Kianjavato emerald (Mananjary deposits, East coast of Madagascar) was formed during metasomatic processes at the contact between pegmatites and hornblendites. The metasomatic exchange was related to a Pan-African tectonometamorphic event.

Fluid inclusions in the Kianjavato emerald and quartz were studied by means of microthermometry and Raman probe analysis. Three main types of inclusions were revealed: CO2-rich, CH4-rich and aqueous-rich, with a salinity of ∼2 wt.% NaCl equiv. The inclusions occurred along the same primary and pseudosecondary trails and were considered to be formed simultaneously. Based on fluid-inclusion data, the conditions of emerald growth were 250°C < T < 450°C and P = 1.5 kbar.

The fluid inclusion data for Kianjavato emerald were compared to the data for another Madagascar emerald, Ianapera. The latter is of similar age, but its genesis was determined by a shearing event. Our fluid inclusion data suggested that shearing was also important as a mechanism of introducing CO2-rich fluid for the genesis of the Kianjavato emerald.

The Paratoo copper deposit, located in the Neoproterozoic to Cambrian Adelaide Geosyncline, South Australia, produced around 360 tons of Cu between 1888 and 1967 from oxidized ores. The deposit is located in the core of a breached, doubly plunging anticline, near a zone of disruption containing brecciated Adelaidean sedimentary rocks and dolerite (‘Paratoo Diapir’), and hosted in dolomitic shales of the Neoproterozoic Burra Formation. Near the surface, the mineralization resides mainly in deeply weathered quartz-magnetite-sulphide (pyrite, chalcopyrite) veins (⩽10 cm wide). At depth, drill cores reveal disseminated magnetite, pyrite, chalcopyrite, copper sulphide and native copper associated with extensive potassic alteration. K-Na-rich fluids also affected the dolerite in the ‘Paratoo diapir’, resulting in the precipitation of K-feldspar, dravite and K-bearing chabazite-Na. The most likely scenario for the genesis of the Paratoo deposit involves circulation of basinal fluids, focusing into the ‘Paratoo Diapir’, and ore precipitation through neutralization by fluid-rock interaction with the dolomitic shales hosting the mineralization.

The Paratoo deposit is deeply weathered, with malachite and chrysocolla (± tenorite and cuprite) containing the bulk of the copper recovered from the shallow workings. A diverse assemblage of secondary REE-bearing carbonate minerals, including the new species decrespignyite-(Y) and paratooite-(La), is associated with the weathered base metal and magnetite ores. Whole-rock geochemical analyses of fresh and mineralized host rock and of vein material reveals that the mineralization is associated with a strong, albeit highly variable, enrichment in light rare earth elements (LREE). This association indicates that REE and base metals were introduced by the same hydrothermal fluid. The strong negative Ce anomaly found in secondary REE minerals and mineralized rock samples suggests an upgrade of the REE contents in the weathering zone, insoluble Ce4+ being left behind.

The Fe-oxide-REE-base metal association at Paratoo is also characteristic of the giant Mesoproterozoic Fe oxide copper gold deposit of Olympic Dam, located 350 km to the NW. A similar association is found in the Palaeozoic deposits of the Mt Painter Inlier, 300 km to the NNE. The widespread occurrence of this elemental association in the Province probably reflects the geochemistry of the basement, which contains numerous Mesoproterozoic granites enriched in REE and U.

The nepheline syenites of the Pilansberg alkaline complex (South Africa) have undergone extensive subsolidus equilibration and alteration with a deuteric Cl- and Na-rich fluid phase. Complex assemblages of secondary minerals result from the replacement of primary alummosilicates, rinkite, eudialyte and fluorapatite. The composition of apatite group minerals formed during these alteration processes reflects the Sr- and rare earth element (REE) content, Na/Cl ratio and pH of the deuteric fluids. Apatite-group minerals are observed to have formed in the following sequence: orthomagmatic fluorapatite; strontian britholite-(Ce); strontian fluorapatite; Sr-apatite; REE-rich Sr-apatite; Sr-Na-REE- rich minerals approaching the stoichiometry of belovite-(Ce) and deloneite-(Ce); britholite-(Ce). Increasing alkalinity of the deuteric fluids is reflected by increasing amounts of Sr replacing Ca in apatite and culminates in the formation of Sr apatite containing 62.1 wt.% SrO (∼4.17 a.p.f.u. Sr). Pilansberg apatite-group minerals form a near-complete solid solution between fluorapatite and a fluorine analogue of Sr apatite with limited solution towards belovite-(Ce), Si-rich belovite-(Ce) and strontian britholite-(Ce).

