Glauconite from the oxidized and reduced zones of soil-geologic columns at two Coastal Plain sites, one in Maryland and one in New Jersey, was examined by Mössbauer spectroscopy. The data indicate that glauconite in the reduced zones had a higher proportion of its structural iron in the ferrous, as opposed to the ferric state. The Fe2+/Fe3+ ratio ranged from 0 to 0.2 for the glauconite from the oxidized zone and was about 0.35 for the glauconite in the reduced zones. Despite the presence of pyrite in the reduced zone, which might be expected to make ferric iron unstable because of the presence of sulfide S, about 75% of the Fe in the glauconite in the reduced zone was in the ferric state. Thin section analysis showed some glauconite in the reduced zones to be intimately associated with pyrite and some aggregates of fine pyrite crystals were locally present in cracks in glauconite pellets. In the oxidized zones, pyrite was absent and the glauconite was more yellow under plane-polarized light, as opposed to more green for the glauconite in the reduced zones. These data indicate that reports of studies of glauconite should stipulate whether samples are from the oxidized or reduced zone of soil-geologic columns.

The mineralogy of partially kaolinized strata interbedded with lignite at the San Miguel mine, Atascosa County, Texas, was investigated by X-ray powder diffraction and optical and scanning electron microscopy. The San Miguel lignite occurs in the lower Jackson Group (late Eocene) of southern Texas. Based on mineralogical and micromorphological data, some of these clay partings are probably volcanic in origin and were exposed to variable degrees of in situ kaolinization in a swamp environment. Coexistence of kaolinite, clinoptilolite, and opal-CT in several of these strata suggests that the partially kaolinized volcanic layers were subjected to a subsequent resilication process following burial. Kaolinite is the dominant mineral in the oldest and most kaolinized volcanic layer (underclay) below the lowest lignite bed (seam D). The kaolinite exhibits a well-developed vermicular morphology. The youngest volcanic layer, which occurs stratigraphically above the uppermost lignite seam, is characterized by pseudomorphs of volcanic glass shards and consists mainly of clinoptilolite. Movement of siliceous ground water from this layer to the underlying strata apparently provided silica-rich solutions from which opal-CT and large (as long as 300 μm) euhedral crystals of clinoptilolite precipitated in the fossilized plant roots, veinlets, and fractures within the underlying strata. Micromorphological relationships between the Sirich (opal-CT and clinoptilolite) and sulfide (marcasite and pyrite) minerals in the fossil roots and fractures suggest that the marcasite formed before and pyrite after the resilication process.

Many of the presently oxidized Georgia kaolins probably existed originally in the reduced (gray) state. For that reason, the distribution of iron sulfides in presently gray kaolins may elucidate features observed in oxidized kaolins. An understanding of the nature of gray kaolins may also aid in the development of processing strategies for the exploitation of these abundant resources. The size, morphology, and degree of crystallite bonding of iron sulfides (pyrite and marcasite) in three gray kaolin cores from the Macon, Georgia kaolin district were examined by X-ray powder diffraction, X-ray fluorescence, scanning electron microscopy, and other physical and chemical methods. Pyrite and marcasite were identified as dominantly gravel- and sand-size equant crystals and crystal aggregates, rather than as framboids. Pyrite crystals commonly showed rough octahedral faces, which extended over minor cube faces. Locally, spiral growth dislocations were also observed. Marcasite was found in radiating, prismatic, and tabular crystals. In general, the marcasite crystal aggregates were much more fragile than those of pyrite. The dominance of octahedral crystal shapes and textures of the pyrite suggest inorganic precipitation from solutions supersaturated with respect to octahedral crystal faces.

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.

Lower Wham Brake is a cypress, rim-swamp artificially enclosed in 1950 as a 22 km2 industrial reservoir by the International Paper Company (IPC)-Bastrop Mill, for regulating downstream water quality. Sediment cores were examined by XRD to differentiate paper-mill effluent deposition from the underlying detrital sediments and by 210Pb decay spectroscopy to determine sediment accretion rates.

Anatase and kaolin from the IPC paper-mill effluent delineated a well-defined, anthropic, silty-clay, A horizon above a clay, 2Ag horizon. Anatase concentrations were no greater than 1.7% in the A horizon and was absent in the underlying 2Agl horizon. Kaolin deposition was significantly correlated to the A horizon by an average increase of 84% above the kaolinite detrital background. Pyrite was detected in the A horizon as a transformation mineral following sulfur reduction of the paper-mill effluent.

