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Research subject . High-magnesium rocks associated with the granitoid massifs of the Urals are represented by gabbro-diorites and their melanocratic varieties (hornblendites), as well as by diorites and quartz diorites. These rocks are composed of amphibole porphyrocrists frequently combined with clinopyroxene and phlogopite immersed in a basis of acid plagioclase with interstitial quartz and potassium feldspar. In addition to a high magnesium content of 0.5–0.8 units, these rocks are characterized by extremely high chromium contents of up to 1200 ppm. Methods . The study of the composition of high-magnesium rocks was performed using an ELAN 9000 inductively coupled plasma mass spectrometer, an SX-100 Cameca electron probe microanalyzer and an energy dispersive device INCAEnergy 450 X-Max 80. The detection limit for Cr 2 O 3 was equal to 0.05 wt. % and 0.2 wt. % for the microanalyzer and the energy dispersive device, respectively. Results . The two main mineral associations related to magmatic and post-magmatic processes are found to be different in terms of chromium behaviour. The average concentrations of chromium oxide in the minerals from the magmatic association varied within the range (wt. %) of 0.10–0.50, 0.29–0.68, 0.08-0.36 and 0.0–1.6 for different samples of clinopyroxene, amphibole, phlogopite and their variations, respectively. The post-magnetic association included minerals representing the products of postmagmatic (hydrothermal) transformation of pyroxenes and alumina amphibole into low-alumina magnesia hornblende, actinolite, titanite, epidote and muscovite. The transformation of chromospinelide at this stage had been accompanied by exchange processes with silicates, as a result of which the silicates were enriched with chromium. The average concentrations of chromium oxide in the minerals of this association were (wt. %) 0.24–0.80, 1.38–3.08, 1.03 and 3.5 in the samples of amphibole, epidote, titanite and muscovite, respectively. Conclusion . It is assumed that the crystallization of the early association of iron-magnesium silicates proceeded from aqueous high-magnesium melts. The subsequent post-magmatic change of such silicates led to the development of phases with a similar and occasionally higher chromium content. This fact can be explained by the interaction of silicates with chromite under the conditions of low fluid oxidation, which was insufficient for the formation of magnetite.

Hydrous phases have been identified to be a significant component of martian mineralogy. Particularly prehnite, zeolites, and serpentine are evidence for low‐grade metamorphic reactions at elevated temperatures in mafic and ultramafic protoliths. Their presence suggests that at least part of the martian crust is sufficiently hydrated for low‐grade metamorphic reactions to occur. A detailed analysis of changes in mineralogy with variations in fluid content and composition along possible martian geotherms can contribute to determine the conditions required for subsurface hydrous alteration, fluid availability and rock properties in the martian crust. In this study, we use phase equilibria models to explore low‐grade metamorphic reactions covering a pressure‐temperature range of 0‐0.5 GPa and 150‐450 °C for several martian protolith compositions and varying fluid content. Our models replicate the detected low‐grade metamorphic/hydrothermal mineral phases like prehnite, chlorite, analcime, unspecified zeolites, and serpentine. Our results also suggest that actinolite should be a part of lower‐grade metamorphic assemblages, but actinolite may not be detected in reflectance spectra for several reasons. By gradually increasing the water content in the modeled whole rock composition, we can estimate the amount of water required to precipitate low‐grade metamorphic phases. Mineralogical constraints do not necessarily require an elevated geothermal gradient for the formation of prehnite. However, restricted crater excavation depths even for large impact craters are not likely sampling prehnite along colder gradients, either suggesting a geotherm of ~ 20 °C/km in the Noachian or an additional heat source such as hydrothermal or magmatic activity.

Exhumed subduction zones frequently show widespread actinolite-chlorite (Act-Chl) dominated compositions, suggesting that this may play an important role in controlling megathrust fault slip. We investigate the frictional behavior of simulated Act-Chl (85:15) gouge mixtures derived from natural mafic metamorphic rocks, under hydrothermal conditions using a ring shear deformation apparatus. Experiments were performed at effective normal stresses (σneff) of 50–200 MPa, pore fluid pressures (Pf) of 50–200 MPa, at temperatures (T) of 23–600 °C. In each experiment we applied a shear displacement (x) of ~10 mm at a constant sliding velocity (v) of 10 μm/s, followed by v-stepping in the range 0.3–100 μm/s, and slide-hold-slide (SHS) tests with hold times (t) ranging from 3 s to 3000 s. We quantified the rate- and state-dependent friction parameter (a-b), and investigated the effect of t on fault healing (Δμpk). The results showed no effects of temperature on the coefficient of friction (μ ≈ 0.6–0.7), or on (a-b), with some experiments showing persistent, displacement-hardening or -weakening trends. Nonetheless, effects of v and of normal stress (σn = σneff + Pf) on (a-b) fall into three temperature regimes: (1) T = 23–100 °C, (2) T = 200–400 °C, and (3) T = 500–600 °C. In Regimes (1) and (3), (a-b) > 0 for all conditions tested, whereas in Regime (2), (a-b) ≤ 0, at σneff = Pf = 50 MPa and v = 0.3–3 μm/s. We discuss on the origin of persistent displacement-hardening or -weakening trends observed, and assess the implications of our data for subduction zone seismogenesis. Extrapolation of (a-b)-data using multiple linear regression suggests that high pore pressure ratios (>0.9) are needed to promote seismogenesis in faults cutting actinolite-chlorite compositions.

Exhumed subduction zones frequently show widespread actinolite-chlorite (Act-Chl) dominated compositions, suggesting that this may play an important role in controlling megathrust fault slip. We investigate the frictional behavior of simulated Act-Chl (85:15) gouge mixtures derived from natural mafic metamorphic rocks, under hydrothermal conditions using a ring shear deformation apparatus. Experiments were performed at effective normal stresses (σn eff) of 50–200 MPa, pore fluid pressures (Pf) of 50–200 MPa, at temperatures (T) of 23–600 °C. In each experiment we applied a shear displacement (x) of ~10 mm at a constant sliding velocity (v) of 10 μm/s, followed by v-stepping in the range 0.3–100 μm/s, and slide-hold-slide (SHS) tests with hold times (t) ranging from 3 s to 3000 s. We quantified the rate- and state-dependent friction parameter (a-b), and investigated the effect of t on fault healing (Δμpk). The results showed no effects of temperature on the coefficient of friction (μ ≈ 0.6–0.7), or on (a-b), with some experiments showing persistent, displacement-hardening or -weakening trends. Nonetheless, effects of v and of normal stress (σn = σn eff + Pf) on (a-b) fall into three temperature regimes: (1) T = 23–100 °C, (2) T = 200–400 °C, and (3) T = 500–600 °C. In Regimes (1) and (3), (a-b) > 0 for all conditions tested, whereas in Regime (2), (a-b) ≤ 0, at σn eff = Pf = 50 MPa and v = 0.3–3 μm/s. We discuss on the origin of persistent displacement-hardening or -weakening trends observed, and assess the implications of our data for subduction zone seismogenesis. Extrapolation of (a-b)-data using multiple linear regression suggests that high pore pressure ratios (>0.9) are needed to promote seismogenesis in faults cutting actinolite-chlorite compositions.