Mafic rocks of the Bushveld Complex at the southeastern end of the western limb, intersected in bore core from the Cullinan Diamond Mine, are described. A 260 m thick ultramafic body of orthopyroxene and chromite cumulate rocks, with mg# – 100*Mg/(Mg+Fe) – values from 77 to 84 and 0.25 to 0.5% Cr2O3 in the pyroxene, is considered to have affinity to the Critical Zone. Such an interpretation considerably extends the eastern limit of Critical Zone rocks of the western limb of the Bushveld Complex. The whole-rock composition of the lower, chilled basal contact of this body has 10% MgO and 500 ppm Cr, and is comparable to magmas considered parental to the Bushveld Complex. Due to intrusion of a younger sill, the upper contact is not preserved in the bore core. The cumulate rocks have higher interstitial component, inferred from incompatible trace element abundances (Zr, Ti and K), than normal Critical Zone rocks, interpreted to be a result of more rapid cooling due to proximity to the basal contact. The near-constancy of mg# in the pyroxene in the entire succession suggests that large volumes of magma flowed through this conduit, with only the liquidus phases of orthopyroxene and chromite being precipitated.

Five generations of sills, intruded into the underlying metasedimentary rocks, are identified. The oldest is tholeiitic, and was metamorphosed prior to the emplacement of the Bushveld Complex. The second equates to the magma proposed as being parental to the Bushveld Complex (2060 Ma). The third represents the products of differentiation of that magma. The fourth is syenitic, and related to the Pienaars River Alkaline Complex (1430–1300 Ma). The fifth is tholeiitic (1150 Ma), and cuts the Cullinan kimberlite.

Polyminerallic, sulphidic mine wastes were treated with KH2PO4-H2O2 solutions to determine whether the formation of solid phosphate coatings inhibits sulphide oxidation and metal and metalloid mobility. The waste rocks were metal (PbZnCu) and metalloid (AsSb) rich and consisted of major quartz, dickite, illite and sulphide minerals (e.g. galena, chalcopyrite, tetrahedrite, sphalerite, pyrite, arsenopyrite) as well as minor to trace amounts of pre- and post-mining oxidation products (e.g. oxides, hydroxides, arsenates and sulphates). Scanning electron microscopy observations of the waste material treated with KH2PO4-H2O2 solutions showed that metal, metal-alkali and alkali phosphate precipitates formed and coatings developed on all sulphides (with the exception of tetrahedrite). The abundance of phosphate phases was dependant on the availability of metal and alkali cations in solution. In turn, the release of cations was dependent on the amount of sulphide oxidation induced during the experiment or the presence of soluble oxidation products. Lead and to a lesser degree Cu and Zn phosphate coatings remained stable during H2O2 leaching, preventing acid generation and metal release. In contrast, the lack of phosphate coating on tetrahedrite and arsenopyrite allowed oxidation and leaching of As and Sb to proceed and mobilized As and Sb did not form phosphate phases. As a result, As and Sb displayed the greatest release from the coated waste. Thus, the application of KH2PO4-H2O2 solutions to partly oxidized, polyminerallic mine wastes suppresses sulphide oxidation and is most effective in inhibiting Pb (Cu and Zn) release. However, the technique appears ineffective in preventing metalloid (As, Sb) leaching from tetrahedrite- and arsenopyrite-bearing wastes.

