsolution of semimetals and production a diverse suite of sulphosalts that occur in fine intergrowths with galena.

The molecular structure of the three vivianite-structure, compositionally related phosphate minerals vivianite, baricite and bobierrite of formula M32+(PO4)2.8H2O where M is Fe or Mg, has been assessed using a combination of Raman and infrared (IR) spectroscopy. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 3460, 3281, 3104 and 3012 cm−1 for vivianite. The high wavenumber band is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH-bending modes where a strong IR band centred around 1660 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH-bending bands fromstrongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. The Raman phosphate PO-stretching region shows strong similarity between the three minerals. In the IR spectra, complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong IR bands around 800 cm−1 are attributed to water librational modes. The spectra of the three minerals display similarities due to their compositions and crystal structures, but sufficient subtle differences exist for the spectra to be useful in distinguishing the species.

The composition of chevkinite and perrierite, the most common members of the chevkinite group, is closely expressed by the formula A4BC2D2Si4O22, where A = (La,Ce,Ca,Sr,Th), B = Fe2+, C = (Fe2+,Fe3+,Ti,Al,Zr,Nb) and D = Ti. The A site is dominated by a strong negative correlation between (Ca+Sr) and the REE. Chondrite-normalized REE patterns are very variable, e.g. in LREE/HREE and Eu/Eu*. The C site is dominated by Ti, Al and Fe2+, in very variable proportions. Most chevkinites and perrierites are close to stoichiometric, with cation sums between 12.9 and 13.5, compared to the theoretical 13. There is no single, generally applicable charge balancing substitution scheme in the group; however, the general relationship

defines a linear array with r2 = 0.91. Chevkinite and perrierite are shown to be compositionally distinct on the basis of CaO, FeO*, Al2O3 and Ce2O3 abundances. Chevkinite forms mainly in chemically evolved parageneses, such as syenites, rhyolites and fenites associated with carbonatite complexes. Perrierite is more commonly recorded from igneous rocks of mafic to intermediate composition. The compositional characteristics and possible structural formulae of other members of the chevkinite group are reviewed briefly.