Renard 65, a diamondiferous pipe in the Neoproterozoic Renard kimberlite cluster (Quebec, Canada), is a steeply-dipping and downward-tapering diatreme comprised of three pipe-filling units: kimb65a, kimb65b, and kimb65d. The pipe is surrounded by a marginal and variably-brecciated country rock aureole and is crosscut by numerous hypabyssal dykes: kimb65c. Extensive petrographic and mineralogical characterization of over 700 m of drill core from four separate drill holes, suggests that Renard 65 is a Group I kimberlite, mineralogically classified as phlogopite kimberlite and serpentine-phlogopite kimberlite. Kimb65a is a massive volcaniclastic kimberlite dominated by lithic clasts, magmaclasts, and discrete olivine macrocrysts, hosted within a fine-grained diopside and serpentine-rich matrix. Kimb65b is massive, macrocrystic, coherent kimberlite with a groundmass assemblage of phlogopite, spinel, perovskite, apatite, calcite, serpentine and rare monticellite. Kimb65c is a massive, macrocrystic, hypabyssal kimberlite with a groundmass assemblage of phlogopite, serpentine, calcite, perovskite, spinel, and apatite. Kimb65d is massive volcaniclastic kimberlite with localized textures that are intermediate between volcaniclastic and coherent, with tightly packed magmaclasts separated by a diopside- and serpentine-rich matrix. Lithic clasts of granite-gneiss in kimb65a are weakly reacted, with partial melting of feldspars and crystallization of richterite and actinolite. Lithic clasts in kimb65b and kimb65d are entirely recrystallized to calcite + serpentine/chlorite + pectolite and display inner coronas of diopside-aegirine and an outer corona of phlogopite. Compositions are reported for all minerals in the groundmass of coherent kimberlites, magmaclasts, interclast matrices, and reacted lithic clasts. The Renard 65 rocks are texturally classified as Kimberley-type pyroclastic kimberlites and display transitional textures. The kimberlite units are interpreted to have formed in three melt batches based on their distinct spinel chemistry: kimb65a, kimb65b and kimb65d. We note a strong correlation between the modal abundances of lithic clasts and the textures of the kimberlites, where increasing modal abundances of granite/gneiss are observed in kimberlites with increasingly fragmental textures.

The Biely Vrch deposit in the Western Carpathians is assigned to the shallow, sulfide-poor porphyry gold deposit type and has an exceptionally low Cu/Au ratio. According to 3-D geochemical models, there is a limited spatial correlation between Au and Cu due to the primary introduction of gold by a salt melt and Cu by low-density vapor. Despite a rough spatial correlation of gold grades with quartz stockwork intensity, gold is hosted mostly by altered rock, exclusively in native form. Three main gold mineral assemblages were recognized here. In the deepest parts of the system, the K- and Ca-Na silicate gold assemblage is associated with minerals of high-temperature alteration (plagioclase, K-feldspar, actinolite), with gold grades and fineness depending on depth and potassium content of the host rock: K-silicate alteration hosts the lowest fineness gold (~ 914), whereas Ca–Na silicate alteration has the highest (~ 983). The intermediate argillic gold assemblage is the most widespread, with gold hosted mainly by chlorite, illite, smectite, and interstratified illite–chlorite–smectite minerals. The gold fineness is mostly variable (875–990) and inherited from the former gold mineral assemblages. The latest advanced argillic gold assemblage has its gold mostly in kaolinite. The extremely high fineness (~ 994) results from gold remobilization by late-stage aqueous magmatic-hydrothermal fluids. Uncommon bonanza-grade appears where the earlier gold mineral assemblages were further enriched by this remobilized gold. Primary precipitation of gold occurred during ascent and cooling of salt melts at 450 to 309 °C, mostly during retrograde quartz solubility.

El Romeral is one of the largest iron oxide-apatite (IOA) deposits in the Coastal Cordillera of northern Chile. The Cerro Principal magnetite ore body at El Romeral comprises massive magnetite intergrown with actinolite, with minor apatite, scapolite, and sulfides (pyrite ± chalcopyrite). Several generations of magnetite were identified by using a combination of optical and electron microscopy techniques. The main mineralization event is represented by zoned magnetite grains with inclusion-rich cores and inclusion-poor rims, which form the massive magnetite ore body. This main magnetite stage was followed by two late hydrothermal events that are represented by magnetite veinlets that crosscut the massive ore body and by disseminated magnetite in the andesite host rock and in the Romeral diorite. The sulfur stable isotope signature of the late hydrothermal sulfides indicates a magmatic origin for sulfur (δ34S between − 0.8 and 2.9‰), in agreement with previous δ34S data reported for other Chilean IOA and iron oxide-copper-gold deposits. New 40Ar/39Ar dating of actinolite associated with the main magnetite ore stage yielded ages of ca. 128 Ma, concordant within error with a U-Pb zircon age for the Romeral diorite (129.0 ± 0.9 Ma; mean square weighted deviation = 1.9, n = 28). The late hydrothermal magnetite-biotite mineralization is constrained at ca. 118 Ma by 40Ar/39Ar dating of secondary biotite. This potassic alteration is about 10 Ma younger than the main mineralization episode, and it may be related to post-mineralization dikes that crosscut and remobilize Fe from the main magnetite ore body. These data reveal a clear genetic association between magnetite ore formation, sulfide mineralization, and the diorite intrusion at El Romeral (at ~ 129 Ma), followed by a late and more restricted stage of hydrothermal alteration associated with the emplacement of post-ore dikes at ca. 118 Ma. Therefore, this new evidence supports a magmatic-hydrothermal model for the formation of IOA deposits in the Chilean Iron Belt, where the magnetite mineralization was sourced from intermediate magmas during the first Andean stage. In contrast, the beginning of the second Andean stage is characterized by shallow subduction and a compressive regime, which is represented in the district by the emplacement of the Punta de Piedra granite-granodiorite batholith (100 Ma) and marks the end of iron oxide-apatite deposit formation in the area.

The geochemical and isotopic investigations were provided on the Upper Eocene Senj mafic intrusion and Mo-Cu mineralization to better understand the tectono-magmatic evolution and metallogeny of the central part of the Alborz magmatic belt. The Senj mafic intrusion is composed of gabbro to monzodiorite and monzonite in lithology, and intruded as a sill into volcano-sedimentary rocks of the Eocene Karaj Formation. The Karaj Formation consists of volcano-sedimentary rocks, such as altered crystalline to shaly tuffs. The Senj intrusion (39.7 ± 0.4 Ma) shows LILE and LREE enrichment and negative anomaly of Nb, Ta and Ti, the geochemical signatures similar to those from subduction-related mafic magmas. The Hf-O zircon analyses yield eHf(t) values of + 4.1 to + 11.1 and δ18O values of + 4.8 to + 6.2‰. The zircon isotopic signatures together with shoshonitic affinity in the Senj mafic samples suggest partial melting of an enriched lithospheric mantle that had already been metasomatized by slab-derived melts and fluids. The Mo-Cu mineralization mainly occurs as veins and veinlets in the volcano-sedimentary rocks of the Karaj Formation and is dominated by molybdenite with minor amounts of chalcopyrite, bornite, pyrite and tetrahedrite-tennantite. The associated gangue minerals are tremolite, actinolite, quartz, calcite, chlorite and epidote. The Senj Mo-Cu deposit formed in volcano-sedimentary rocks following the emplacement of the Late Eocene Senj sill. The source of molybdenite in the Senj deposit is dominantly from crustal materials as it is revealed by Re contents in the molybdenite minerals (0.5 to 0.7 ppm). In fact, the molybdenite occurrence may be a remobilization process related to the emplacement of the Senj mafic magma.