Five of the six sediment cores showed an inflection in the excess 210Pb activity profile consistent with a present-day reduction in sediment supply. The average modern sedimentation rate was 0.05 cm yr−1. Average sedimentation observed during historic accretion was 0.22 cm yr−1, about 4.4 times greater than the modern rate of accretion. Reduction in sediment accretion can be attributed to upstream levees completed in 1934 and loss of organic accumulation following the 1950 reservoir impoundment. However, radiometric dating could not precisely correlate the geochronology of kaolin/anatase introduction due to complex oxidation/reduction cycles concurrent with the modern accretion regime.

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.

Millimetric to centimetric green grains widespread in pelagic calcareous sediments recovered at a water depth of3000 m near the Costa Rica margin were studied by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. Samples were collected, during the Ticoflux II expedition, from the upper bioturbated part of four sedimentary cores (0.13–3.75 m below seafloor). The sediments are calcareous and siliceous nanofossil oozes (coccoliths, diatoms, radiolarians, etc.).

Green grains show generally a concentric zoning with a green rim in which smectite largely predominates over pyrite and a black core in which pyrite is prevalent. Observations by SEM indicate that this zoning results from a progressive inward alteration and replacement of the accumulations of pyrites by smectites. The high-resolution TEM observations of the smectite-pyrite interfaces suggest that the replacement of pyrites by smectite occurs through a dissolution-precipitation process with the formation of a gel. The pyrite matrix is composed of a huge number of very small (0.5–22 µm) pyrite octahedra, a typical texture resulting from the pyritization of organic material in early diagenetic environments.

The accurate mineralogical and crystal chemical characterization of the smectites indicate that they are Fe3+-montmorillonites (Fe3+-rich smectite with a dominant octahedral charge, rarely recorded in the literature). The formation of such Fe3+-montmorillonites forming green grains could be explained by two successive diagenetic redox stages: (1) reducing stage: early pyritization of the organic matter by microbial reduction within reducing micro-environments; (2) oxidizing stage: Fe3+-montmorillonite crystallized in space liberated after dissolution of pyrite connected with the rebalancing of the redox conditions of the micro-environments with the oxidizing surrounding sediments.

The state of iron in coal gangue minerals is an important factor in determining the potential for value-added utilization of this solid waste; this is especially true for the coal gangue coming from the Pingshuo open-pit mine in China. The objective of the present study was to characterize the petrological, mineralogical, and chemical states of Fe in the coal gangue from the Carboniferous Taiyuan Formation. Methods used included polarizing microscopy, X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), X-ray fluorescence, micro-Fourier-transform infrared (micro-FTIR) spectroscopy, and Mössbauer spectroscopy. The coal gangues are mudstones, silty mudstones, and pelitic siltstones, which are composed primarily of kaolinite, quartz, feldspar, pyrite, illite, and magnesite. In coal gangue, the Fe was found to occur in ferruginous minerals, in crystal-lattice substitutions, or in a colloidal state. The ferruginous minerals in the coal gangue are pyrite and marcasite, and the pyrite morphologies are framboidal, euhedral octahedral crystals, subhedral granular crystals, and irregular crystals. The results of SEM–EDS and micro-FTIR confirmed that the lattice substitution of Fe in the coal gangue minerals occurred mainly in kaolinite, resulting in two types of kaolinite: iron-containing and iron-free kaolinite. The former may be transformed from volcanic biotite and the latter from volcanic feldspar. The Mössbauer spectra of kaolinite showed intense doublets with isomer shift and quadrupole splitting values consistent with tetrahedrally coordinated Fe3+ and ocahedrally coordinated Fe2+, suggesting the presence of two types of substitution sites: (1) Fe2+ replacing Al3+ in the octahedral sheet; and (2) Fe3+ replacing Si4+ in the tetrahedral sheet. This study has important theoretical significance for the high-value utilization of coal gangue.

