Synthetic pentlandite surfaces were subjected to oxidation by a range of inorganic oxidants, and the resultant alteration of the surface studied by a range of surface-sensitive spectroscopic techniques. The oxidants used were air during heating to relatively low temperatures (150°C), steam, ammonium hydroxide, hydrogen peroxide, and sulphuric acid. Electrochemical oxidation was also undertaken. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), conversion electron Mössbauer spectroscopy (CEMS), and spectral reflectance measurements were used to characterize the surface compositions. New data for the binding energies of core electrons in pentlandite and violarite, based on the fitted XPS spectra, are proposed. For pentlandite and violarite respectively, values of 707.3 eV and 708.4 eV for the Fe 2p3/2, 853.0 eV and 853.2 eV for the Ni 2p3/2, and 161.2 eV for the S 2p in both sulphides, were obtained. After oxidation the pentlandite surfaces indicated nickel enrichment in the subsurface, with the formation of violarite. The immediate oxidized surface, of approximately 10Å thickness, indicated a range of iron oxides and hydroxides (Fe3O4, Fe2O3 and FeOOH, with possible Fe1−xO and Fe(OH)3), nickel oxide (NiO), and iron sulphates (FeSO4, Fe2(SO4)3). The proportions of the phases present in the surface layer are inferred to be a consequence of both the strength of the oxidant employed, and the thermodynamic stability of the phases, as can be illustrated using partial pressure and Eh/pH diagrams. A sequence of oxidation is proposed, accounting for the sub-surface enrichment in violarite, and the development of the oxidized surface, which is inferred to have a major affect on the rates of oxidation.

A nomenclature is proposed for the alluaudite and wyllieite complex series which is based on sequentially distributing the cations in the cell according to increasing polyhedral size, matching that size with increasing ionic radii of the cations. For oxidized members, the largest site may be partly occupied to empty after all the cations have been distributed. This is supported by structural study.

For alluaudites, the cell formula is X(2)4X(I)4 M(I)4M(2)8(PO4)12 and is written according to decreasing size of the discrete sites. The X(I) and X(2) sites are appended as suffixes in the trivial nomenclature, that is specific name—X(I)X(2).

For wyllieites, the cell formula is X(2)4X (1a)2X(1b)2M(I)4M(2a)4A14(PO4)12. The X(1a), X(1b), and X(2) sites are appended as suffixes in the trivial nomenclature, that is specific name--X(la) X(Ib)X(2).

The nomenclature proposed is:

Seventeen analyses are discussed (of which five are new) for alluaudite and four analyses (of which three are new) for wyllieites. Their distribution is given parenthetically above. One analysis revealed predominant Mg2+ in M(2). It is named maghagen-dortite.

Six new analyses are presented for the arrojadite family of minerals including re-examination of dickinsonite from Branchville, Connecticut. Al3+ is always present. We propose X1 Al (OH,F)(PO4)12, Z = 4, where X = large cations (K+, Ba2+, Pb2+, etc.), Y = Na1+, Ca2+, and M = Fe2+ Mn2+, Mg2+. A range of cations X, Y, M, and Al between 76.8 and 85.9 in the cell (84 for proposed formula) suggests the likelihood of some vacancies in the structure.

Tertiary alkali basaltic rocks from the Southern Highlands, New South Wales, contain two types of clinopyroxene crystals, which exhibit excellent morphological development of hour-glass zoning. These are small, quench clinopyroxene crystals and large, abundant, euhedral phenocrysts. Electron microprobe analyses show that the different zone sectors derive from compositional differences, with variation in TiO2 and Al2O3 contents inversely with SiO2 content being most significant. Increased depth of colour of titanaugites depends on increased coupled substitution of Al for Si in tetrahedral sites and of Ti3− in an M1 site, while pleochroism is enhanced by increasing Fe content. It is suggested that the formation of hour-glass zoning is determined by an environment of crystallization where initial crystal growth is rapid relative to ionic diffusion in the melt, resulting in different chemistry for different growth directions within the crystal. This implies that, under certain conditions, kinetic factors, as well as the chemical composition of the host magma, may be significant in determining the chemical composition of phases precipitated, particularly where more than one crystallographic direction of growth is possible.