Forearc peridotite is generally characterized by low Mg# (= Mg/[Mg + Fe2+] atomic ratio) at a given Cr# (= Cr/[Cr + Al] atomic ratio) of chromian spinel compared to common abyssal peridotite. This may be due to (1) smaller modal abundance of spinel and/or (2) lower equilibrium temperature, for the forearc peridotite. Forearc peridotite has the same amount of spinel as abyssal peridotite, eliminating the first possibility. Spinel in harzburgite and dunite from the Hahajima Seamount at the Izu-Bonin forearc, has a large Cr#, >0.57, and the Mg# is slightly variable towards low values at a given Cr#. The Mg# of spinel cores decreases strongly with a decrease in size. This is due to cooling along with hydration, which gave rise to a compositional variation of Ca-amphibole, from edenitic hornblende (high-temperature) to tremolite (low-temperature) in the Hahajima peridotite. The average two- pyroxene temperature of the Hahajima peridotite, 921°C, is less than that of the abyssal peridotite (1138°C), which is not consistent with a size-dependent Mg# of spinel for the latter. Forearc peridotite has been cooled effectively by H2O released from the subducted slab, causing a small Mg# of their spinels.

The aim of this study is to provide the first detailed mineralogical and fluid-inclusion description of emeralds from the Delbegetey deposit (Kazakhstan). The characteristic features of Delbegetey emeralds are established: they have dissolution figures on crystal faces, bluish colour and distinct colour zoning; the refractive indices are ω = 1.566–1.570, ε = 1.558–1.562, and the specific gravity is 2.65±0.005, relatively low for natural emeralds; they have very small concentrations of the impurities (Fe, Mg, Na and others) typical of other emeralds, and contain Cr and V; there is a significant preponderance of vapour in fluid inclusions of all types and there is liquid-to-vapour homogenization of primary fluid inclusions (at 395–420°C). The lattice oxygen isotope composition data obtained (δ18O SMOW value of 11.3%o) situate the deposit within the range characteristic of other granite-related emerald deposits. Emerald crystallization took place in low-density (0.40–0.55 g/cm3) aqueous fluid, with the following chemical composition (mol.%): 75.6-97.4 H2O, 0.0-18.4 CO2, 0.0-0.9 CH4, and 4.06-9.65 wt.% NaCl equiv. salinity. According to the calculated isochores, the pressure of formation of the Delbegetey emeralds can be estimated at 570–1240 bar.

Chalcedony and agates from a variety of world-wide hosts have been examined using cathodoluminescence (CL). Gaussian fitting of the experimental data shows that there are two dominant spectral emissions at ∼400 and ∼660 nm. A third subordinate peak is also found at ∼470, ∼560 or ∼620 nm. An age-related link is shown between the respective decreasing and increasing relative intensities of the 660 and 620 nm emissions. It is proposed that this change is due to a condensation reaction between neighbouring Si–OH groups eliminating water and forming a strained Si-O-Si bond.

Agates from a variety of hosts and regions produced no clear demonstrable CL distinctions. However, a set of Western Australian agates was examined from host rocks that had been subjected to burial metamorphism. Cathodoluminescence produced different spectral emissions in the petrographic fibrous and granular regions of these agates. One agate shows a partial transformation of the petrographic fibrosity into granularity. This conversion is characterized by emission bands at 570 nm and 460 nm. Similar emission-band changes were produced by heating Brazilian agates for 35 days at 300°C. The identification of these changes in agate could serve as an indicator of palaeoheating within the parent rock.

The Lovozero alkaline massif is the largest of the world's layered peralkaline intrusions (∼650 km2). We describe the evolution of clinopyroxene from the liquidus to the late residual stage throughout the whole vertical section (2.5 km thick) of the Lovozero Complex. Microprobe data (∼990 analyses) of the clinopyroxenes define a relatively continuous trend from diopside containing 15–20% hedenbergite and 10–12% aegirine components, to pure aegirine. The main substitutions during the evolution of the Lovozero pyroxenes are (Na,Fe3+,Ti) for (Ca,Mg,Fe2+). The composition of the pyroxene changes systematically upwards through the intrusion with an increase in Na, Fe3+ and Ti and decrease in Ca and Mg.

The compositional evolution of the Lovozero pyroxene reflects primary fractionation processes in the alkaline magma that differentiated in situ from the bottom to the top of the magma chamber as a result of magmatic convection, coupled with the sedimentation of minerals with different settling velocities.

The temperature interval of pyroxene crystallization is very wide and probably extends from 970 to 450°C. The redox conditions of pyroxene crystallization in the Lovozero intrusion were relatively low, approximating the QFM buffer.

