Tidal mudflats are locally enriched in heavy metals at the head of Strangford Lough in Northern Ireland, where drainage from the hinterland enters the sea lough via a tidal canal in an urban area. To characterize the metallic contaminants and investigate their provenance, heavy particles separated from stream, canal and estuarine sediments were analysed by electron microprobe and laser Raman microspectroscopic methods. Potential metal sources are mineralization in the catchment area and industrial or domestic pollution. Anthropogenic particles include metallic grains, alloys and compounds of Pb, Zn, Cu, Fe, Cr and Sn. Alteration of metallic particles includes de-zincification of brass in freshwater sediment and replacement of Cu wire by covellite in brackish to marine sediment. Mobility of Cu, Fe and S in canal and estuarine sediments is indicated by the authigenic growth of framboidal Fe sulphide on oxide substrates and of chalcopyrite rims on covellite. Intricate colloform and platy crystalline textures suggest a cyclical deposition of covellite and chalcopyrite under conditions of varying redox and salinity. Lead and Cr mobility in the contaminated estuarine sediment is shown by the authigenic formation on Pb-rich substrates of heterogeneous Pb- and Cr-rich sulphate-phosphate compounds and Pb-oxychlorides.

A thermodynamic prediction of the Gibbs free energy of formation (ΔGfo) of nukundamite (empirical composition Cu5.5FeS6.5) was made in order to specify whether the nukundamite + chalcopyrite or the bornite + pyrite assemblage is stable in the Cu-Fe-S system. The results of calculations using previously reported data of ΔGfo values of some Cu-Fe-sulphide minerals in equilibrium with nukundamite indicate that the total free energy of the nukundamite + chalcopyrite assemblage is appreciably higher than that of the bornite + pyrite assemblage in the temperature range 250–400°C. This means that nukundamite + chalcopyrite is a metastable assemblage under common ore-forming conditions.

The occurrence of nukundamite is not uncommon in the Fijian kuroko deposits in contrast to the Japanese kuroko deposits. A thermochemical treatment for this phenomenon leads to the interpretation that the black ore containing nukundamite in the Fijian deposit was formed under relatively highsulphidation and low-pH conditions. This suggestion is in good agreement with the present experimental result that the bornite + pyrite assemblage was produced in the temperature range 350–250°C by using near-neutral hydrothermal solutions.

The kinetics and mechanisms of dissolution of the major base metal sulphide minerals, pyrite, chalcopyrite, galena and sphalerite in acidic (chloride) media have been investigated. Minerals were ground in air, then dissolved in air-equilibrated solutions at pH 2.5, while monitoring the redox potential. Solution samples were analysed by ICP-AES and HPLC, and surfaces of residual sulphides analysed using XPS. Dissolution of aerial oxidation products on pyrite particles in the first 15 min apparently led to a sulphur-rich surface, and was followed by slower dissolution of pyrite itself, driven by oxygen reduction, and resulting in net production of protons. Chalcopyrite dissolution resulted in a Cu, S-rich (near) surface layer, accompanied by net consumption of protons. Apparently incongruent dissolution of galena and sphalerite may reflect the formation of elemental S at the surface. The rates of dissolution of chalcopyrite, galena and sphalerite in the presence of pyrite were determined, respectively, as 18, 31 and 1.5 times more rapid than in single-mineral experiments. These data were consistent with galvanically-promoted mineral oxidation of the other sulphides in the presence of pyrite. In the case of galena, the experimental data suggested extensive release of Pb ions and development of a sulphur-rich surface during galvanically-promoted dissolution.

The oxidation of chalcopyrite and pyrite was examined using Fe-K- and Cu-K-edge REFLEXAFS spectroscopy. The Fe XANES of the pyrite proved to be a very sensitive indicator of oxidation, revealing the development of a goethite-like surface species; the EXAFS data showed an increasing O:S ratio with the degree of oxidation and gave Fe–O distances of c. 1.9 Å. On the oxidized chalcopyrite surfaces, the development of Fe-O and Cu-O species was observed, with both the XANES and EXAFS revealing the progressive development of these species with oxidation. Differences in the sensitivity of the XANES and EXAFS to the degree of oxidation can be related to the degree of long range order and changes in the intensity of the pre-edge feature of the Fe are a function of its oxidation state and coordination geometry in the surface species.

