Transmission electron microscopy/analytical electron microscopy (TEM/AEM) were utilized to study pyrite and sphalerite inclusions in chlorite or mixed-layer chlorite-corrensite from an analcimized ash bed in the Etalian stage (Middle Triassic), South Otago, New Zealand. These sulfide inclusions occur as elongated crystals up to 1 × 15 µm in size, within lens-shaped voids between separated, deformed (001) layers of (primarily) chlorite and mixed-layer chlorite-corrensite grains of typical detrital shape or chlorite packets in chlorite-mica stacks (intergrowths of chlorite and phengite packets) up to 40 × 150 µm in size. Relict biotite layers within chlorite, mixed-layer chlorite-corrensite and berthierine have textures implying replacement of the former by the latter, whereas in other unaltered samples only fresh biotite was observed. Anatase occurs in otherwise Ti-free chlorite, whereas relict biotite contains significant Ti (0.3 moles per 22 oxygen atoms). No sulfide minerals have been found in fresh biotite and phengite.

Mass balance considerations indicate that S and Zn were introduced via pore fluids and that the Fe was provided by the decomposition of biotite to secondary phyllosilicates. The alteration of biotite and the reaction of biotite to form chlorite and pyrite is controlled by aH+/aK+ as well as oxidation of reduced S species or reduction of oxidized S species from solution. Simple calculations with the observed compositions of chlorite and biotite suggest that some of the Fe in biotite was actually removed in solution rather than precipitated in pyrite and chlorite. Similar textures are abundant in ferroan phyllosilicates elsewhere, implying that the mechanism may apply widely to precipitation of sulfides in phyllosilicates during early diagenesis of sediments.

Valsassina (Lombardy, Northern Italy) is located in the Lombard Southern Alps and is characterised by the presence of a metamorphic basement, by a major late Variscan intrusive complex and by Carboniferous–Permian volcano-sedimentary cover units. These rocks host a pervasive system of inadequately studied mineralised veins. These veins are characterised by base metal (Pb, Zn, Cu and Fe) and complex polymetallic assemblages.

In this study, we have investigated the ore textures, mineral compositions of sulfides and sulfosalts (by EMPA–WDS and LA–ICP–MS analyses), and stable isotopes (C and O) in carbonate gangue minerals of various mineralised veins to determine the conditions of deposition of these ore deposits. Two different vein families can be recognised in Valsassina: NNW–SSE veins characterised by a complex polymetallic sulfide–sulfosalt assemblage, also with Ni–Co–Fe arsenides and other Ag–Bi-bearing minerals; and NE–SW veins with a simpler, base metal sulfide assemblage. The Ni–Co-bearing NNW–SSE veins have some distinctive features of the ‘five-element vein’ type deposits, with the Ni–Co–Fe arsenide ore stage pre-dating a sulfide-tetrahedrite-dominated ore stage. LA–ICP–MS data for pyrite and sphalerite, and stable isotopic compositions (C and O) of the carbonate gangue minerals, show no clear differences between the two families of veins, which are probably linked genetically. The isotopic compositions of the Valsassina vein carbonates are closely comparable with the signature of several major five-element ore districts. Preliminary temperature estimates for the Valsassina vein systems were based on the sphalerite composition, applying the GGIMFis geothermometer. The estimated temperatures for the sulfide-dominated ore stage post-dating the Ni–Co minerals precipitation range between 100 and 250°C. The crosscutting relationships, observed for all the veins with the host rocks, suggest a possible late to post Variscan (late Permian) age, making these vein systems comparable with other late–post Variscan polyphase hydrothermal events affecting large sectors of the Southern Alpine domain.