The mineralogical characteristics of halloysite in rectorite pelite in the Zhongxiang area, Hubei, China, were investigated using X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy methods. The results show that halloysite crystals exhibit euhedral lamellar, tubular or club-like, and needle-like or fibre-like morphologies, indicating that they crystallized from a significantly water-saturated environment. The mineral assemblage of the rectorite pelite is rectorite, halloysite, illite, gypsum, pyrite and rutile, suggesting a weak supergene alteration. Several features related to crystallization of halloysite were noted. Growth of halloysite on rectorite edge surfaces in voids and twins of halloysite on a nanometer scale with composition plane (110) were found in the Zhongxiang rectorite pelite, and, in particular, the tapered ends of tubes suggest that halloysite crystallized from solution. Disaggregation of lamellar halloysite particles into parallel clusters of single tubular halloysite crystals suggests that because of significant [H2O] activity in the environment, halloysite may have been derived from the alteration of rectorite.

Mississippi Valley type galena deposits emplaced into Carboniferous limestones throughout the Mendip Hills during the late Permian or Triassic period were locally exposed to the action of seawater during the Jurassic period following regional uplift and erosion of the intervening strata. Oxidation of galena initiated the deposition of manganate minerals from the seawater, and these adsorbed heavy metals from both the seawater and local environment. A subsequent hydrothermal event heated the lead-manganate deposits causing decomposition of the galena and creating the conditions which led to the formation of the suite of unusual secondary minerals – including a number of rare oxychlorides – now found at Merehead. Heating of the manganate phases converted them to Mn oxides and released the entrained heavy metals which were then incorporated into unusual mineral phases. The impervious Mn oxide coating which enclosed the cooling Pb-rich areas isolated them chemically, leading to closed-system behaviour. The high-T phases at Merehead are similar to those found in the Pb-bearing silicic skarns at Långban, whilst the suite of secondary minerals which evolved in the closed-system environments bears striking similarities to the ‘anomalous sequence’ of minerals found at the Mammoth-St. Antony Mine. The complexity of these formation processes probably explains the rarity of Mendip-type Pb-Mn deposits. The collective importance of the disconformity, the hydrothermal event, and subsequent sealing of the deposits are recognized for the first time, and the temperature of the hydrothermal event is shown to have been much greater than has heretofore been realized. Silurian volcanic strata underlying the Carboniferous limestones which have previously been assumed to be the source of heavy metals are shown to have been uninvolved in the process.

The Limousin ophiolite (French Massif Central) occurs as elongate bodies forming a (nearly) continuous suture zone between two major lithotectonic units of the French Variscan belt. The mantle section of the ophiolite is made of diopside-bearing harzburgite, harzburgite and dunite characteristic of a lherzolite-harzburgite ophiolite type (LHOT). The plutonic section is essentially composed of troctolites, wehrlites and gabbros locally intruded by ilmenite-rich mafic dykes. All the rocks were strongly affected by an ocean-floor hydrothermal metamorphism. The composition and evolution of primary magmatic phases (olivine, clinopyroxene, plagioclase and spinel) throughout the lowermost magmatic sequence correspond to those described in oceanic cumulates (ODP data). The Limousin ophiolite is thus of MOR type instead of SSZ type. The whole lithological section, the mineral chemistry, the extensive hydrothermal oceanic alteration and the relatively thin crustal section are typical of a slow-spreading ridge ocean (i.e. Mid-Atlantic ridge). Comparison of the Limousin ophiolite with other ophiolites from European Variscides suggests that the oceanic domain was actively spreading during the Late Palaeozoic and extended from the Armorican massif to the Polish Sudetes.