The interaction between chalcopyrite and illite particles was analysed using ζ-potential measurements and flotation tests. Statistically designed tests were used to examine the factors controlling flotation (frother concentration, dispersant concentration, froth height, airflow rate and amount of clay). Furthermore, the significance levels of the impacts of these factors on responses (chalcopyrite grade/recovery, pyrite grade/recovery, dynamic froth stability and mean bubble diameter) were determined. Chalcopyrite and pyrite ζ-potentials were measured in the presence of illite. The addition of 15% illite to the chalcopyrite, especially between pH 11 and 12, shifted the ζ-potential values closer to that of pure illite, indicating complete surface coating of chalcopyrite with illite. In the flotation experiments, better results were obtained in terms of chalcopyrite grade at a low airflow rate and a high froth height. With increasing froth height there was a decline in the gangue mineral recovery as the residence time of the froth increased. The most significant factor increasing pyrite recovery was the amount of clay. Although illite is considered to be the least problematic clay mineral for flotation, as reported in the literature, an illite content of as low as 5% in the ore decreased chalcopyrite grade by 3.83%. While K and Na contents of 4% were detected after flotation without the addition of illite, their abundance increased to 5.7% after the addition of illite.

Using a combination of simulated data and pyrite isotopic reference materials, we have refined a methodology to obtain quantitative δ34S measurements from atom probe tomography (APT) datasets. This study builds on previous attempts to characterize relative 34S/32S ratios in gold-containing pyrite using APT. We have also improved our understanding of the artifacts inherent in laser-pulsed APT of insulators. Specifically, we find the probability of multi-hit detection events increases during the APT experiment, which can have a detrimental effect on the accuracy of the analysis. We demonstrate the use of standardized corrected time-of-flight single-hit data for our isotopic analysis. Additionally, we identify issues with the standard methods of extracting background-corrected counts from APT mass spectra. These lead to inaccurate and inconsistent isotopic analyses due to human variability in peak ranging and issues with background correction algorithms. In this study, we use the corrected time-of-flight single-hit data, an adaptive peak fitting algorithm, and an improved deconvolution algorithm to extract 34S/32S ratios from the S2+ peaks. By analyzing against a standard material, acquired under similar conditions, we have extracted δ34S values to within ±5‰ (1‰ = 1 part per thousand) of the published values of our standards.

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.

To study thermal desulfurization of pyrite (FeS2), we conducted in situ neutron diffraction experiments in the temperature range 298–1073 K. On heating, pyrite remained stable up to 773 K, at which it started to decompose into pyrrhotite (Fe1−xS) and S2 gas. Rietveld analysis of the neutron data from 298 to 773 K allowed determination of the thermal expansion coefficient of pyrite (space group Pa$\bar 3$) to be αV = 3.7456 × 10−5 K−1, which largely results from the expansion of the Fe–S bond. With further increase in temperature to 1073 K, all the pyrite transformed to pyrrhotite (Fe1−xS) at 873 K. Unit-cell parameters of Fe1−xS (space group P63/mmc) increase on heating and decrease on cooling. However, the rates in cell expansion are larger than those in contraction. This hysteresis behavior can be attributed to continuous desulfurization of pyrrhotite (i.e., x in Fe1−xS decreases) with increasing temperature until the stoichiometric troilite (FeS) was formed at 1073 K. On cooling, troilite underwent a magnetic transition to an orthorhombic structure (space group Pnma) between 473 and 573 K. In addition, using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) implemented with a differential scanning calorimeter, we performed kinetic measurements of pyrite decomposition. Detailed peak profile and Arrhenius (k = A exp(−Ea/RT)) analyses yielded an activation energy Ea of 302.3 ± 28.6 kJ/mol (based on DTA data) or 302.5 ± 26.4 kJ/mol (based on TGA data) and a ln(A) of 35.3 ± 0.1.

The Georgia, USA, kaolins contain three major occurrences of Fe-sulphide minerals, namely (1) in burrow structures, (2) as nodules associated with lignite and (3) as finely disseminated material. We have used sulphur isotope analysis and X-ray powder diffraction to understand these three occurrences in order to gain insight into the diagenetic conditions and microbial influences affecting the kaolin mineralogy. Burrows and nodules are dominated by corroded marcasite with thin pyrite overgrowths. The δ34S composition of each sulphide sample has internal fractionations (δ34Shigh – δ34Slow) ranging from 22‰ to 67‰. The secondary pyrite phase tends to be the most 34S depleted, with a low δ34S value of –47‰, whereas marcasite displays a δ34S range from 30‰ to +33‰. Early acidic environments from organic acids could have facilitated the initial marcasite crystallization, with a pH increase during later diagenesis producing pyrite overgrowths. Sulphide formation would have continued until burial restricted the diffusion of sea-water sulphate. At this point, the metabolism of sulphate-reducing bacteria would have been retarded, producing δ34S values ranging from –30‰ (open sulphate supply) to +40‰ (highly restricted sulphate supply). Under the nutrient-starved conditions of later-diagenesis, disproportionate sulphur-reducing bacteria would likely have become more dominant, yielding additional δ34Ssulphide fractionation and producing the observed fractionation (δ34Ssulphate – δ34Ssulphide) values of +67‰.