Uranium–lead isotopes and trace elements of titanite from the Chengchao iron skarn deposit (Daye district, Eastern China), located along the contact zones between Triassic marine carbonates and an early Cretaceous intrusive complex consisting of granite and quartz diorite, were analyzed using laser ablation inductively coupled plasma mass spectrometry to provide temporal constraints on iron mineralization and to evaluate its potential as a reference material for titanite U–Pb geochronology. Titanite grains from mineralized endoskarn have simple growth zoning patterns, exhibit intergrowth with magnetite, diopside, K-feldspar, albite and actinolite, and typically contain abundant primary two-phase fluid inclusions. These paragenetic and textural features suggest that these titanite grains are of hydrothermal origin. Hydrothermal titanite is distinct from the magmatic variety from the ore-related granitic intrusion in that it contains unusually high concentrations of U (up to 2995 ppm), low levels of Th (12.5–453 ppm), and virtually no common Pb. The REE concentrations are much lower, as are the Th/U and Lu/Hf ratios. The hydrothermal titanite grains yield reproducible uncorrected U–Pb ages ranging from 129.7 ± 0.7 to 132.1 ± 2.7 Ma (2σ), with a weighted mean of 131.2 ± 0.2 Ma [mean standard weighted deviation (MSWD) = 1.7] that is interpreted as the timing of iron skarn mineralization. This age closely corresponds to the zircon U–Pb age of 130.9 ± 0.7 Ma (MSWD = 0.7) determined for the quartz diorite, and the U–Pb ages for zircon and titanite (130.1 ± 1.0 Ma and 131.3 ± 0.3 Ma) in the granite, confirming a close temporal and likely genetic relationship between granitic magmatism and iron mineralization. Different hydrothermal titanite grains have virtually identical uncorrected U–Pb ratios suggestive of negligible common Pb in the mineral. The homogeneous textures and U–Pb characteristics of Chengchao hydrothermal titanite suggest that the mineral might be a suitable internal reference material for U–Pb dating.

Dissolution kinetic experiments of actinolite in water were performed using a flow-through reactor at temperatures from 20 to 400 °C and 23.5±0.5 MPa. The results indicate that the steady-state release rates of the different elements of actinolite vary with temperature. Generally, Ca, Mg, Fe, and Al dissolve more quickly than Si at temperatures from 20 °C to near 300 °C, but slower from 300 to 400 °C. The Si release rate increases with temperatures from 20 to 300 °C and then decreases from 300 to 400 °C. Si release rate reaches the maximum at 300 °C. Amorphous Si-rich surface layers occur at temperature 300 °C. Water property variations within the critical region strongly affect the dissolution rates and the modification of surface.

The Half Dome Granodiorite, Yosemite National Park, California, is recognized in the field by euhedral, fresh-looking, black hornblende phenocrysts up to 2 cm in length. This variety of granodiorite typifies intermediate-age hornblende-phyric units of Cretaceous nested plutonic suites in the Sierra Nevada batholith. Although only inclusions of feldspar are evident in hand samples, the phenocrysts are riddled with up to 50% inclusions of every major mineral found in the host granodiorite plus metamorphic minerals formed during cooling. Amphibole compositions within single phenocrysts vary from actinolite with less than 1 wt% Al 2 O 3 to magnesiohornblende with over 8 wt%. Elemental zoning within the amphibole is highly irregular on the micrometer scale, showing patches and polygonal zones with dramatically different compositions separated by sharp to gradual transitions. The chemical compositions of entire phenocrysts are equivalent to hornblende plus a small proportion of biotite, suggesting that the non-biotite inclusions are the result of metamorphism of the phenocrysts. Backscattered electron imaging shows evidence of brecciation that may have been the result of volume changes as hornblende was converted to actinolite. Pressure calculations using the Al-in-hornblende barometer show unreasonably wide variations on the micrometer scale that cannot have been produced by temperature or pressure variations during crystallization. These hornblende phenocrysts would thus be unsuitable for geobarometry, and caution must be used to avoid similarly zoned phenocrysts in the application of the Al-in-hornblende geobarometer.

Documentation of textures, modes and compositions of minerals in metamorphosed basalts across two greenschist-to-lower amphibolite facies sequences (Flin Flon, Manitoba and Rossland, British Columbia) was combined with a compilation of the literature data to assess equilibrium and disequilibrium processes across this important transition zone. At Flin Flon and Rossland, the greenschist–amphibolite facies transition occurs over a narrow spatial interval marked by hornblende-in, oligoclase-in and actinolite-out isograds. The data suggest the existence of stable miscibility gaps separating coexisting actinolite and hornblende, and coexisting albite and oligoclase, in the lowermost amphibolite facies. However, actinolite and hornblende show a divergence in compositions going upgrade across the oligoclase-in isograd, suggestive of disequilibrium between the new, progressively more aluminous hornblende and metastably persisting actinolite. Likewise, coexisting albite and oligoclase compositions show no evidence for converging compositions at higher temperatures, suggesting they do not remain in equilibrium across a miscibility gap. Compositional gaps within epidote phases are attributed to disequilibrium preservation of lower grade epidote compositions to higher grade conditions, rather than the existence of a miscibility gap at greenschist and amphibolite facies conditions. Recognition of equilibrium and disequilibrium relations highlights the difficulty of using natural compositional datasets to extract information on miscibility gaps and more generally to extract a–X relationships. The greenschist-to-amphibolite facies transition is controlled principally by the consumption of chlorite, which primarily occurs upon crossing the oligoclase-in isograd, concomitant with conversion of actinolite to hornblende and albite to oligoclase. The result is a focused pulse of devolatilization over a small spatial and thermal interval.

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ 18 O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ 18 O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes. Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ 34 S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition of copper or was cotransported with copper, and (2) sulfur isotope analysis may be useful in evaluating southeast Missouri iron deposits for copper and possibly for gold.

The wholerock major and trace element composition of drill cutting samples are compared to drill core samples from adjacent depths in the seawater recharged Reykjanes geothermal system in Iceland. The first appearance of alteration minerals and lithologies in drill cutting samples is a useful tool for interpreting broad subsurface characteristics. However, use of drill cutting samples for determining igneous affinity and elemental exchanges during hydrothermal alteration is problematic. Samples recovered from immediately above and below the cored intervals in wells RN-17B and RN-30 demonstrate that drill-cutting samples are biased towards preservation of least altered primary igneous minerals and more resistant alteration minerals, including albite, quartz, and epidote, with preferential loss of finer-grained and less resistant minerals including chlorite and actinolite. This selective recovery obscures elemental exchanges resulting from hydrothermal alteration processes. For some elements, compositional variations (enrichments and depletions) measured from 9.5 m of core exceeds that observed in ∼3000 m of cutting analyses. Concentration ratios of hydrothermally immobile elements including Zr, Nb, V, Y, HREE, Hf, Ta and Th in deep (>2245 m) spot drill core samples record bimodal, trace element-enriched and trace element-depleted precursor compositions similar to subaerial Reykjanes Peninsula basalts. The same elements in nearly 3000 m of drill cutting samples from well RN-17 overwhelmingly reflect the more common trace element-enriched igneous precursor, demonstrating that mixing of drill cutting samples obscures details of their igneous affinity. A new and different drill rig was used to deepen well RN-17 below 2266 m in a sidetrack hole (RN-17ST), which resulted in a change in drilling conditions, accompanied with an increased well deviation angle from ∼0° to ∼4°. Wholerock geochemical results for drill cutting samples from RN-17ST are homogenous for virtually every element; suggesting the change in drilling conditions resulted in extreme mixing of the drill cuttings. Anomalously high concentrations of Cu, Ni, Cr and Ta in some drill cutting samples likely reflects contamination of drill cutting samples by metal alloys used in drill bits and drill collars or more resistant spinel and sulfide phases.