Published electron microprobe analyses of mattheddleite, a lead sulpho-silicate apatite from Leadhills, Scotland, have 9–13% IV site deficiencies. However, galena was used as a standard for S, which suggested that low S resulted from a shift in the S-Kα peak. Wavelength scans with a PET crystal show that the S-Kα peak is shifted down by 0.0026 Å for sulphates relative to sulphides. Quantitative analyses show a ∼30% increase of S in mattheddleite using a celestite standard, which fills the IV site, but with Si > S, on average Pb5S1.2Si1.8O11.7Cl0.6(OH)0.4. Direct analysis of oxygen with the electron microprobe implies that the charge imbalance engendered from the inequality of Si and S is compensated with substitution of a vacancy (□), as in Pb5S1.2Si1.8[O11.7□0.3] [Cl0.6(OH)0.4] or Pb5S1.2Si1.8[O11.7(Cl, OH)0.73]. [Cl,OH)0.7 □0.3]. Calculation of OH as l–C1 suggests the presence of both OH- and Cl-dominant mattheddleite at Leadhills, but direct analysis of H is needed to confirm the dominance of OH in the channel site. Wavelength-dispersive analyses of S in apatite and other sulphates must be undertaken with sulphate standards: use of sulphide standards yields a negative error on the order of 10–20% in the resultant S concentration. Reactions of mattheddleite with other Pb minerals at Leadhills show that their stability depends on fluid composition as well as pressure and temperature. An X-ray map of Cl shows complex zoning between Cl-poor and Cl-rich mattheddleite, recording rapid changes in the fluid chemistry during late-stage hydrothermal processes at Leadhills.

The uptake of inorganic Hg2+ and organometallic CH3Hg+ from aqueous solutions by 11 different natural zeolites has been investigated using a batch distribution coefficient (Kd) method and supported by a preliminary voltammetric study. The effect of mercury concentration on the Kd response is shown over an environmentally appropriate concentration range of 0.1–5 ppm inorganic and organometallic Hg using a batch factor of 100 ml g-1 and 20 h equilibration. Analcime and a Na-chabazite displayed the greatest methylmercury uptakes (Kd values at 1.5 ppm of 4023 and 3456, respectively), with mordenite as the smallest at 578. All uptake responses were greater for methylmercury than for the inorganic mercuric nitrate solutions, suggesting a distinctive sensitivity of zeolites to reaction with different types of solute species. It is likely that this sensitivity is attributable to the precise nature of the resultant Hg-zeolite bonds. Additionally, both the Si-Al ratio and the Na content of the initial natural zeolite samples are shown to influence the Kd responses, with positive correlations between Kd and Na content for all zeolites excluding mordenite.

The Pan-African orogenic shield rocks of eastern Egypt were intruded by several anorogenic within- plate granitic complexes, including Mounts Abu-Kharif and El-Dob. These two massifs were emplaced at the intersection of a fault system and a shear zone. The two massifs are made up of hypersolvus peralkaline granites, consisting essentially of perthitic alkali feldspar (55–65 vol.%), quartz (30–35%), and alkali amphibole (ferrorichterite to arfvedsonite; 5–12%), with accessory zircon, apatite and ilmenite. The rocks are evolved in composition, are relatively enriched in Nb (53–75 ppm), Y (34–72 ppm), Zr (421–693 ppm), Ga (26–29 ppm), and the REE (294–562 ppm), and depleted in Al, Mg, Ca, Sr, Ba and Eu. The REE patterns are sub-parallel, LREE -enriched over HREE , and show prominent negative Eu anomalies. The rocks exhibit mineralogical and chemical traits typical of within-plate A-type granites. Rb-Sr radiometric age dating produced a Cambrian age of 522±21 Ma, and an initial 87Sr/86Sr ratio of 0.7080±0.0042. Thus, the investigated peralkaline granitic rocks were emplaced following the termination of the Pan-African orogeny. The rocks are interpreted to have formed in an extensional tectonic environment during a phase of cooling, relaxation, crustal attenuation, and fracturing of the newly-formed shield.

Results of geochemical modelling indicate that the magma may have formed by a large degree of batch partial melting (F = 0.57) of Pan-African calc-alkaline shield rocks, which had been metasomatized possibly by a Na-rich fluid. The volatile flux may have caused fenitization-type reactions along fissures and re-activated Pan-African fractures prior to anatexis, and is considered to have played a role as an important agent of heat transfer. Shear heating, caused possibly by a rapid change in the direction of plate motions beneath eastern Egypt during the Early Palaeozoic, is likely to have produced temperatures necessary for crustal anatexis. The confining pressure must have been released by fissuring of the crust. Magma ascent may have been facilitated by reactivation of pre-existing Pan-African fractures.