Clasts of metamorphosed Cadomian granites from the ∼50—60 Ma Carpathian flysch in Gródek near the Rożnowskie Lake (Silesian Unit, SE Poland) are studied. They are considered to represent the Silesian Ridge, one of the hypothetical, currently unexposed source areas that supplied Carpathian sedimentary basins with clastic material. The gneisses preserve several examples of corona textures that include cores of primary monazite surrounded by polygonal grains of secondary apatite with thorianite inclusions, with intermediate zones of lamellar grains of secondary monazite and outermost rims of clay minerals, or various combinations thereof. Preservation of the complete textures is rare with polygonal apatite with thorianite inclusions, lamellar grains of monazite and clay minerals being particularly prevalent. Locally, polygonal apatite with thorianite inclusions surrounded by allanite and REE-epidote corona with a bastnasite-synchysite phase occurs also. The textures observed developed during primary monazite breakdown and replacement by secondary minerals. The variation in reaction products indicates that alteration was strictly dependent on the local chemical system.

Europium LIII-edge X-ray absorption near-edge structure (XANES) was employed to determine the Eu(II)/Eu(III) ratios in minerals. This ratio can be determined based on the peak-area ratio of white lines, the resonance peak, in normalized XANES spectra for Eu(II) and Eu(III) species. For precise determination of the Eu(II)/Eu(III) ratios, however, it was revealed that the transition probabilities for each individual Eu(II) and Eu(III) species in the system must be quantified, because we found that the peak area in normalized XANES spectra is different in each Eu(II) and Eu(III) species. Despite this ambiguity, the method was applied to Eu in natural hydrothermal apatites (Eu = 39 and 64 ppm) and fluocerite (Eu = 282 ppm). The relationship between the Eu(II)/Eu(III) ratio in these hydrothermal minerals, and the distribution coefficients of Eu(II) and Eu(III) were discussed, taking into account Eu anomalies in their REE patterns. It is considered that by combining the Eu(II)/Eu(III) ratios determined by XANES and the degree of Eu anomaly in REE patterns, we can provide new information on the distribution of Eu(II) and Eu(III) in various geochemical studies.

The accessory minerals rutile and apatite have been studied in 77 known porphyry copper deposits. Their value as indicators has been well established on the basis of specific chemical and paragenetic variations which they show.

Rutile occurs as the only Ti-mineral in the quartz-sericite zone, is dominant in the biotite-orthoclase zone, and is generally found in the inner fringes of the chlorite-epidote zone. It forms in these zones mainly as a result of the destruction of sphene, but also from biotite and hornblende.

The length: width ratio of rutile crystals is 1·5:1 in the centre of a porphyry system, increasing gradually outward to 2:1. A characteristic red colour displayed in thin section is attributed to a high copper content ranging from 100 to 500 ppm. The ratio of Cr+V:Nb+Ta is also unusually high.

Apatite shows evidence of a complicated history of corrosion and redeposition accompanied by outward migration during the life of the porphyry system. The migration parallels that of copper and typically extends far into the host rocks. The apatite is enriched in chlorine. A plot of a versus c shows a clear separation of apatites of various genetic types, including tin and molybdenum porphyries.

Sericitization in three separate pulses of the Rosses Granite Ring Complex, Co. Donegal, Ireland, has been investigated texturally and chemically using electron microscopy, electron microprobe and fluid inclusion thermometry. The sericitization, which is restricted to the cores of plagioclase, is associated with pores which are abundant in the cores, but absent in the margins. Alkali feldspar, although porous, is unaltered. Associated with the sericitization is alteration of the adjacent primary plagioclase within the cores of grains to a more sodic composition.

It is postulated that the sericitization resulted from the action of externally derived secondary hydrothermal fluids, which gained access to the pores in the plagioclase via now sealed microfractures, formed either by contraction during cooling of the Rosses Complex, or more likely by hydraulic fracturing by the fluids themselves. Limited fluid/rock ratios restricted the degree of sericitization within the host plagioclase, whilst an absence of alteration in alkali feldspar may have been due to the inaccessibility of pores in the alkali feldspar to the hydrothermal fluids at the time of alteration. Fluid inclusion data suggest that the fluids were of low salinity, and that the sericitization took place at an early stage in the cooling history of the Rosses Complex at temperatures between 400 and 600°C. It is further contended that greisenization in the Rosses Complex predated the sericitization and that the greisenization may have been due solely to volatile-rich late-stage magmatic fluids.