Microanalysis of Fe 3+ /∑Fe in geological samples using synchrotron-based X-ray absorption spectroscopy has become routine since the introduction of standards and model compounds. Existing calibrations commonly use least-squares linear combinations of pre-edge data from standard reference spectra with known coordination number and valence state acquired on powdered samples to avoid preferred orientation. However, application of these methods to single mineral grains is appropriate only for isometric minerals and limits their application to analysis of in situ grains in thin sections. In this work, a calibration suite developed by acquiring X-ray absorption near-edge spectroscopy (XANES) data from amphibole single crystals with the beam polarized along the major optical directions (X, Y, and Z) is employed. Seven different methods for predicting %Fe 3+ were employed based on (1) area-normalized pre-edge peak centroid, (2) the energy of the main absorption edge at the location where the normalized edge intensity has the highest R 2 correlation with Fe 3+ /∑Fe, (3) the ratio of spectral intensities at two energies determined by highest R 2 correlation with Fe 3+ /∑Fe, (4) use of the slope (first derivative) at every channel to select the best predictor channel, (5 and 6) partial least-squares models with variable and constant numbers of components, and (7) least absolute shrinkage and selection operator models. The latter three sophisticated multivariate analysis techniques for predicting Fe 3+ /∑Fe show significant improvements in accuracy over the former four types of univariate models. Fe 3+ /∑Fe can be measured in randomly oriented amphibole single crystals with an accuracy of ±5.5–6.2% absolute. Multivariate approaches demonstrate that for amphiboles main edge and EXAFS regions contain important features for predicting valence state. This suggests that in this mineral group, local structural changes accommodating site occupancy by Fe 3+ vs. Fe 2+ have a pronounced (and diagnostic) effect on the XAS spectra that can be reliably used to precisely constrain Fe 3+ /∑Fe.

In the Bogazkale region (Corum, Central Anatolia), pieces of Neotethyan oceanic lithosphere are found in an ophiolitic melange. Within the melange, there are occurrences of isolated diabase dykes that intrude serpentinized and carbonatized ultramafics. The diabases are phaneritic, holocrystalline and equigranular, and consist of plagioclase and hornblende as the main primary mineral phases. They have all undergone low-grade alteration, to varying extents, as reflected by the presence of secondary minerals, including chlorite, epidote, prehnite and actinolite. Immobile trace element systematics suggest that all diabases are of subalkaline basalt composition and display negative Nb anomalies in the N-MORB-normalized plots. They also display flat to slightly LREE-depleted patterns in chondrite-normalized diagrams. The relative Th (and La) enrichment coupled with N-MORB-like HFSE composition of the diabases suggests their derivation from a depleted mantle source metasomatized by slab-derived fluids/melts. Overall trace element characteristics are consistent with an oceanic back-arc origin. 40Ar-39Ar radiometric dating on the hornblende grains extracted from the two diabase dykes yield ages of 176.30 ± 0.52 Ma and 178.82 ± 0.80 Ma (Toarcian, Early Jurassic). This suggests the existence of an intra-oceanic subduction zone within the Izmir-Ankara-Erzincan (IAE) Ocean during the Early Jurassic, which can also be traced along the western (Vardar Zone) and the eastern (Sevan/Akera ophiolites) extensions of the Northern Neotethys. This result requires the presence of a Northern Neotethyan oceanic crust of pre-Early Jurassic age, which in turn may suggest that oceanization of the IAE Ocean have occurred during the Late Triassic or earlier.

Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) mineralization emplaced at shallow level, a few hundred meters below the paleo-surface, at the border of a large diatreme–dome complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts are found in the diatreme breccia and in quartz–monzonite porphyry dikes. Such mineralized veins in clasts allow investigation of high-temperature porphyry-style mineralization developed in the deep portions of magmatic–hydrothermal systems. Quartz in porphyry-style veins contains silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of high-temperature (> 600 °C) quartz–molybdenite–(chalcopyrite)–(pyrite) veins are found in the clasts. Early, thin (1–2 mm), and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have been defined, based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions of K-feldspar, biotite, rutile, and minor titanite and (ii) HT1px veins with inclusions of actinolite, augite, titanite, apatite, and minor rutile. Using an emplacement depth of the veins of between 2 and 3 km (500 to 800 bar), derived from the diatreme breccia architecture and the supposed erosion preceding the diatreme formation, multiple mineral thermobarometers are applied. The data indicate that HT1 veins were formed at temperatures > 700 °C. HT2 veins host assemblages of polyphase brine inclusions, generally coexisting with low-density vapor-rich inclusions, trapped at temperatures around 600 °C. Rhyolitic silicate melt inclusions found in both HT1 and HT2 veins represent melt droplets transported by the ascending hydrothermal fluids. LA-ICP-MS analyses reveal a chemical evolution coherent with the crystallization of an evolved rhyolitic melt. Quartz from both HT1 and HT2 veins also contains secondary, low-temperature (~ 300 °C) brine and aqueous fluid inclusions that record the cooling of the system. Both vein types are locally crosscut and/or reopened by a pre-diatreme polymetallic event consisting of pyrite, sphalerite with “chalcopyrite disease,” galena, chalcopyrite, tetrahedrite–tennantite, and minor quartz. LA-ICP-MS analyses of mineral and high-temperature fluid inclusions hosted in HT1 and HT2 veins and in situ secondary-ion mass spectrometry oxygen isotope analyses of vein quartz indicate a magmatic signature for the mineralizing fluids with no major meteoric water input and allow reconstruction of the source and chemical evolution of fluids that formed these porphyry-style veins as snapshots of the early and deep mineralizations at Cerro de Pasco. This detailed study of the porphyry-type mineralization hosted in clasts offers a unique opportunity to reconstruct the late magmatic and early hydrothermal evolutions of porphyry mineralization underlying the world-class Cerro de Pasco epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) deposit.

The Blockspruit fluorite prospect, located in North West State of the Republic of South Africa, occurs within an actinolite rock zone that was emplaced into the Kenkelbos-type granite of Proterozoic age. There are a large number of termite mounds in the prospect. For geochemical prospecting for rare earth elements (REEs), in total, 200 samples of termite mound material were collected from actinolite rock and granite zones in the prospect. Geochemical analyses of these termite mound materials were conducted by two methods: portable X-ray fluorescence (XRF) spectrometry and inductively coupled plasma-mass spectrometry (ICP-MS). Comparison of the two methods broadly indicates positive correlations of REEs (La, Ce, Pr, Nd, and Y), in particular Y and La having a strong correlation. As the result of modal abundance analyses, the actinolite rock at surface mainly consists of ferro-actinolite (89.89 wt%) and includes xenotime (0.26 wt%) and monazite (0.21 wt%) grains as REE minerals. Termite mound materials from actinolite rock also contain xenotime (0.27 wt%) and monazite (0.41 wt%) grains. In addition, termite mound materials from the actinolite rock zone have high hematite and Fe silicate contents compared to those from granite zone. These relationships suggest that REE minerals in termite mound materials originate form actinolite rock. Geochemical anomaly maps of Y, La, and Fe concentrations drawn based on the result of the portable XRF analyses show that high concentrations of these elements trend from SW to NE which broadly correspond to occurrences of actinolite body. These results indicate that termite mounds are an effective tool for REE geochemical prospection in the study area for both light REEs and Y, but a more detailed survey is required to establish the distribution of the actinolite rock body.

The oxygen isotope compositions of eclogite and amphibolite garnets from Franciscan Complex high-grade blocks and actinolite rinds encasing the blocks were determined to place constraints on their fluid histories. SIMS oxygen isotope analysis of single garnets from five eclogite blocks from three localities (Ring Mountain, Mount Hamilton, and Jenner Beach) shows an abrupt decrease in the δ18O value by ~1–3 ‰ from core to rim at a distance of ~120 ± 50 μm from the rim in nine out of the 12 garnets analyzed. In contrast, amphibolite garnets from one block (Ring Mountain) analyzed show a gradual increase in δ18O value from core to rim, implying a different history from that of the eclogite blocks. Values of δ18O in eclogite garnet cores range from 5.7 to 11.6 ‰, preserving the composition of the eclogite protolith. The abrupt decrease in the δ18O values of the garnet rims to values ranging from 3.2 to 11.2 ‰ suggests interaction with a lower δ18O fluid during the final stages of growth during eclogite facies metamorphism (450–600 °C). We hypothesize that this fluid is sourced from the serpentinized mantle wedge. High Mg, Ni, and Cr contents of actinolite rinds encasing the blocks also support interaction with ultramafic rock. Oxygen isotope thermometry using chlorite and phengite versus actinolite of rinds suggests temperatures of 185–240 °C at Ring Mountain and Mount Hamilton. Rind formation temperatures together with the lower δ18O garnet rims suggest that the blocks were in contact with ultramafic rock from the end of garnet growth through low-temperature retrogression. We suggest a tectonic model in which oceanic crust is subducted at the initiation of subduction and becomes embedded in the overlying mantle wedge. As subduction continues, metasomatic exchange between high-grade blocks and surrounding ultramafic rock is recorded in low δ18O garnet rims, and later as temperatures decrease, with rind formation.

