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The chemical composition of the continental crust cannot be adequately explained by current models for its formation, because it is too rich in Ni and Cr compared to that which can be generated by any of the proposed mechanisms. Estimates of the crust composition are derived from average sediment, while crustal growth is ascribed to amalgamation of differentiated magmatic rocks at continental margins. Here we show that chemical weathering of Ni- and Cr-rich, undifferentiated ultramafic rock equivalent to ~1.3 wt% of today’s continental crust compensates for low Ni and Cr in formation models of the continental crust. Ultramafic rock weathering produces a residual that is enriched in Ni and also silica. In the light of potentially large volumes of ultramafic rock and high atmospheric CO2 concentrations during the Archean, chemical weathering must therefore have played a major role in forming compositionally evolved components of the early Earth’s crust., The concentration of Ni and Cr of the continental crust cannot be explained by formation models involving differentiated magmatic rocks. Here, the authors show that hydrothermal alteration and chemical weathering of ultramafic rock compensates for the low Ni and Cr concentrations of island arc-type magmatic rocks.

High-grade fault-hosted manganese deposits at the Woodie Woodie Mine, East Pilbara, are predominantly hydrothermal in origin with a late supergene overprint. The dominant manganese minerals are pyrolusite, braunite, and cryptomelane. The ore bodies are located on, or near the unconformities between the Neoarchean Carawine Dolomite and the Paleoproterozoic Pinjian Chert breccia (weathering product of Carawine Dolomite), and sedimentary units of the overlying ca 1300–1100 Ma Manganese Group. Stratabound manganese is typically located above or adjacent to steep fault-hosted manganese. The ore bodies range in size from 0.2 to 5.5 Mt with an average of 0.5 Mt. Historically, over 35 Mt of manganese has been mined at Woodie Woodie, and current ore resources are 29.94 Mt at 39.94% Mn, 6.96% Fe (resource and reserves statement, June 2011, Consolidated Minerals Pty Ltd). Manganese mineralization at Woodie Woodie is related to northwest–southeast directed extension and basin formation during the Mesoproterozoic. Basin architecture is generally well preserved and major manganese occurrences are localised along growth faults which down-throw the Pinjian Chert Breccia into local extensional basins. Manganese ore bodies are typically located on steep 2nd and 3rd order structures that extend off the major growth faults. Mineralized structures display a dominant northeast-trend reflecting the direction of maximum dilation during northwest–southeast extension. A paragenetic sequence is identified for the manganese ore at Woodie Woodie, with early hydrothermal braunite–pyrolusite–cryptomelane–todorokite–hausmannite, overprinted by late supergene oxides. Preliminary fluid inclusion studies in quartz crystals intergrown with pyrolusite and cryptomelane indicate that primary and pseudosecondary inclusions display a range of salinities from 1 to 18 eq. wt.% NaCl and trapping temperatures estimated to be from 220o to 290o at 1 kbar pressure. A lead–manganese oxide (coronadite) is common in manganese ores at Woodie Woodie, and Pb-isotope studies of 40 lead-rich ore samples from 16 pits indicate mineralization occurred within an age range of 955–1100 Ma. A mixed source is suggested for the lead, but was predominantly basalts and/or volcanogenic sedimentary units (e.g., Jeerinah Formation) of the ca 2700 Ma Fortescue Group. The typically high Mn:Fe ratios and enrichment in elements such as Pb, As, Cu, Mo, Zn are consistent with a dominantly hydrothermal origin for the manganese at Woodie Woodie. Supergene manganese is distinguished from hypogene manganese by a marked enrichment in REE in the supergene manganese. An early structural framework, established during Neoarchean rifting, provides a major structural control on manganese ore distribution. The Woodie Woodie mine corridor is located in a zone of oblique strike-slip extension on major northwest-trending transform faults and north-trending oblique normal faults. A major transform structure at the southern end of the Woodie Woodie mine corridor (Jewel-Southwest Fault Zone) likely acted as a major fluid conduit for manganese-bearing hydrothermal fluids and this would account for the concentration of significant manganese ore occurrences to the north and south of this structure.