Zoning texture in sphalerite has been described in many studies, although its genesis and ore formation process are poorly constrained. In this investigation, we compare the in situ trace element and isotopic composition of colour-zoned sphalerites from Nayongzhi, South China, to explain the zoning growth process. Petrographic observations identified two broad types of zoned sphalerite, core–rim (CR) and core–mantle–rim (CMR) textures. Each zoned sphalerite displays two or three colour zones, including brown core, light colour bands and/or pale-yellow zones. In situ laser ablation inductively coupled plasma mass spectrometry trace-element analyses show that the three colour zones display variable trace-element compositions. Brown cores exhibit distinctly high Mn, Fe, Co, Ge, Tl and Pb concentrations, whereas pale-yellow and light colour zones have elevated Ga, Cd, Sn, In and Sb concentrations. Copper, Sb, In and Sn show slight variations between pale-yellow and light zones, the latter having higher In and Sn, but lower Cu and Sb abundances. Given the low concentration range of Pb, Ge, Tl, Mn Sb, Cd, etc., the colour of sphalerite is attributed mainly to Fe compositional variation. The δ34S values of sphalerite from Nayongzhi range from +22.3 to +27.9‰, suggesting reduced sulfur was generated by thermochemical sulfate reduction of marine sulfate in ore-hosted strata. Single-crystal colour-zoned sphalerite exhibits intracrystalline δ34S variation (up to 4.3‰), which is attributed to the δ34S composition of H2S in the original fluid. The lack of correlation between trace elements and δ34S values indicates episodic ore solution influxes and mixes with the reduced sulfur-rich fluid derived from the aquifers of the ore-hosted strata, which play a key role in the formation of the zoned Nayongzhi sphalerite. In conclusion, in situ trace element and S isotope studies of zoned sphalerite crystals might provide insight into the ore-forming process of MVT deposits.

Samples from the sphalerite-dominated zone of a seafloor massive sulfide chimney, the Satanic Mills Chimney of the PACMANUS hydrothermal field, have been investigated to determine the internal macrostructure and microstructure of this zone, the phases present, and the distribution of metals. A combination of electron probe microanalysis, electron backscattered diffraction, and x-ray diffraction has been used. At the macroscale, this zone of the chimney wall is heavily porous and is comprised primarily of sphalerite, enclosing minor chalcopyrite, pyrite, and wurtzite. A Pb–As sulfosalt layer of possible microbial origins is present at the outer edge of the sphalerite matrix, next to a pore. The sphalerite has grown in globules on the order of 300 μm in diameter. At the microscale, the sphalerite features a colloform texture and a duplex-type grain structure consisting of either fine-grain regions in the center surrounded by coarse-grained regions or radiating coarse grains only. Pb- and As-rich bands have been detected in the colloform sphalerite, and growth twins have been observed in both the sphalerite and chalcopyrite crystals. A qualitative description of the growth of a typical globule is given, including nucleation, crystal growth, and solute redistribution.

The Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province is one of the most productive areas of Pb–Zn resources in China. The Fule deposit occurs in Permian carbonate and contains Pb–Zn reserves exceeding 1 Mt. To investigate the sulphur source, in situ S isotopic analysis of sphalerite and pyrite was carried out using nanoscale secondary-ion mass spectrometry. The results show that the δ34S values of the sulphide minerals range from +16.1‰ to +23.0‰, higher than that of marine sulphates hosted in Permian carbonate rocks (+11‰), but similar to that of sulphates over a broader area (+12.9‰ to +25.9‰). The sulphates in the regional rocks could therefore represent an important source of S for the Fule deposit via thermochemical sulphate reduction. The S source of the Fule deposit is different from those of most other Pb–Zn deposits in the SYG Pb–Zn mineralization province, which were mainly derived from the ore-bearing strata. The δ34S values of the early to late generations and some single sulphide crystals from the cores to rims show a slight increasing trend, implying that partial Rayleigh fractionation took place in the Fule deposit. It is suggested that the Fule sulphide precipitation resulted from the mixing of a metalliferous fluid with a H2S-rich fluid derived from the regional strata. Combining the geology, mineralogy and S isotope results with previous Pb isotope studies, it is suggested that the Fule deposit should be attributed to a Mississippi Valley type deposit.

Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In3+ replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (NS = 2.4–2.5, RAu–S = 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au2S clusters predominate, with a small admixture of the Au+ solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu+ with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn2+↔Me++Me3+. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.

Optical microscopy of doubly polished thin sections of North Pennine sphalerite has revealed a range of previously unrecognised textures for the Alston Block mineralisation. Delicate growth zoning, interrupted by numerous solution disconformities, was seen in transmitted light. Two principal varieties of growth-banded sphalerite are recognised; the earlier (Type 1) is characterised by the development of thin opaque bands. Type 2 has colour bands between yellow and brown, correlated with iron content. In Type 1, iron levels (up to 3 wt.%) are not sufficient to account for the observed opacity. Ultra-violet and infra-red techniques failed to detect any organic inclusions. Electron microscopy revealed locally high concentrations of sub-micrometre inclusions, both beam-stable and beam-unstable, and a variety of growth-related crystal defects.

Fluid inclusion thermometry in both sphalerite varieties and the accompanying quartz gangue implies a saline mineralising fluid (20–25 wt.% equiv. NaCl) at a relatively low temperature (100° to 140°C). Tubular inclusions are conspicuous. A deformation-induced lamelliform optical anisotropy is superimposed on a growth-related grid-iron anisotropy. Growth band offset is apparent where the deformation fabric cross-cuts the growth banding. Deformation on {111} twin and slip planes was indicated by electron microscopy.

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.

A recent investigation of sphalerite from Akoluk deposit, Ordu, NE Turkey, revealed the possible presence of a new activator element in the sphalerite structure. The sample was studied under a reflected light microscope coupled with a cold-stage cathodoluminescence (CL) system which revealed a unique banding in the sphalerite. The same sample was subsequently examined using the backscattered electron and luminescence modes in an electron microscope, the results of which were later confirmed in terms of chemical composition by electron probe microanalyses (EPMA). Detailed evaluation of the EPMA data indicated the presence of a new CL activator element in the sphalerite structure. The data also indicate that Hg2+ in the sphalerite crystal structure substitutes for Zn in a simple manner and for Cd and Cu in a coupled manner. Spectral analysis indicated a bright yellow and orange-red blend (more like brown) CL colour with λmax centred at 580 nm, probably due to Cd and Mn ions, and relatively broad emission bands ranging from 525 to 690 nm with λmax centred at 580 and 700, due probably to Cu, Cd and Hg. This study reports that Hg in the sphalerite crystal lattice behaves as an activator and/or co-activator element resulting in emissions of CL colours that range from yellow with purple shades to shades of brown, based on their varying contents.

Over the past several decades, thinking about chemical processes in rocks had been dominated by experimental and theoretical treatments of mineral equilibrium, which is the state from which the time variable has been excluded. But, to an extent exceeding that of any of our sister sciences, we in geology are concerned with the behaviour of things as a function of time; thus equilibrium is but one of several interesting boundary conditions. Textures, (defined as the spatial relations within and among minerals and fluids, regardless of scale or origin) provide a means to sort out and identify successive states. In fact, it is the pattern of evolution of those states that enables us to deduce the processes. We may well draw the analogy with thermodynamics and kinetics, respectively:

equilibrium textures and phase assemblages, via thermodynamic analysis → definition of conditions of equilibration,

whereas

kinetics, as displayed in disequilibrium textures → sequence of events and processes of mineralization.

The interpretation of textures is one of the most difficult yet important aspects of the study of rocks and ores, and there are few areas of scientific endeavour that are more subject to misinterpretation. Although the difficulties are many, the opportunites for new understanding are also abundant. Textural interpretations have many facets: some are well established and accepted; some that are accepted may be wrong; others are recognised to be speculative and controversial; and we trust that still other textural features remain to be described and interpreted. This paper will deal principally with low-temperature, epigenetic ore deposits, and will emphasise silica and sphalerite; but extension to other materials is not unreasonable.