The Caspiche porphyry gold-copper deposit, part of the Maricunga gold-silver-copper belt of northern Chile, was discovered in 2007 beneath postmineral cover by the third company to explore the property over a 21-year period. This company, Exeter Resource Corporation, has announced a proven and probable mineral reserve of 1,091 million tonnes (Mt) averaging 0.55 g/t Au, all but 124 Mt of which also contain 0.23% Cu, for a total of 19.3 Moz of contained gold and 2.1 Mt of copper. The deposit was formed in the latest Oligocene (~25 Ma) during the first of two volcanic and corresponding metallogenic epochs that define the Maricunga belt. The gold-copper mineralization is centered on a composite diorite to quartz diorite porphyry stock, within which five outward-younging phases are routinely distinguished. The centrally located, early diorite porphyry (phase 1) hosts the highest-grade ore, averaging ~1 g/t Au and 0.4% Cu. The subsequent porphyry phases are quartz dioritic in composition and characterized by progressively lower gold and copper tenors. Stock emplacement was both pre- and postdated by the generation of large-volume, andesite-dominated breccias, with tuffaceous matrices, which are believed to be shallow portions of diatremes. The deposit is characterized by a central gold-copper zone and partially overlapped but noneconomic molybdenum halo. The gold-copper mineralization in the lower half of the deposit accompanies quartz ± magnetite-veined, potassic-altered rocks, whereas the shallower mineralization occurs within quartz-kaolinite–dominated, advanced argillic alteration. Upper parts of the advanced argillic zone are characterized by siliceous ledges, some auriferous, composed of vuggy residual quartz and/or silicified rock. The chalcopyrite-pyrite mineralization in the potassic zone was partially transformed to high sulfidation-state sulfides and sulfosalts during the advanced argillic overprint, although the underlying chalcopyrite-bornite assemblage was mainly too deep to be affected. The deposit terminates downward in a sulfide-deficient, potassic-calcic zone defined by K-feldspar, actinolite, and magnetite, which formed at the expense of biotite. A relatively minor, shallowly inclined zone of intermediate sulfidation epithermal gold-zinc mineralization, comprising narrow veinlets and disseminations, abuts the late-mineral diatreme contact. Supergene sulfide oxidation throughout the deposit is relatively shallow, and chalcocite enrichment extremely minor. The Caspiche deposit is thought to have been emplaced at relatively shallow paleodepths, within the southern, flat-bottomed part of the premineral diatreme vent. Earliest porphyry system development, probably north of the present deposit, appears to have been aborted by diatreme formation. Much of the gold and copper in the Caspiche deposit was introduced during the potassic alteration stage, with the highly telescoped, advanced argillic overprint being responsible for only minor redistribution of the two metals, and the addition of arsenic. The late-mineral diatreme was emplaced west of the Caspiche deposit, and caused destruction of only its uppermost peripheral parts. The late-mineral diatreme was both pre- and postdated by advanced argillic alteration. Finally, the intermediate sulfidation epithermal gold-zinc zone was localized by the enhanced permeability provided by intense fracturing along the underside of the upward-flared, late-mineral diatreme contact.

Thin- to medium-bedded, stratiform calc-silicate deposits (banded skarns) are a peculiar, but important, component of the supracrustal successions in the Palaeoproterozoic Bergslagen mining district of central Sweden. They are referred to as “skarn-banded leptites” in the literature and are common in areas and at stratigraphic levels that contain iron oxide and base metal sulphide deposits. The stratigraphic hanging wall of the stratabound Ryllshyttan Zn–Pb–Ag + magnetite deposit at Garpenberg, contains approximately 100–150 m of interbedded aluminous skarn beds and rhyolitic ash-siltstones. The skarn beds are mineralogically variable and dominantly composed of grandite, spessartine, epidote, actinolite, quartz, clinopyroxene, and locally magnetite. Integrated field-mapping, and whole-rock lithogeochemical, microscopic and mineral chemical analyses suggest that the stratiform skarn beds are the products of at least two discrete hydrothermal events and subsequent metamorphism. The first event comprised accumulation in a quiescent subaqueous environment, below wave base, of calcareous and ferruginous sediments rich in Fe, Mn, Ca, and Mg. These chemical sediments were deposited concurrently with rhyolitic ash-silt sedimentation, thus forming a (now metamorphosed) laminated calcareous Fe formation with both a detrital rhyolitic component and rhyolitic siltstone interbeds. Positive Eu-anomalies and negative Ce-anomalies for normalized rare earth element analyses of skarn beds suggest that the iron may have been derived from exhalation of hot and reduced hydrothermal fluids, which upon mixing with more oxidized seawater, precipitated Fe oxides and/or carbonates that settled from suspension to the seafloor. The size of the positive Eu-anomalies of the chemical sediments are modified by the content of rhyolitic volcaniclastic material, which has a negative Eu anomaly, such that positive Eu-anomalies are only observed in skarn beds that possess a minor volcaniclastic component. Subsequently, the calcareous Fe formations were subjected to post-depositional alteration by hydrothermal fluids, locally yielding more manganoan and magnesian assemblages. The Mn-alteration is manifested by lateral gradations from epidote-grandite-clinopyroxene±magnetite rocks into significantly more Mn-rich quartz-spessartine rocks and massive andradite rocks over distances of less than 10 cm within individual skarn beds. Magnesian alteration is manifested by the development of discordant zones of pargasite para-amphibolites and formation of stratiform pargasite rocks texturally similar to the interlaminated grandite-epidote-ferroan diopside rocks. The latter increase in abundance towards the Ryllshyttan deposit and are associated with pre-metamorphic/pre-tectonic K–Mg–Fe±Si alteration (now biotite-phlogopite-garnet-cordierite-pargasite rocks) that is related to base metal mineralization. The zone of Mn- and Mg-altered skarn beds extends beyond the zone of pervasive K–Mg–Fe±Si alteration around Ryllshyttan. This suggests that the skarn bed progenitors, or their sedimentary contacts against rhyolitic ash-siltstones, acted as conduits to outflowing hydrothermal fluids. The chemical and mineralogical imprint, imposed on affected beds by alteration, may serve as indicators of proximity to intense K–Mg–Fe±Si alteration envelopes around other base metal sulphide deposits in Bergslagen. The last recorded event comprised syn-tectonic veining of competent massive andradite skarn beds. The veins contain quartz-albite-epidote-ferroan diopside-actinolite assemblages.