The affinity between certain organic compounds and clays has been known for many years. Lloyd reported the adsorptive capacity of fuller's earth for alkaloids in 1916 without theorizing extensively about the mechanism. Smith reacted organic bases and their salts with bentonite and presented evidence that the reaction was one of base-exchange or metathesis, while Hauser has discovered that certain organic compounds of bentonite have the property of swelling and dispersing in organic liquids. This paper reports observations on the rather striking conversion of bentonite from the hydrophilic to the organophilic condition and proposes a mechanism to explain the observed phenomena.

Mineral compositions of small peridotite bodies in an Ordovician collision zone of the Vermont Appalachians provide important clues to their tectonic environment of origin. The bodies have been deformed and partially serpentinized under greenschist- to lower amphibolite-facies conditions during the Ordovician and Devonian. Before serpentinization, the peridotite bodies were dunite as shown by their mineral assemblage and by their high MgO, and low Ti and Al whole-rock contents. Despite deformation and metamorphism, remnant olivine and spinel grains occur; their compositions are taken to represent conditions prior to regional metamorphic events. High Mg/(Mg+Fe) in olivine and very high Cr/(Cr+Al) in spinel indicate that the peridotites formed as highly-depleted mantle residues. The compositions are similar to those in harzburgite and dunite from some ophiolites and from fore-arc regions of subduction zones. Accordingly, the southern Vermont peridotites probably formed in a forearc, supra-subduction zone during the Early Palaeozoic. They were subsequently emplaced by obduction of the upper plate of an east-facing subduction complex.

Understanding the biogeochemical behaviour of arsenic in the weathering and shallow subsurface environment depends critically upon determining the nature and distribution of the chemical species present in natural waters. To this end, coupled ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) is widely used, though species fractionation during ultrasonic nebulization, and matrix-dependent ionization in the plasma are analytical issues that need to be addressed. Hexapole collision cell technology is shown to be effective in suppressing chloride-based polyatomic interferences. Irrespective of the analytical technique used, As(III)/As(V) ratios of natural waters may change substantially during storage due to (1) differential adsorption of arsenic species on hydrated ferric oxides (HFOs); and (2) microbial activity. A wide range of apparently contradictory speciation changes observed by various workers can be rationalized in terms of the differences of microbial consortia present in different water samples. Arsenic speciation in certain water types can be stabilized for days or even weeks by combined filtration, acidification and refrigeration whilst the addition of EDTA and the use of 0.1 mm filters is indicated for iron-rich waters and waters with high activities of redox-active bacteria, respectively. Although the use of hydrochloric acid has been reported elsewhere as resulting in the apparent oxidation of As(III), we show that for certain water types it acts as an extremely effective preservative of arsenic speciation.

The Nanga Parbat massif is a rapidly eroding, thrust-related antiform that is distinct from other regions of the Himalayan orogen in being both intruded by Late Miocene-Pliocene anatectic granites and permeated by a vigorous hydrothermal system. Exhumation is achieved by erosion during thrusting along the Liachar thrust in the apparent absence of extensional tectonics. At depths in excess of 20 km, small batches of leucogranitic melt have been generated by fluid-absent breakdown of muscovite from metapelitic lithologies. These melts ascend several kilometres prior to emplacement, aided by low geothermal gradients at depth and by interaction with meteoric water as they reach shallow levels. At intermediate depths (∼15 km) limited fluid infiltration is restricted to shear zones resulting in localised anatexis. Within the upper 8 km of crust, magmatic and meteoric fluid fluxes are channelised by active structures providing a feedback mechanism for focusing deformation. Leucogranite sheets show a range of pre-full crystallization and high-temperature crystal-plastic textures indicative of strain localisation onto these sheets and away from the country rocks. At subsolidus temperatures meteoric fluids promote strain localisation and may trigger cataclastic deformation. Since near-surface geothermal gradients are unusually steep, the macroscopic transition between distributed shearing and substantial, but localised, cataclastic deformation occurred at amphibolite-facies conditions (∼600°C). Even with the greatest topographic relief in the world, the meteoric system of Nanga Parbat is effectively restricted to the upper 8 km of the crust, strongly controlled by active structures.