Trace mineral assemblages in the bornite- and chalcopyrite-rich Cu-Fe zone of the Ocna de Fier-Dognecea skarn deposits, Banat, SW Romania provide additional constraints on the genesis of this classic zoned skarn system. Observed assemblages substantiate a model, in which the Cu-Fe zone forms the proximal fluid-plume root of the system. Observed trace mineral assemblages in the magnesian forsterite-bearing skarns crystallized at ~650°C in a volatile-rich environment, evidenced by widespread phlogopite, ludwigite, valleriite and apatite. The entire assemblage thus belongs to the initial stage of skarn formation. Prolonged cooling led to sequential exsolution of trace mineral phases from bornite and chalcopyrite during the retrograde stage, although still at temperatures in excess of 500°C. Bornite is typified by the abundance of exsolved phases along cleavage planes and along crystal margins, notably chalcopyrite and pyrrhotite, but also cobalt pentlandite, carrollite, wittichenite, galena, mawsonite, silver and electrum. Chalcopyrite hosts cobalt pentlandite, carrollite, wittichenite, galena and a sequence of Se- and Te-bearing minerals (kawazulite, bohdanowiczite, hessite, volynskite), along, although not restricted to, grain margins. The assemblage bornite-chalcopyrite-magnetite, with the trace phases, cobalt pentlandite, carrollite, wittichenite and various Se- and Te-bearing minerals represents a characteristic assemblage common to a disparate range of deposits formed at temperatures in excess of 500°C in the presence of volatiles and typified by relatively low fS2 fluids.

Chalcopyrite samples from Mt Isa, Australia have been experimentally shortened by up to 30% at temperatures up to 450°C at a constant confining pressure of 300 (400) MPa, and different strain rates in the range from 10-5 to 10-8 sec-1. After deformation, the X-ray pole figures show a maximum of (220/204) perpendicular to the compression axis for each of the samples, which has already been described for room temperature experiments by Lang (1968). The overlapping pseudocubic peaks of chalcopyrite can be separated into true tetragonal peaks by neutron diffraction texture analysis using a position sensitive detector combined with profile analysis (Will et al., 1989). The five investigated samples each show a combination of two or four main orientations of the crystallites, which represent neither a pseudocubic nor a tetragonal fibre texture.

Concentration data are reported for 18 trace elements in chalcopyrite from a suite of 53 samples from 15 different ore deposits obtained by laser-ablation inductively-coupled plasma-mass spectrometry. Chalcopyrite is demonstrated to host a wide range of trace elements including Mn, Co, Zn, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi. The concentration of some of these elements can be high (hundreds to thousands of ppm) but most are typically tens to hundreds of ppm. The ability of chalcopyrite to host trace elements generally increases in the absence of other co-crystallizing sulfides. In deposits in which the sulfide assemblage recrystallized during syn-metamorphic deformation, the concentrations of Sn and Ga in chalcopyrite will generally increase in the presence of co-recrystallizing sphalerite and/or galena, suggesting that chalcopyrite is the preferred host at higher temperatures and/or pressures. Trace-element concentrations in chalcopyrite typically show little variation at the sample scale, yet there is potential for significant variation between samples from any individual deposit. The Zn:Cd ratio in chalcopyrite shows some evidence of a systematic variation across the dataset, which depends, at least in part, on temperature of crystallization. Under constant physiochemical conditions the Cd:Zn ratios in co-crystallizing chalcopyrite and sphalerite are typically approximately equal. Any distinct difference in the Cd:Zn ratios in the two minerals, and/or a non-constant Cd:Zn ratio in chalcopyrite, may be an indication of varying physiochemical conditions during crystallization.

Chalcopyrite is generally a poor host for most elements considered harmful or unwanted in the smelting of Cu, suggesting it is rarely a significant contributor to the overall content of such elements in copper concentrates. The exceptions are Se and Hg which may be sufficiently enriched in chalcopyrite to exceed statutory limits and thus incur monetary penalties from a smelter.

This work presents a systematic study that evaluates the feasibility and reliability of local band gap measurements of Cu(In,Ga)Se2 thin films by valence electron energy-loss spectroscopy (VEELS). The compositional gradients across the Cu(In,Ga)Se2 layer cause variations in the band gap energy, which are experimentally determined using a monochromated scanning transmission electron microscope (STEM). The results reveal the expected band gap variation across the Cu(In,Ga)Se2 layer and therefore confirm the feasibility of local band gap measurements of Cu(In,Ga)Se2 by VEELS. The precision and accuracy of the results are discussed based on the analysis of individual error sources, which leads to the conclusion that the precision of our measurements is most limited by the acquisition reproducibility, if the signal-to-noise ratio of the spectrum is high enough. Furthermore, we simulate the impact of radiation losses on the measured band gap value and propose a thickness-dependent correction. In future work, localized band gap variations will be measured on a more localized length scale to investigate, e.g., the influence of chemical inhomogeneities and dopant accumulations at grain boundaries.

X-ray powder diffraction data for CuGa0.15In0.85Se2 and CuGa0.50In0.50Se2 are reported. Indexing of the X-ray diffraction powder pattern and the Rietveld refinement confirmed that these compounds crystallize in the tetragonal crystal system, with space group I-42d (No. 122) and lattice parameters of a=5.7528(2) Å and c=11.5225(3) Å for CuGa0.15In0.85Se2 and a=5.6847(1) Å and c=11.2817(1) Å for CuGa0.50In0.50Se2. The CuGaxIn1−xSe2 system presents the chalcopyrite type crystal structure (CuFeS2) and corresponds to two stacked zinc-blende unit cells. The metal atoms Cu, In, and Ga are regularly ordered in the unit cell. Every Se atom is tetrahedrally bonded to two Cu and two In and Ga atoms.