The Hasancelebi deposit in eastern Turkey, with proven reserves of 95 million metric tons, is a copper-gold-bearing iron oxide deposit. It is chiefly hosted by rocks that underwent widespread sodic-calcic and potassic styles of alteration. In the Hasancelebi district, pervasive Na-Ca and K-Fe alteration types are overprinted by sericitization and by late alteration that occur in multiple, overprinting systems. The age of hydrothermal alteration and mineralization (ca. between 74-68 Ma) overlaps with the age of alkaline magmatism in the Hasancelebi district. Crystallization and cooling of alkaline magmatism is associated with hydrothermal features that spanned the duration of the district’s igneous history. The 40Ar/39Ar and U-Pb geochronology of magmatism indicate that the hydrothermal system was synchronous with diabase and syenite and/or microsyenite porphyry intrusions and consisted of several discrete phases of Na-Ca and K-Fe alteration. The oldest alteration (phase 1) formed at ca 74.4 to 74.3 Ma; it is spatially and temporally associated with the emplacement of diabase dikes and contains scapolite and phlogopite. The next younger alteration (phase 2) formed at about 71.3 Ma and is spatially and temporally associated with syenite porphyry and microsyenite porphyry intrusions. It consists of scapolite, garnet, pyroxene, and actinolite that are superimposed on the first alteration phase. The next alteration assemblage (phase 3) formed at about 68.6 Ma and consists of phlogopite 2 and magnetite mineralization. Still later alteration (phase 4) overprints phases 1, 2, and 3 and consists of sericite-quartz, chalcopyrite, hematite, calcite, fluorite, and barite. Oxygen ( δ 18O) and hydrogen ( δ D) isotope analyses were carried out on phlogopite, sericite, barite, calcite, fluorite, and quartz representing the mineral assemblage formed during phases 1 and 4 of the hydrothermal alteration. The calculated δ 18O (H2O) and δ D (H2O) composition of the fluids that formed preore K-Fe alteration and postore alteration of phase 4 range between 15.1 to 8.5 and −124 to −85.6 per mil, respectively, and partially overlap the range for traditional magmatic waters. Oxygen and H isotope compositions from alteration minerals highlight two major points: Na-Ca and K-Fe alteration assemblages are likely derived from high-temperature primary magmatic fluids, and late sericitization is likely derived from fluids exsolved from cooling alkaline plutons during hydrothermal fracturing and consequent degassing at moderate temperatures. The initial ɛ Ndi values of the alteration zones range from −2.02 to −2.08, close to the calculated ɛ Nd value of associated syenite porphyry at the time of alteration ( ɛ Nd (68.64Ma; −1.9). Nd-Sr isotope compositions combined with 40Ar-39Ar and U-Pb geochronology of the associated alteration suggest that the fluids were sourced from coeval diabase dikes and syenite porphyry and/or microsyenite porphyry intrusions. The rare earth element characteristics, 40Ar-39Ar and U-Pb geochronology of alteration and fresh magmatic rocks, δ 18O, δ D, Nd, and Sr isotope systematics together suggest that the fluids responsible for the high- to moderate-temperature assemblages are largely derived from the coeval alkaline igneous rocks (diabase and microsyenite porphyry dikes) that intrudes the sedimentary-volcanosedimentary basin.

A dark-green nephrite boulder collected from Pleistocene glacial outwash gravels, West Coast of New Zealand, has a 6.1 cm thick weathering rind composed of an inner pale-green-white bleached zone (3.5 cm) and an outer brown oxidised zone (2.6 cm). The primary mineralogy of the boulder is monomineralic actinolite with small amounts of secondary Al-substituted goethite within the weathering-rind. Outwards from the unweathered nephrite core, SiO2, FeO, MgO, CaO, Na2O and density decrease, while Fe2O3, Al2O3, Cr, H2O+, H2O− and bulk oxidation ratio increase. The generalised weathering reaction can be characterised as: actinolite+H2O+H+=Fe-hydroxide+silicic acid+(Ca2+, Mg2+, Na+)aq. Assuming that alumina was immobile during weathering, isocon analysis indicates a mass decrease of −24% and a volume change of −26% in the bleached zone and a mass decrease of −52% and volume change of −58% in the oxidised zone with 7–84% depletion of all elements except Fe3+ and H2O− which indicates gains of 47–51% and 42...

To determine the petrographic contrasts between ilmenite- and magnetite-series magmas, we assessed the rock descriptions, modal compositions, and whole-rock chemical compositions for ilmenite- and magnetite-series gabbroic masses in the Ryoke and San-in belts and focused on the primitive phases of the two plutonic belts. We obtained the following results: (1) The San-in gabbroids contain variable modal amounts of magnetite, up to 5.8%, whereas no magnetite was detected in the Ryoke gabbroids. The outcrop measurements of magnetic susceptibility exhibited good positive correlation with the magnetite contents of the outcrop samples. (2) As compared to the San-in gabbroids, the Ryoke gabbroids are generally less abundant in alteration minerals such as chlorite and fibrous actinolite and more abundant in olivine- and orthopyroxene-bearing phases. (3) The rock texture and whole-rock chemical compositions indicate that the Ryoke gabbroids have more cumulative characteristics than the San-in gabbroids. The compositional differences between them can be mainly explained by the differences between their degrees of crystal accumulation. (4) We were unable to detect any significant differences between the N-MORB normalized patterns of trace-elements and REEs in the Ryoke and San-in gabbroids. Features (2) and (3) may be responsible for the differences between the emplacement depths of the Ryoke and San-in gabbroic masses, although these features are independent of redox states. Feature (4) suggests that the two gabbroids have a common petrogenetic background. Based on these results, we conclude that the contamination of Ryoke gabbroic magma by sediments is insignificant, having little or no effect on redox states. It is more likely that the divergent redox states of the two gabbroic magmas are primarily attributable to the differences in the volatile components involved in the fO2 buffer reactions.

Alteration veins containing Cl-poor actinolite and actinolitic hornblende are a common feature throughout the Archean-aged gneisses and granitoids along the northern margin of the Sudbury Igneous Complex, Ontario, Canada. Crosscutting relations and structural measurements show that the veins postdate the Sudbury impact event but predate the emplacement of footwall-style Cu-Ni-PGE (platinum-group element) sulfide ores. The veins are four to five times more abundant in brecciated, mineralized outcrop than in unbrecciated, barren outcrop. Analyses of vein-hosted amphibole by electron microprobe (EMP) and laser ablation ICP-MS (LA-ICP-MS) show elevated concentrations of Ni (up to ~100 times background; increasing from ~100 ppm to ~1.0 wt %), Cu (up to ~4 times background) and Sn (up to ~2.5 times background) in proximity to sulfide veins. Copper and Sn contents in amphibole are only anomalous within 10 to 20 m of mineralization and require quantification by LA-ICP-MS. However, anomalous Ni concentrations in vein-hosted amphibole may be detected with a high level of confidence solely by EMP up to ~700 m from mineralization in rocks that contain no visible sulfides in hand sample or thin section and show no bulk rock Ni or Cu anomalies. The relationship between the Ni content in amphibole (in ppm) and mineralization proximity (distance “D” in meters) is given by the following equation: \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \[[Ni]_{amp}\ =\ 5100\ (D)^{{-}0.45}.\] \end{document} The data indicate wide-scale Ni mobility in hydrothermal solutions in the Sudbury footwall. The formation of Ni-rich amphibole in the fracture networks, by either the growth of primary Ni-rich amphibole or metasomatic Ni enrichment of preexisting (Ni-poor) amphibole, was associated with circulation of a sodium- and halogen-rich fluid between ~390o and 550oC. Nickel may have been released into the footwall environment by extensive hydrothermal alteration of Ni-rich contact-style sulfide ores that lie in the hanging wall of the Cu-rich footwall-style ores. In the footwall rocks, pre-existing fracture networks (now amphibole-bearing veins) acted as common structural pathways, first for the circulation of early Ni-rich fluids associated with leaching in the contact region and the onset of footwall mineralization, and second for the emplacement of Cu-rich footwall-style sulfide veins. Other metal concentrations in amphibole (Pb, Zn, Co) show no relationship to mineralization proximity. These metals may have been derived locally from country rocks during alteration reactions that promoted amphibole growth in the fractures. Identification of fracture-hosted amphibole with anomalous Ni contents in thin section, or Ni-Cu-Sn anomalous amphibole grains liberated from surface-weathered rocks hosting sulfide veins may serve as useful proximity indicators for hidden footwall-style sulfide deposits at Sudbury.