Over 200 sediment samples taken from ten holes drilled in the Galapagos Hydrothermal Mounds Field during D.S.D.P. Leg 70 have been analysed for twenty-one elements. The three main sediment lithologies recognized are siliceous carbonate ooze, Mn-oxide crust, and an Fe-rich silicate (nontronite), the latter two being of hydrothermal origin. The major element composition of the hydrothermal deposits is similar in each mound hole, suggesting that formation conditions and hydrothermal solution composition have been constant both geographically and with time. The large variations which occur in the concentration of some trace elements in the Mn-oxide crusts and in transition metal ratios in the nontronite compared with the pelagic ooze suggests a hydrothermal supply to the mounds of Li, Mo, Pb, and Ba in addition to Mn, Fe, and silica.

The data are compatible with suggestions that the nontronite formed at depth in the pelagic sediment blanket by replacement of biogenic ooze, whilst the Mn crusts formed at or near the sediment-water interface. Pelagic sediments in the mounds which have not been replaced are similar in composition to pelagic sediments from non-mounds holes.

Millimetric, ellipsoidal monazite nodules found within Lower Palaeozoic sedimentary rocks in Wales, south-west England and Brittany are characterised by a pronounced zonation of light and heavy REE, an inclusion fabric of low-grade metamorphic minerals indistinguishable from the host rock and a low Th content. They are interpreted as the product of in situ recrystallization of detrital monazites derived from pegmatitic or granitic source rocks and are potentially useful as indicators of Lower Palaeozoic sedimentary rock provenance.

Sustaining Earth, in the face of both technology thrusts and population dynamics, depends on our ability to maintain a delicate balance between human-promoted planetary modification and decline thresholds for land (soils), water, atmosphere, and biological systems. Mineralogy, as much as any other single science, will be central to this process. A set of links between Earth sustainability issues and the science of mineralogy are formulated and discussed in this discourse. The strongest ties exist in the areas of mineral-water and mineral-atmosphere interactions. Minerals are also particularly important in human disease generation. In addition, due to the role of minerals as invaluable economic resources, the environmental consequences of mining also come into play. New subdisciplines have recently emerged to bring mineralogy even closer to Earth sustainability issues, particularly mineral-microbe interaction science and nanomineralogy

In the Swedish KBS-3 repository concept, there is potential for gas to be generated from corrosion of ferrous materials under anoxic conditions, combined with the radioactive decay of the waste and radiolysis of water. A full understanding of the probable behaviour of this gas phase within the engineered barrier system (EBS) is therefore required for performance assessment. We demonstrate key features from gas transport experiments on pre-compacted Mx80 bentonite, under laboratory and field conditions, and discuss their implications in terms of a conceptual model for gas migration behaviour. On both scales, major gas entry is seen to occur close to the sum of the porewater and swelling pressures of the bentonite. In addition, gas pressure at breakthrough is profoundly sensitive to the number and location of available sinks for gas escape. Observations of breakthrough can be explained by the creation of dilatational pathways, resulting in localized changes in the monitored porewater pressures and total stresses. These pathways are highly unstable, evolving spatially and temporally, and must consequently influence the gas permeability as their distribution/geometry develops.

Such observations are poorly embodied by conventional concepts of two-phase flow, which do not fully represent the key processes involved. Although dilatancy based models provide a better description of these processes, the paucity of data limits further development and validation of these models at present.

The commissioning and operation of apparatus for neutron diffraction at simultaneous high temperatures and pressures is reported. The basic design is based on the Paris-Edinburgh cell using opposed anvils, with internal heating. Temperature is measured using neutron radiography. The apparatus has been shown in both on-line and off-line tests to operate to a pressure of 7 GPa and temperature of 1700°C. The apparatus has been used in a neutron diffraction study of the crystal structure of deuterated brucite, and results for 520°C and 5.15 GPa are presented. The diffraction data that can be obtained from the apparatus are of comparable quality to previous high-pressure studies at ambient temperatures, and are clearly good enough for Rietveld refinement analysis to give structural data of reasonable quality.