A new style of komatiite-associated sulfide-poor platinum-group element (PGE: Os, Ir, Ru, Rh, Pt, Pd) mineralisation has been identified at Wiluna in the strongly nickel sulfide (NiS) mineralised Agnew – Wiluna Greenstone Belt, Western Australia. The komatiite sequence at Wiluna is ∼200 m thick and comprises a basal pyroxenite layer, a thick ortho-to-mesocumulate-textured peridotite core, which is overlain by rhythmically layered wehrlite, oikocrystic pyroxenite and thick upper gabbroic margins. Pegmatoid and dendritic (harrisitic) domains are common features, whereas spinifex-textured horizons and flow-top breccias are absent. The presence of anomalous PGE-enriched horizons (ΣPt – Pd = 200 – 500 ppb) in the oikocrystic pyroxenite and in the layered melagabbro and gabbronorite horizons directly overlying the wehrlite unit is due to the presence of fine-grained (1 – 10 μm) platinum-group minerals (PGMs). More than 70 PGM grains were identified, and a considerable mineralogical variability was constrained. ...

The Mount Keith (MKD5) nickel sulfide deposit is one of the largest komatiite-hosted nickel sulfide deposits in the world; it is hosted by a distinctive spinifex-free, cumulate-rich, ultramafic horizon/unit termed the Mount Keith Ultramafic (MKU). The Mount Keith Ultramafic shows significant variation along its lateral extent. The internal architecture is made up of adcumulate-textured pods and lenses, which are flanked by thinner meso- and orthocumulate-textured units, overlain by pyroxenitic and gabbroic horizons. The lateral and vertical changes in the geometry and internal architecture reflect variations in the lithological association and emplacement conditions along the strike extent of the belt. The chilled margins of the Mount Keith Ultramafic unit contain ∼1,200 ppm Ni. Olivine cumulates average ∼2,500–3,500 ppm Ni, with few exceptions (Ni > 4,500 ppm) reflecting occurrence of minor nickel sulfides, whereas pyroxenites and gabbros generally contain, respectively, ∼1,500–2,000 and ∼100–1,000 ppm Ni. Olivine cumulates generally contain low Cr concentrations ( 5,000 ppm Cr). The internal stratigraphy of the Mount Keith Ultramafic unit may be subdivided into two groups based on rare earth element distribution. The chilled margins and the internal units of the Main Adcumulate domain display LREE-enriched patterns [(La/Sm)n > 1–3] and negative Eu, Hf, Zr, Nb, and Ti anomalies. The internal units in the Western Mineralized Zone generally display flat chondrite-normalized REE patterns and only minor negative Nb anomalies. The pattern of platinum-group element (PGE) distribution varies greatly along the strike extent of the Mount Keith Ultramafic unit. The chilled margins display relatively low absolute concentrations [PGE (excl. Os) ∼16 ppb] and relatively fractionated patterns, with subchondritic Pt/Pd ratios (∼1.5), and superchondritic Pd/Ir ratios (∼3). The PGE trends in the thick adcumulate-textured pods containing widespread nickel sulfide mineralization display positive correlation with sulfide abundance, whereas fractionated pyroxenites and gabbros in the thinner domains display highly depleted PGE concentrations and generally show compatible PGE trends. The nickel sulfide ore typology and style vary greatly along the strike extension of the Mount Keith Ultramafic unit. Basal massive nickel sulfide mineralization (e.g., Sarah’s Find) occurs in the thinner meso- and orthocumulate-textured units, whereas stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit) is hosted in the adcumulate-textured pods. We hypothesize that the very low PGE content of the initial liquid of the Mount Keith Ultramafic unit indicates that the initial magma pulse that penetrated through the dacite host-rock had already equilibrated with sulfides at depth and/or carried entrained immiscible sulfide blebs. We argue that upon emplacement, the intruding magma experienced a significant thermal shock at the contact with water-saturated volcaniclastic breccias. The sudden chilling would have increased the viscosity of the magma, possibly to the point where it was no longer able to sustain the suspension of the immiscible sulfide liquid. As a result, the sulfide blebs coalesced and formed the basal massive sulfide nickel sulfide mineralization at the base of the sill (i.e., Sarah’s Find). Prolonged focused high volume magma flow within the sill resulted in the emplacement of a thick, lens-shaped accumulation of olivine adcumulate. Local variations in intensive parameters other than crustal assimilation (e.g., T, fO2, fS2) may be principally responsible for sulfide supersaturation and controlled the local distribution of stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit), generally localized within the core of the thicker dunite lenses.