Ore and gangue minerals react internally, or with their environment, at widely ranging rates, ranging from the almost inert pyrite, arsenopyrite, well-crystallised quartz, and tourmaline to the notoriously fickle copper/iron and copper/silver sulfides. Arrested or incomplete reactions may be identifed by textural criteria and, when appropriately quantified, can provide guides to the duration of geological processes.

In recent years so much emphasis has been placed on isotopes, fluids, chemistry, and deposit and process models that the textural features have been ignored. In part this oversight occurs because we have grown accustomed to using superposition, cross-cutting, pseudomorphism, mutual intergrowths, exsolution and so on as off-the-shelf tools, to be grasped and applied without evaluation or even description. Surely science must build on previous work without constant and exhaustive reassessment, but for mineral textures a little reassessment may yield substantial benefit.

Banded sphalerite from Bleiberg, Austria, contains ubiquitous relics of Fe-thiosulphates and Fesulphites up to 50 μm in size. Zn, Pb, Ni and As form admixtures ranging from a few to 12 wt.% in these compounds. It is suggested that banded sphalerite is formed by a replacement of banded thiosulphate and thiosulphite precursors. This suggestion is supported by a significant admixture of Fe 0.41-8.20 wt.%) and the presence of goethite inclusions in banded sphalerite. In contrast, crystalline ZnS intergrown with the banded variety is Ni-free and contains only 0.06-0.14 wt.% Fe.

Banded pyrite contains inclusions of Fe-thiosulphate up to 200 μm in size. These thiosulphates contain (wt.%): 0.09-1.92 Zn, and 2.67−4.02 Pb. Pyrite formed by replacement (breakdown) of Fethiosulphate precursors contains 3.69-3.83 wt.% Pb.

It is suggested that banded sulphides precipitate from solutions carrying sulphur with mixed valances, and crystalline sulphides grow from solutions where the dominant dissolved sulphur is in the form of sulphidic anions.

We have developed a cluster variation method (CVM) model based on cuboctahedral and octahedral basis clusters containing 13 and 6 atoms, respectively, and applied it to the analysis of the thermodynamic mixing properties of (Zn,Fe)S solid solutions. The model, in which the internal energy of the lattice is approximated by next to nearest neighbour (nnn) pair interactions and many-body interactions associated with nearest neighbour (nn) equilateral triangles, describes the FeS contents of sphalerites equilibrated with pyrrhotite and pyrite, and with pyrrhotite and iron metal within experimental uncertainties. The model predicts moderate deviations from ideality; the mean values of the Lewis and Randall activity coefficient of FeS and ZnS are, 1.48 and 1.03, respectively. Predictions of the model are in qualitative agreement with cell-edge data. The model also predicts that sphalerites undergo long-range ordering to lower-symmetry structures at temperatures only slightly below those investigated experimentally, a result in agreement with inferences from an existing Mössbauer investigation of synthetic sphalerites.

More realistic models in which interactions are ascribed to larger species (nn triangular and centred square species) predict that such long-range ordering occurs at even higher temperatures and underscore the need for better characterization of the structures of (Zn,Fe)S minerals.

Gold-silver vein deposits in the Taebaeksan district, Korea, coexist in time and space with a variety of other deposit types such as skarns, hydrothermal carbonate replacement bodies and Carlin-like deposits and reflect proximity to a magmatic source. The seven gold-silver deposits within the district show common features such as multiple complex veins, an abundance (up to 30% in ore) of base-metal sulphides, a wide range of Ag/Au ratios and the common occurrence of carbonate. Quartz-vein textures indicate open-space-filling at shallow crustal levels. On the basis of Ag/Au ratios of ore, mode of occurrence, and associated mineral assemblages, the seven deposits studied can be classified as follows; Au-dominant type (Group I), Au-Ag type (Group II), Ag-dominant type (Group IIIA) and base-metal and Ag-dominant type (Group IIIB). Group I is characterized by paragenetically early Pb-Zn basemetal sulphides with electrum and late, rare Ag-sulphides and Ag-sulphosalts, whereas Group III contains more Ag-sulphides and/or Ag-sulphosalts. Group II is gold-rich, but transitional to Group III. The Au contents and FeS contents of electrum and sphalerite, respectively, from all of the deposits decreased as mineralization proceeded. Temperature and log fS2 conditions of gold-silver mineralization tend to decrease from Group I and II to Group III deposits (i.e. 340–270°C, –9.3 to –11.8 bar, 320–240°C, –9.5 to –10.3 bar, 250–160°C, –12.5 to –16.9 bar, respectively) as well as from the main to late stages of mineralization in each deposit. The systematic mineralogy and variation of physicochemical conditions in Groups I, II and III are thought to be due to their relative positions with respect to a magma source that is genetically related to a low-to-intermediate-sulphidation porphyry system. Au-rich deposits are proximal to a magmatic source, whereas Ag-rich deposits are more distal.