Microstructural and petrological analyses of gabbroic rocks sampled from the Godzilla Mullion, located along the Parece Vela Basin spreading ridge (Parece Vela Rift), Philippine Sea, reveal the development of a ductile shear zone in the lower crust. The shear zone is interpreted to represent a detachment fault within an oceanic core complex. Microstructures indicative of intense deformation, characterized by porphyroclastic textures consisting dominantly of coarse plagioclase porphyroclasts and lesser clinopyroxene porphyroclasts in a fine-grained matrix, are observed within samples of gabbroic rocks dredged near the breakaway area of the Godzilla Mullion (dredge site D6). Samples are classified into three types based upon the grain-size of fine-grained plagioclase in the matrix: coarse (80–130 µm), medium (25 µm), and fine (∼ 10 µm). Although the chemical composition of plagioclase porphyroclasts is consistently An 40–50 among all sample types, the compositions of fine grains in the matrix vary with decreasing grain-size, being An 40–50 for the coarse-type, An 30–40 for the medium-type, and An 5–30 for the fine-type. This finding implies that the composition of fine-grained plagioclase in the matrix is related to the following retrograde reaction that occurred during deformation: clinopyroxene + plagioclase + Fe–Ti oxide + fluid → hornblende + plagioclase. Plagioclase crystal-preferred orientations also show a gradual change with grain-size, varying from a (010)[100] pattern for the coarse-type, (010)[100] and (001)[100] patterns for the medium-type, and a weak (001)[100] pattern or random orientations for the fine-type. These patterns are interpreted to result from a change in the deformation mechanism of plagioclase from dislocation creep to grain-size-sensitive creep with decreasing temperature, thereby leading to strain softening and localization during cooling. Although secondary amphibole occurs ubiquitously within all samples, the chemical composition of amphibole varies from pargasitic hornblende (i.e. brown hornblende) to actinolite (i.e. green hornblende) within each of the sample types. However, amphibole in the coarse-type shows no evidence of deformation, whereas brown hornblende in the medium- and fine-types is plastically deformed. As a consequence, we argue that the microstructural development of the gabbroic rocks occurred during uplift-related cooling of the gabbro body and that a primary shear zone developed near the breakaway area at depth under anhydrous conditions at high temperatures above 850 °C; the shear zone subsequently evolved during progressive retrogression in association with hydration of the shear zone, possibly resulting in the development of the detachment fault that gave rise to the Godzilla Mullion.

The Empire Cu-Zn skarn deposit is unusual because of the proximal position of Zn mineralization, abundance of endoskarn, and the extremely vermicular texture of quartz phenocrysts in the related intrusive rocks. Cu-Zn skarn occurs at the contact between Upper Mississippian White Knob limestone and the granite porphyry phase of the Mackay Stock which consists, from early to late, of quartz monzodiorite, granophyre, granite porphyry, porphyritic granite, and many dikes. The late phases have high F and also extremely vermicular quartz phenocrysts. Endoskarn is more abundant than exoskarn. The earliest alteration of the intrusive rocks consists of disseminated diopsidic pyroxene (Di64Hd36 to Di88Hd12), actinolite, and titanite. This assemblage was cut by early scapolite (Me18 to Me35, mostly Me18-26) and/or green pyroxene (Di14Hd80 to Di20Hd77) veinlets, with or without wollastonite halos. These early veins were then cut by main-stage endoskarn veins that typically have a garnet + minor pyroxene inner zone, a wollastonite and/or pyroxene ± Ca-rich plagioclase (An56 to An89) envelope, and a halo containing disseminated, fine-grained alteration minerals of the same assemblage as the envelope. Some veins contain only the envelope assemblage and are interpreted to represent the alteration front. The inner zone locally contains vesuvianite. Where many veins intersect, endoskarn is massive. Pyroxene is zoned around fluid conduits; the distal pyroxene is Fe rich (hedenbergitic) whereas the proximal pyroxene is Fe poor (diopsidic). The garnet changes in the opposite way, being Fe poor-Al rich (grossularitic) in locations distal to the fluid conduits, and Fe rich (andraditic) in proximal locations. In contrast, in the exoskarn, all pyroxene is diopsidic and garnet is andraditic. Weak, retrograde alteration composed of quartz + calcite + chlorite with minor fluorite, talc, and epidote overprinted both endoskarn and exoskarn. Magnetite precipitated after garnet-pyroxene in both endoskarn and exoskarn. Sphalerite precipitated together with chalcopyrite in proximal locations and is associated with retrograde alteration. Other ore minerals include minor molybdenite, bornite, pyrite, galena, arsenopyrite, native Au, as well as supergene minerals such as chrysocolla, malachite, azurite, native Cu, and limonite. Fluid xenoliths from pyroxene in early endoskarn veinlets homogenize at >600°C. Massive endoskarn and exoskarn replacing limestone inclusions in granite porphyry formed at 500° to >700°C, whereas the highest temperature inclusions, >700°C, occur in narrow garnet + minor pyroxene veins. Fluid inclusions in exoskarn replacing wall rock have homogenization temperatures of 500° to 650°C. Retrograde alteration and Cu-Zn mineralization occurred at 250° to 300°C. Fluid inclusions in prograde minerals contain daughter minerals, whereas fluid inclusions in retrograde minerals do not, indicating a decrease in salinity with time. Late-stage fluids have low eutectic temperatures, indicating the possible presence of KCl, NaCl, FeCl2, CaCl2, MgCl2, K2CO3, and/or Na2CO3. Formation of the unusually abundant endoskarn, the proximal position of Zn mineralization, and the extremely vermicular texture of quartz phenocrysts are all believed to have been promoted by the high F content of the magmatic fluid. These features may serve as exploration indicators of associated high F mineralization such as buried porphyry Mo deposits.

The Jinbaoshan Pt–Pd deposit in Yunnan, SW China, is hosted in a wehrlite body, which is a member of the Permian (∼260 Ma) Emeishan Large Igneous Province (ELIP). The deposit is reported to contain one million tonnes of Pt–Pd ore grading 0.21% Ni and 0.16% Cu with 3.0 g/t (Pd + Pt). Platinum-group minerals (PGM) mostly are ∼10 μm in diameter, and are commonly Te-, Sn- and As-bearing, including moncheite (PtTe2), atokite (Pd3Sn), kotulskite (PdTe), sperrylite (PtAs2), irarsite (IrAsS), cooperite (PtS), sudburyite (PdSb), and Pt–Fe alloy. Primary rock-forming minerals are olivine and clinopyroxene, with clinopyroxene forming anhedral poikilitic crystals surrounding olivine. Primary chromite occurs either as euhedral grains enclosed within olivine or as an interstitial phase to the olivine. However, the intrusion has undergone extensive hydrothermal alteration. Most olivine grains have been altered to serpentine, and interstitial clinopyroxene is often altered to actinolite/tremolite and locally biotite. Interstitial chromite grains are either partially or totally replaced by secondary magnetite. Base-metal sulfides (BMS), such as pentlandite and chalcopyrite, are usually interstitial to the altered olivine. PGM are located with the BMS and are therefore also interstitial to the serpentinized olivine grains, occurring within altered interstitial clinopyroxene and chromite, or along the edges of these minerals, which predominantly altered to actinolite/tremolite, serpentine and magnetite. Hydrothermal fluids were responsible for the release of the platinum-group elements (PGE) from the BMS to precipitate the PGM at low temperature during pervasive alteration. A sequence of alteration of the PGM has been recognized. Initially moncheite and atokite have been corroded and recrystallized during the formation of actinolite/tremolite, and then, cooperite and moncheite were altered to Pt–Fe alloy where they are in contact with serpentine. Sudburyite occurs in veins indicating late Pd mobility. However, textural evidence shows that the PGM are still in close proximity to the BMS. They occur in PGE-rich layers located at specific igneous horizons in the intrusion, suggesting that PGE were originally magmatic concentrations that, within a PGE-rich horizon, crystallized with BMS late in the olivine/clinopyroxene crystallization sequence and have not been significantly transported during serpentinization and alteration.