The MKD5 nickel deposit is hosted by the Mount Keith Ultramafic Complex (MKUC), a dunite body of komatiitic affinity located in the Agnew-Wiluna Greenstone Belt, Western Australia. The internal architecture of the MKUC comprises seven distinct internal units that range from extreme adcumulate dunite to relatively fractionated pyroxenitic and gabbroic horizons. The MKUC is divided into three packages of units. The main adcumulate domain (MAD), which is situated in the lower portion of the complex, contains the bulk of disseminated nickel sulfide and is dominated by coarse adcumulate olivine textures. Overlying the MAD is an upper fractionated zone, which is dominated by mesocumulate-to-orthocumulate peridotite with domains containing oikocrystic pyroxenite and gabbroic lenses. An aerially restricted unit comprising texturally and chemically distinct olivine cumulate rocks is known as the western mineralized zone (WMZ). The fractionation trend between the MAD and UPZ indicates a westerly facing for the MKUC, conformable with the bounding stratigraphy. In the MKUC, truncation of some of the uppermost internal stratigraphic units by the hangingwall contact indicates that the unit has undergone structural modification since its emplacement and suggests that a proportion of the upper section has been removed by faulting. Furthermore, vertical and lateral textural transitions within the internal stratigraphy suggest that the MKUC (excluding the WMZ) was emplaced from an essentially continuous magma flow, with the MAD representing the period of highest magma flux and the major constructional period of emplacement. Conversely, the WMZ is interpreted to represent a later pulse of ultramafic magma, emplaced stratigraphically above the main MKUC. Comparison of the MKUC with other komatiitic dunites from both within the Agnew-Wiluna Greenstone Belt and worldwide indicates that despite apparent geometrical differences between lens and sheet komatiitic dunites, a broad facies architecture can be defined. We suggest that the differences in geometry are related to differing degrees of flow localization within dunitic units and are a function of both differences in the thermal characteristics and the degree of litho-facies heterogeneity of the enclosing lithologies.

The ultramafic horizons of the Wiluna domain (Agnew-Wiluna Greenstone Belt, Western Australia) form two main tabular and sheet-like fractionated units, which generally comprise a 5-10m-thick basal pyroxenite layer, a 50-100m-thick meso-to-orthocumulate-textured peridotite horizon, which is overlain by a core of wehrlite, ranging 10-50m in thickness, grading upwards into oikocrystic pyroxenites (30-50m-thick) and upper gabbroic margins (30-50m-thick). Primary textures are exceptionally well preserved: pegmatoidal and dendritic (harrisitic) olivine domains are common in all lithologies, whereas spinifex-textured horizons and flowtop breccias are absent. The fractionation sequence and the geochemical profile of the two ultramafic units are almost indistinguishable, suggesting that the belts may have been structurally duplicated. The ultramafic units display a steady trend towards increasing Fe content up stratigraphy, above a narrow basal zone showing a reversed trend. Calculated Ni contents of cumulus olivines indicate that the magma remained sulfur-undersaturated up to about the middle of the unit, where fractionation of a small proportion of sulfide (R>1000) occurred and depleted the upper fractionated levels in Ni. The presence of various anomalous PGE-enriched horizons (SPt-Pd= 200-300 ppb) in the fractionated pyroxenite layer directly overlying the basal ortho-mesocumulate-textured unit indicates the occurrence of localised weak reef-style PGE mineralisation. Reef-style PGE mineralisation at Wiluna is more similar in stratigraphic setting, style and composition to PGE-rich disseminated Fe-Cu sulfide mineralisation zones within thick differentiated intrusions (e.g. Platinova reef in the Skaergaard intrusion) rather than to other zones in komatiite-hosted systems.