Chemical modification of chromian spinel at low-T alteration was examined in detail for a podiform chromitite from a Tethyan ophiolitic mélange belt at Rayat, northeastern Iraq. The chromitite is highly brecciated and the matrix has been completely altered, producing chlorite and carbonate (dolomite and calcite). High-Cr, low-Fe3+ spinel has formed along the margins and cracks of chromian spinel grains throughout the alteration, associated with unaltered primary spinel and magnetite without ferritchromite. In associated harzburgites, only ferritchromite is found instead of the high-Cr, low-Fe3+ spinel. The high-Cr, low-Fe3+ secondary spinel apparently has chemical properties of mantle origin, plotted at the extension of ordinary mantle spinels on compositional spaces. The character is due to subtraction of Al as chlorite with the addition of an amount of magnetite component from the silicate matrix, which is small in volume relative to peridotite and composed of highly magnesian olivine (up to Fo97). We should treat high-Cr chromian spinels with caution in highly altered mantle-derived rocks, especially chromitite and other rocks with highly magnesian olivine, as well as in detrital particles for provenance study.

We have investigated the chemical zoning of garnet in three texturally different eclogite types from the Leaota Massif, Romania, to test the various zonation patterns of Ca, Fe, Mg and Mn as indices of time-lines in porphyroblastic garnets. Mn zonation was found to mark various growth stages very well. It indicates in each of our three case studies a complex growth history dominated by multiple nucleation and coalescence, but also interrupted by partial resorption, as shown by morphological characteristics. Chemical variations of the main elements in garnet during prograde high-pressure metamorphism define time-lines other than those of Mn which decrease, highlighting the stages of porphyroblastic growth. In particular, the Ca/Mn, Mg/Mn and Mg/Fe ratios are useful in late growth stages, when low Mn contents and radial gradients do not allow a satisfactory resolution of Mn time-lines. These ratio-based time-lines further substantiate the potential of Mn time-lines in revealing non-concentric porphyroblastic growth. This is important in order to correctly relate garnet growth stages to stable mineral assemblages, a prerequisite for a reliable derivation of the metamorphic history of the host rock.

Corundum xenocrysts from alkaline basalt fields differ in characteristics and hence lithospheric origins. Trace element, fluid/melt inclusion and oxygen isotope studies on two eastern Australian corundum deposits are compared to consider their origins. Sapphires from Weldborough, NE Tasmania, are magmatic (high-Ga, av. 200 ppm) and dominated by Fe (av. 3300 ppm) and variable Ti (av. 400 ppm) as chromophores. They contain Cl, Fe, Ga, Ti and CO2-rich fluid inclusions and give δ18O values (5.1–6.2‰) of mantle range. Geochronology on companion zircons suggests several sources (from 290 Ma to 47 Ma) were disrupted by basaltic melts (47 ± 0.6 Ma). Gem corundums from Barrington, New South Wales, also include magmatic sapphires (Ga av. 170 ppm; δ18O (4.6–5.8‰), but with more Fe (av. 9000 ppm) and less Ti (av. 300 ppm) as chromophores. Zircon dating suggests that gem formation preceded and was overlapped by Cenozoic basaltic melt generation (59–4 Ma). In contrast, a metamorphic sapphire-ruby suite (low-Ga, av. 30 ppm) here incorporates greater Cr into the chromophores (up to 2250 ppm). Fluid inclusions are CO2-poor, but melt inclusions suggest some alkaline melt interaction. The δ18O values (5.1–6.2‰) overlap magmatic sapphire values. Interactions at contact zones (T = 780–940°C) between earlier Permian ultramafic bodies and later alkaline fluid activity may explain the formation of rubies.

Bannisterite is a modulated 2:1-type phyllosilicate having ten octahedral sites with hydroxyl groups in trans, cis and combined trans-cis configurations. Each octahedral site, depending on its proximity to the layer modulation, is exposed to a different degree of distortion. The electric field gradient at the Fe site and the site distortion are used to propose a model for the site assignment and oxidation mechanism in bannisterite. The results show that two models are compatible with the experimental results of fitting the spectrum of bannisterite. However, the model which allows for site distortion accounts better for the observed line overlap of the [6]Fe2+ sites. Accordingly, the octahedral sites with a greater degree of distortion are assigned to the [6]Fe2+ with lower electric quadrupole splitting, and the octahedral sites with lower site distortion are assigned to the [6]Fe2+ with higher electric quadrupole splitting. Moreover, the ease of oxidation decreases in the order trans > trans-cis > cis.