In the Gåsborn area, West Bergslagen, central Sweden, Fe-rich, indium-bearing (0.1–2.0wt.% In) sphalerite is replaced by Fe-poor sphalerite containing minute inclusions of chalcopyrite, roquesite and an unnamed In-Zn-rich phase. Fe-rich, In-bearing sphalerite is primary; indium occurs as a roquesite molecule in solid solution. Fe-poor sphalerite, roquesite, chalcopyrite and the unnamed In-Zn-rich phase were formed from In-bearing sphalerite by secondary processes, characterized by the so-called ‘chalcopyrite disease’.

The dispersion and sediment-water partitioning of Pb and Zn have been studied in the Conwy River, North Wales. Analysis included major and trace element water chemistry and concentrations of sediment-hosted Pb and Zn. In situ solution pH, Eh, temperature and conductivity were also measured. Sediments were characterized via SEM, XRD, nitric acid leaching and sequential chemical extraction to quantify metal distribution and sediment phase associations. Dissolved and sediment-bound Pb and Zn within river and estuary waters and sediments have been used to calculate whole sediment- and phase-specific apparent partition coefficients.

Weathering of galena and sphalerite, associated with the Llanrwst Mining Field, provide point sources of elevated dissolved and sedimentary Pb and Zn in the upper catchment. Dissolved Pb is actively adsorbed onto sedimentary surface coatings of Fe-Mn (hydr)oxides and organics whilst Fe-Mn (hydr)oxides, organics and carbonates were the main hosts for Zn. Systematic changes in metal sorption are evident between the estuary and the upper catchment, with organic matter becoming progressively more important upstream. This change is ascribed to the sorptive properties of sedimentary organic material. Solution pH, [Cl] and aqueous metal speciation are the dominant solution controls on metal partitioning. Laboratory sorption experiments parallel Pb sorption behaviour in the natural system.

Back-scattered electron imaging with a scanning electron microscope was applied to the intimate association of fine chalcopyrite grains and sphalerite (‘chalcopyrite disease’) in synthesized products and natural specimens, in order to distinguish between diagnostic features of two formation mechanisms: replacement and coprecipitation. In the synthetic chalcopyrite disease in Fe-bearing sphalerite formed by a replacement reaction, chalcopyrite occurs as fine lamellae, which are also observed in relatively Fe-rich growth bands of the natural zoned sphalerite. Ellipsoidal to lens-like habits of chalcopyrite appear in sphalerite that has undergone extensive replacement reactions. These textures may have grown steadily from the lamellar chalcopyrite by consuming the FeS component dissolved in the sphalerite. All the sphalerite samples formed by the coprecipitation mechanism are Fe-poor, hosting triangular or irregularly bleb-like inclusions of chalcopyrite. This variety of chalcopyrite morphology could be attributed to diffusion rates and variations in fluid saturation, and their effect on the rate of crystal growth. Thus, in both replacement and coprecipitation the chalcopyrite habit depends strongly both on the FeS content of the host sphalerite and on kinetic factors, and is significant when interpreting chalcopyrite disease textures in natural samples.