The MKD5 nickel deposit at Mount Keith is hosted within the Mount Keith Ultramafic Complex, a thick komatiitic dunite body previously interpreted as either a large volume lava flow or as a dikelike intrusion. The upper contact relationships of the dunite body are critical for the evaluation of an extrusive versus intrusive origin. New drill core examined during this study has revealed preserved upper contact relationships between the Mount Keith Ultramafic Complex and the enclosing dacitic volcanic rocks. These contacts have lobate geometries with apophyses of the ultramafic material intruding the overlying dacite and dacitic xenoliths within the ultramafic rock along all observed margins. These contact features indicate an intrusive relationship between the Mount Keith Ultramafic Complex and the enclosing stratigraphy, which is consistent with the lack of definitive extrusive features. Our new interpretation of the Mount Keith Ultramafic Complex suggests that thick komatiitic dunite bodies may be regarded as subvolcanic sills emplaced within and below an extrusive komatiite pile. Importantly this model implies that komatiitic dunite bodies are not an integral or even necessary feature of a komatiite flow field.

In most documented occurrences, violarite (FeNi2S4) occurs as a product of the supergene alteration of primary pentlandite or millerite. Earlier experimental phase relations studies predicted the possible existence of a stable violarite–pentlandite tie line, though there has been little field evidence supporting this hypothesis, and the preferred topology in the Ni-Fe-S system involves a pyrite–millerite tie line. This paper documents the occurrence of violarite-pentlandite±pyrite assemblages which, on the basis of mineral chemistry and textural evidence, appear to be hypogene. Primary cobaltian violarite (with 2.1–13.2 wt.% Co) occurs as lamellae in pentlandite in the MKD5 nickel sulphide orebody at Mount Keith, central Western Australia. These lamellae are interpreted to be of exsolution origin. Cobalt is preferentially partitioned into violarite, resulting in high Ni:Co ratios in the associated pentlandite relative to pentlandite in violarite-free assemblages. Hypogene violarite-millerite±pentlandite assemblages were also noted. In all hypogene assemblages, violarite differs in both textural and mineral chemical characteristics from supergene violarite from the upper portions of the MKD5 orebody. The implications of the assemblages for the known low-temperature phase relations in the Ni-Fe-S-(Co) system are discussed.

Woodallite is a new Cr-rich member of the hydrotalcite group from the large, low-grade Mount Keith nickel deposit, in the northeastern Goldfields district of Western Australia. Woodallite occurs as whorls and clusters of minute platelets up to 6 mm across in lizardite+brucite-altered dunite. Individual platelets are typically 10–100 µm in maximum dimension and are often curved. Associated minerals include chromite, lizardite, iowaite, pentlandite, magnetite, tochilinite and brucite. Electron microprobe analysis gave: Mg 25.90 wt.%; Cr 10.81; Fe 4.86; Al 0.68; Cl 9.89; S 0.03; Si 0.01; Ni 0.01; Na 0.01, yielding (after correction for loss of volatiles) an empirical formula of Mg6.19(Cr1.21Fe0.51Al0.15)∑1.87(OH)16[Cl1.62(CO3)0.17(SO4)0.01]·4H2O, by analogy with the hydrotalcite group. The simplified formula is Mg6Cr2(OH)16Cl2·4H2O. Combined thermogravimetric analysis and mass spectroscopy showed a two-stage weight loss of 12.7% and 27.3% occurring over the ranges 25–300°C and 300–660°C, respectively. The first weight loss is attributed to loss of interlayer water, chlorine-bearing species (e.g. HCl) and some CO2, the second to loss of hydroxide water, remaining CO2 and Cl species. The mineral is deep magenta to purple in colour, transparent, with a resinous to waxy lustre, and a perfect basal {0001} cleavage. Woodallite has a Mohs hardness of 1.5–2, and a pale-pink to white streak. The strongest lines in the X-ray powder pattern are [dobs (Iobs) (hkl)] 8.037 (100) (003); 4.021 (48) (006); 2.679 (1) (009); 2.624 (3) (012); 2.349 (5) (015); 2.007 (6) (0,0,12); 1.698 (2) (0,1,11); 1.524 (2) (23). These lines were indexed on a hexagonal cell with a = 3.103(2), c = 24.111(24)Å, V = 201.14 Å3 and Z = 3/8. The new mineral is isostructural with the hydrotalcite group and has space group Rm. The measured density is 2.062 gm/cm3. Woodallite is uniaxial negative with ω = 1.555 and ε = 1.535 (white light); pleochroism is distinct from violet to pinkish lilac. Woodallite forms as a result of hydrothermal alteration of primary magmatic chromite by Clrich solutions at temperatures

Phase relations along the join bornite (Cu5FeS4)-digenite (Cu8.52Fe0.12S4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite-digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu5FeS4-Cu9S5. The thermal anomalies are correlated with structural phase transitions in componen phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu5FeS4 and T = 265°C. This temperature corresponds to that of the tricritical intermediate-high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.