Jeffbenite, ideally Mg3Al2Si3O8, previously known as tetragonal-almandine-pyrope-phase ('TAPP’), has been characterized as a new mineral from an inclusion in an alluvial diamond from São Luiz river, Juina district of Mato Grosso, Brazil. Its density is 3.576 g/cm3 and its microhardness is ∼7. Jeffbenite is uniaxial (-) with refractive indexes ω = 1.733(5) and ε = 1.721 (5). The crystals are in general transparent emerald green.

Its approximate chemical formula is (Mg262Fe2+0.27)(Al186Cr016)(Si2 g2Al018)O12 with very minor amounts of Mn, Na and Ca. Laser ablation ICP-MS showed that jeffbenite has a very low concentration of trace elements. Jeffbenite is tetragonal with space group I42d, cell edges being a = 6.5231(1) and c = 18.1756(3) Å. The main diffraction lines of the powder diagram are [d (in Å), intensity, hkl]: 2.647, 100, 2 0 4; 1.625, 44, 3 2 5; 2.881, 24, 2 1 1; 2.220, 19, 2 0 6; 1.390, 13, 4 2 4; 3.069, 11,2 0 2; 2.056, 11,2 2 4; 1.372, 11,2 0 12.

The structural formula of jeffbenite can be written as (M1)(M2)2(M3)2(T1)(T2)2O12 with M1 dominated by Mg, M2 dominated by Al, M3 dominated again by Mg and both T1 and T2 almost fully occupied by Si. The two tetrahedra do not share any oxygen with each other (i.e. jeffbenite is classified as an orthosilicate).

Jeffbenite was approved as a new mineral by the IMA Commission on New Minerals and Mineral Names with the code IMA 2014-097. Its name is after Jeffrey W. Harris and Ben Harte, two world-leading scientists in diamond research. The petrological importance of jeffbenite is related to its very deep origin, which may allow its use as a pressure marker for detecting super-deep diamonds. Previous experimental work carried out on a Ti-rich jeffbenite establishes that it can be formed at 13 GPa and 1700 K as maximum P-T conditions.

A new mineral, yurmarinite, Na7(Fe3+,Mg,Cu)4(AsO4)6, occurs in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with hatertite, bradaczekite, johillerite, hematite, tenorite, tilasite and aphthitalite. Yurmarinite occurs as well-shaped, equant crystals up to 0.3 mm in size, their clusters up to 0.5 mm and thin, interrupted crystal crusts up to 3 mm × 3 mm on volcanic scoria. Crystal forms are {101}, {011}, {100}, {110} and {001}. Yurmarinite is transparent, pale green or pale yellowish green to colourless. The lustre is vitreous and the mineral is brittle. The Mohs hardness is ∼4½. One direction of imperfect cleavage was observed, the fracture is uneven. D (calc.) is 4.00 g cm−3. Yurmarinite is optically uniaxial (−), ω = 1.748(5), ε = 1.720(3). The Raman spectrum is given. The chemical composition (wt.%, electron microprobe data) is Na2O 16.85, K2O 0.97, CaO 1.28, MgO 2.33, MnO 0.05, CuO 3.17, ZnO 0.97, Al2O3 0.99, Fe2O3 16.44, TiO2 0.06, P2O5 0.12, V2O5 0.08, As2O5 56.68, total 99.89. The empirical formula, calculated on the basis of 24 O atoms per formula unit, is (Na6.55Ca0.28K0.22)S7.05(Fe2.48 3+Mg0.70Cu0.48Al0.23Zn0.14Ti0.01Mn0.01)S4.05(As5.94P0.02V0.01)S5.97O24. Yurmarinite is rhombohedral, R c, a = 13.7444(2), c = 18.3077(3) Å, V = 2995.13(8) Å3, Z = 6. The strongest reflections in the X-ray powder pattern [d, Å (I)(hkl)] are: 7.28(45)(012); 4.375(33)(211); 3.440(35)(220); 3.217(36)(131,214); 2.999(30)(223); 2.841(100)(125); 2.598(43)(410). The crystal structure was solved from single-crystal X-ray diffraction data to R = 0.0230. The structure is based on a 3D heteropolyhedral framework formed by M 4O18 clusters (M = Fe3+ > Mg,Cu) linked with AsO4 tetrahedra. Sodium atoms occupy two octahedrally coordinated sites in the voids of the framework. In terms of structure, yurmarinite is unique among minerals but isotypic with several synthetic compounds with the general formula (Na7–x ☐x )(M 3+x 3+ M 1–x 2+)(T 5+O4)2 in which T = As or P, M 3+ = Fe or Al, M 2+ = Fe and 0 ≤ x ≤ 1. The mineral is named in honour of the Russian mineralogist, petrologist and specialist in studies of ore deposits, Professor Yuriy B. Marin (b. 1939). The paper also contains a description of the Arsenathaya fumarole and an overview of arsenate minerals formed in volcanic exhalations.