Sulphur isotope ratio measurements (δ34S) of diagenetic pyrite are commonly used to identify S sources and mechanisms of sulphide formation in basinal sediments. This study reports such data for a diagenetic pyrite nodule from the Brent Group sandstones of the northern North Sea at three sampling scales: 50 cm (core subsample), 500 μm (laser microprobe) and 50 μm (ion microprobe). Similar δ34S variations are found by the laser and ion microprobe techniques. There is a very wide range in δ34S (<−10% to >+50%) within the nodule and isotopically heavy S (δ34S >+20%) is common at all scales. The nodule δ34S distribution does not fit a Rayleigh fractionation pattern. The laser microprobe sampling at 100–500 μm scales seems to be adequate to characterize S isotope variations in this material.

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.

There is an association between the development of cleavage domes, a texture reflecting the displacement of insoluble matrix grains by porphyroblasts growing under a bulk hydrostatic stress, and textural sector-zoning. This has been found in garnet, staurolite, chiastolite, pyrite and possibly emerald porphyroblasts. Sector-zoned porphyroblasts form by lineage growth normal to the crystal faces. This causes several distinctive textures (type 1 inclusions and type 2 intergrowths, inclusion bands, growth prongs), all of which are directly or indirectly related to displacement growth. Graphite or other carbonaceous material is ubiquitous in samples showing textural sector-zoning.

The origin in rocks of the common iron sulphides, pyrrhotine, Fe1-xS and pyrite, FeS2 and their behaviour during geochemical processes is best considered using the simplified redox reaction: 2FeS ⇌ FeS2 + Fe2+ + 2e−.

Thus pyrrhotine is more reduced than pyrite and is the stable iron sulphide formed from magmas except where relatively high oxygen fugacities result from falling pressure or hydrothermal alteration. Pyrite, on the other hand, is the stable iron sulphide in even the most reduced sedimentary rocks where it usually forms during diagenesis through bacteriogenic reduction of sulphate; it is stable throughout the pressure/temperature range endured by normal sedimentary rocks. Pyrrhotine after pyrite or sulphate in metasediments of regional metamorphic origin results mainly from progressive reduction on metamorphism due to the presence of graphite-buffered fluids. Pyrrhotine and/or pyrite may be precipitated from hydrothermal solutions on epigenetic or syngenetic mineralization but pyrrhotine will only be preserved if protected from oxidation to pyrite or to more oxidized species. Exhalative pyrrhotine appears to have been more common in Precambrian times and/or in depositional environments destined to become regionally metamorphosed. FeS can be considered to be the soluble iron sulphide, rather than FeS2, in reduced aqueous systems although pyrite may precipitate from solution as a result of redox reactions. The relatively soluble nature of FeS explains the observed mobility of iron sulphides in all rock types.

Two distinct generations of pyrite, with different morphologies, are described from the Proterozoic Broken Hill-type Pinnacles deposit in western NSW. The earlier, py1, forms concentric layers interpreted as colloform banding. Although the textures are somewhat similar to those observed in supergene alteration zones, textural relationships in fresh rocks suggest that these are pre-metamorphic and that the pyrite formed as the result of precipitation from hydrothermal fluids in open veins, vugs and fissures. The second generation, py2, post-dates py1 and forms euhedral overgrowths on it. It is interpreted as being synchronous with the main phase of base metal sulphide mineralisation. The textures reported here are previously unrecorded for Broken Hill-type mineralisation, and have implications for the regional identification of feeder zones to the Broken Hill deposit. The evidence supports a model in which mineralising conditions at the Pinnacles were characterised by slightly higher oxygen and lower sulphur fugacity (further constrained by Fe contents of sphalerite) than at Broken Hill, where pyrrhotite is the major Fe sulphide.

The pre-metamorphic textures observed in the pyrite at the Pinnacles deposit are also unusual because they have survived granulite facies metamorphism and five phases of deformation, whereas previously the preservation of such textures has not been recognised at metamorphic grades greater than amphibolite facies.