Intermediate compositions along the bornite–digenite join exsolve during quenching from above-solvus temperatures. This involves vacancy clustering and cation ordering processes, and is facilitated by fast cation diffusion rates in the presence of a large (10–25%) metal vacancy population. Samples of six different compositions across the bornite–Cu9S5 join, synthesised from component elements in sealed quartz capsules, were water-quenched from 600°C and analysed using high-resolution neutron powder diffraction (HRPD). Time-of-flight spectra measured at room temperature showed all intermediate compositions had exsolved into mixtures of bornite and low digenite with a 5.0a superstructure. No evidence for the presence of any other phase was found. Variations in the lattice parameters of the exsolved bornite phase were observed for different bulk compositions across the join, and ascribed to variations in the degree of order. Bornite exsolved from digenite-rich compositions may not be fully ordered due to the much lower solvus temperatures at the Cu-rich end of the solid solution. As only slight differences were observed between the diffraction patterns of a visibly exsolved and a rapidly quenched sample of the same bulk composition, the formation of optically-visible exsolution lamellae on {100} is ascribed to a process of coalescence of sub-microscopic domains initially formed during the quenching process. The rapid kinetics of exsolution at geologically low temperatures, explains the lack of authenticated natural occurrences of intermediate compositions in the solid solution in nature, and the limited degree of stoichiometric variation observed in end-members.

The transformation of pentlandite, (Ni,Fe)9S8, to violarite, (Ni,Fe)3S4, has been investigated under mild hydrothermal conditions, at constant values of pH (range 3 to 5) controlled by the acetic acid/sodium acetate buffer. At 80°C, 20(4) wt% of the pentlandite transforms to violarite in 33 days; with the addition of small amounts of Fe3+(CH3COO)2(OH) and H2S the reaction reaches 40(4) wt% completion in this time. At 120 °C and a pressure of 3.5 bars the reaction is complete in 3 days at pH 3.9. Electron backscatter diffraction and backscattered electron imaging reveal that the reaction textures are typical of a coupled dissolution-reprecipitation reaction, rather than a solid state electrolytic process as has been previously reported. The gap between the dissolution front and the precipitation front of violarite is less than 400 nm. The violarite produced by these hydrothermal transformations is texturally similar to supergene violarite, being fine grained, porous and finely cracked.

The thermal expansion coefficients for natural troilite, FeS, Ni-rich pyrrhotite, Fe0.84Ni0.11S, and Ni-poor pyrrhotite, Fe0.87Ni0.02S, were measured during cooling by in situ neutron powder diffraction over the temperature range 873–373 K. Between 873 and 573 K, the mean thermal expansion coefficients for the three compositions are 7.4(3)×10−5{FeS}, 8.0(4)×10−5{Fe0.84Ni0.11S} and 8.5(4)×10−5K−1{Fe0.87Ni0.02S}. Below 573 down to 373 K, the first two increase considerably to 14.1(7)×10−5{FeS} and 9.3(5)×10−5{Fe0.84Ni0.11S} while the latter sample shows no significant variation, 8.4(5)×10−5K−1. Below 573 K, the thermal expansion is highly anisotropic, with Δa/100 K−1ranging from 0.89(9)% {FeS} to 0.48(12)% {Fe0.87Ni0.02S} while Δc/100 K−1ranges from −0.39(11)% {FeS} to −0.13(2)% {Fe0.87Ni0.02S}.Upon cooling through 573 K, troilite and pyrrhotite undergo a transition where the FeS6octahedra distort and in the case of pyrrhotite, cation-vacancy clustering occurs. The thermal expansion coefficients are bigger for low cation-vacancy concentrations and decrease as the pyrrhotites become less stoichiometric. This indicates that the thermal expansion in these minerals is damped by vacancy ordering or clustering. The thermal expansion coefficients for troilite and pyrrhotite are amongst the largest reported for sulphide minerals and their role in the formation of ore textures is discussed briefly.