A suite of ultramafic-mafic alkaline igneous rocks in the Damodar Valley, eastern India, contains carbonate, phosphate and titanate minerals that are not characteristic or common in minettes or lamproites, but are typical of orangeites (Group II kimberlite) from southern Africa. Phlogopite grains from the Damodar alkaline rocks yield mean 40Ar/39Ar ages of 116.6±0.8 Ma, 113.5±0.5 Ma and 109.1±0.7 Ma (1σ errors) using laser dating techniques. These ages are similar to the Rb-Sr ages of African orangeites, which lie mostly in the range 121 to 114 Ma. Prior to this study, only one possible occurrence of orangeite (the ∼820 m.y.-old Aries pipe, Western Australia) was known outside the Kaapvaal craton and its environs. If the Damodar alkaline rocks are bona fide orangeites, it is likely that they were generated at depths of >150 km, within the stability field of diamond.

Minerals isostructural with sapphirine-1A, sapphirine-2M, and surinamite are closely related chain silicates that pose nomenclature problems because of the large number of sites and potential constituents, including several (Be, B, As, Sb) that are rare or absent in other chain silicates. Our recommended nomenclature for the sapphirine group (formerly aenigmatite group) makes extensive use of precedent, but applies the rules to all known natural compositions, with flexibility to allow for yet undiscovered compositions such as those reported in synthetic materials. These minerals are part of a polysomatic series composed of pyroxene or pyroxene-like and spinel modules, and thus we recommend that the sapphirine supergroup should encompass the polysomatic series. The first level in the classification is based on polysome, i.e. each group within the supergroup corresponds to a single polysome. At the second level, the sapphirine group is divided into subgroups according to the occupancy of the two largest M sites, namely, sapphirine (Mg), aenigmatite (Na), and rhönite (Ca). Classification at the third level is based on the occupancy of the smallest M site with most shared edges, M7, at which the dominant cation is most often Ti (aenigmatite, rhönite, makarochkinite), Fe3+ (wilkinsonite, dorrite, høgtuvaite) or Al (sapphirine, khmaralite); much less common is Cr (krinovite) and Sb (welshite). At the fourth level, the two most polymerized T sites are considered together, e.g. ordering of Be at these sites distinguishes høgtuvaite, makarochkinite and khmaralite. Classification at the fifth level is based on XMg = Mg/(Mg + Fe 2+) at the M sites (excluding the two largest and Ml). In principle, this criterion could be expanded to include other divalent cations at these sites, e.g. Mn. To date, most minerals have been found to be either Mg-dominant (XMg > 0.5), or Fe2+-dominant (XMg < 0.5), at these M sites. However, XMg ranges from 1.00 to 0.03 in material described as rhönite, i.e. there are two species present, one Mg-dominant, the other Fe2+-dominant. Three other potentially new species are a Mg-dominant analogue of wilkinsonite, rhönite in the Allende meteorite, which is distinguished from rhonite and dorrite in that Mg rather than Ti or Fe3+ is dominant at Ml, and an Al-dominant analogue of sapphirine, in which Al > Si at the two most polymerized T sites vs. Al < Si in sapphirine. Further splitting of the supergroup based on occupancies other than those specified above is not recommended.