Mineralization, involving vanadian-chromian silicates, has been studied in Lower Paleozoic, carbon-rich amphibole schists with pyrite and pyrrhotite near Pezinok, southwest Slovakia. A detailed electron microprobe study has revealed the presence of V,Cr-rich garnet, clinozoisite, and muscovite, associated with amphiboles (magnesiohornblende, tremolite, actinolite, and edenite), diopside, and albite. The garnet contains 5-19 wt% V 2 O 3 , 5-11 wt% Cr 2 O 3 , and 2-13 wt% Al 2 O 3 (16-64 mol% goldmanite, 19-36 mol% uvarovite, and 9-59 mol% grossular end-members). The garnet is unzoned or shows V-rich cores and Al-rich rims, or irregular coarse oscillatory zoning with V, Cr, and Al, locally involving Ca and Mn as well. The V,Cr-rich clinozoisite to mukhinite and "chromian clinozoisite" contains 2-9.5 wt% V 2 O 3 and 1.5-11 wt% Cr 2 O 3 ; the muscovite contains 2.5-8 wt% V 2 O 3 and 0-7 wt% Cr 2 O 3 . The mineralization originated from primarily V-, Cr-, and C-rich mafic pyroclastic rocks, affected by volcano-exhalative processes. These rocks were weakly metamorphosed during early Hercynian regional metamorphism (Ml), followed by late-Hercynian contact metamorphism (M2) with crystallization of V,Cr-rich silicates, diopside, amphiboles, phlogopite, titanite, albite, quartz, carbonate, pyrite, and pyrrhotite. The youngest Alpine(?) retrograde metamorphic event (M3) is connected with production of V.Cr-poor muscovite, clinochlore, clinozoisite, pumpellyite-(Mg), prehnite, quartz, and carbonates, under prehnite-pumpellite facies conditions.

The occurrence of actinolite in magnetite deposits of possible mag-matic origin has prompted an experimental investigation of theupper thermal stability of Mg-rich actinolite to determine how thestability of actinolite changes with increasing Fe content.Experiments were carried out primarily on the compositionalre-equilibration of natural tremolite [molar Fe/(FeþMg)¼Fe-number ¼0 014] in the presence of synthetic clinopyroxene(Ca

The paper presents materials on the fabric of the western, southwestern, and southern exocontact zones of the Khibina alkaline pluton and metavolcanic rocks of the Il’mozerskaya Formation of the Paleoproterozoic Imandra-Varzuga riftogenic structure. The volcanics of the Imandra-Varzuga structure were originally metamorphosed to the greenschist facies (at temperatures of ≥300°C and pressures of ≥2.0–2.5 kbar) and were afterward metamorphosed to the pyroxene-hornfels facies under the thermal effect the Khibina pluton with the development of a hornfels zone 150–400 m thick. According to their composition, the hornfelses are subdivided into three zones: inner, intermediate, and outer. The inner zone is up to 30 m thick and consists of hornfelses of clinopyroxene-plagioclase composition with olivine as a typomorphic mineral and with variable amounts of amphibole. The intermediate zone occurs at a distance of 30–200 m from the pluton, is separated from the inner zone by the olivine isograde, and consists of amphibole-clinopyroxene-plagioclase hornfelses. The outer zone, 200–400 m away from the contact of the pluton, is made of fine-grained melanocratic hornblende hornfelses. The thermal transformations of the metavolcanics involved the gradual replacement of their low-temperature mineral assemblage (actinolite + albite) by a higher temperature one (clinopyroxene + amphibole + andesinebytownite ± olivine). Our data on the chemical composition of the rock-forming minerals of the hornfelses indicate that the olivine is ferrohortonolite-fayalite, the clinopyroxene belongs to the augite-ferroaugite series, and occasional orthopyroxene grains (which were found only in the intermediate zone) are ferrohypersthene. The amphibole in the hornfelses of the intermediate zone and the outermost (farthest from the contact) part of the inner zone is edenite, a Ca amphibole. The amphibole in hornfelses near the contact is kataphorite of the Na-Ca amphibole group. The plagioclase composition generally corresponds to andesine and bytownite and is albite-oligoclase near the contact with the pluton. The hornfelses adjacent to the contact bear rare sanidine grains. The mineral thermo-and barometry of the hornfelses yielded temperatures of 700–640°C and pressures of 1–1.5 kbar. The temperature determined for the zone exactly at the contact was approximately 700°C, which corresponds to the initial temperature of the rocks in contact with the magma and is close to the crystallization temperature of the nepheline syenites of the Khibina pluton.

To investigate the water budget in deep accretionary prisms, we undertook a detailed petrologic analysis of garnet-bearing amphibolites in the subduction-origin high-pressure Sanbagawa metamorphic belt, Japan. We obtained a continuous P–T path of exhumation by the application of differential thermodynamics to compositional zoning in both garnet and amphibole. The P–T path is characterized by three stages of decompression: (1) heating decompression from 1.5 GPa and 550 °C to 1.1 GPa and 600 °C; (2) isothermal decompression toward 0.8 GPa and 580 °C; and (3) cooling decompression to 0.3 GPa and 400 °C. Comparison with the results of numerical modeling of the thermal structures of subduction zones suggests that the peak-pressure condition is warmer than the slab surface temperature in a typical subduction zone, but is consistent with subduction of a young slab during the Sanbagawa metamorphism. The heating decompression just after the peak-pressure condition is explained by heating from the mantle wedge during ascent of the metamorphic body in the accretionary prism; heating stops when the metamorphic body reaches crustal depths. Mass balance calculations for the mineral reactions in an amphibolite reveal that the dehydration associated with the growth of Ca-poor garnet takes place during heating decompression, whereas hydration takes place during cooling decompression by the breakdown of garnet and pargasite to form chlorite and actinolite. Such a transition from dehydration to hydration in the exhuming metabasite body in an accretionary prism generates fluids between the continental Moho and the slab surface and may explain the seismic activity above the subduction plate boundary, such as supra-slab earthquakes.

The Bjorkdal quartz vein-hosted gold deposit is located ~25 km northwest of Skellefte in northern Sweden, within a Paleoproterozoic volcanosedimentary sequence at the margin of a quartz-monzodiorite granitoid. Northeast-trending (030°– 050°) quartz veins from the eastern open pit within the Bjorkdal deposit contain quartz, scheelite, tourmaline, calcite, and sulfides, with visible gold. Vein quartz shows undulatory extinction and sutured margins or is polycrystalline in form, features which suggest postcrystallization deformation. Coarse scheelite crystals (>5 mm) within the quartz veins are crosscut by thin veins of quartz, calcite, sulfides, and gold. The calcite in these crosscutting fractures is variably replaced by biotite or actinolite. Tourmaline from the quartz veins has low total REE contents (

The Lac des Iles Pd mine, with reserves of 88 million metric tons (Mt) containing 1.51 g/t Pd, is hosted by the 2.69 Ga Lac des Iles intrusive complex in the southern Wabigoon subprovince of the Superior province of Canada. The known economic concentration of Pd occurs in the Mine Block intrusion, the central body of the intrusive complex, where gabbroic rocks range from leucogabbro to pyroxenite and show complicated textures, such as breccias, magma mingling, and pods and veins of pegmatite. The ore is characterized by low concentrations of sulfide (typically less than 3 vol %) and exceptionally high Pd contents (Pd/Pt ~10, Pd/Au ~13). Detailed mapping of the southern Roby and Twilight zones shows that early leucocratic rocks are barren and that the bulk of Pd was introduced by late melanocratic magmas. The average concentration of Pd in the melanocratic rocks, excluding the High-Grade zone, is estimated to be ~4 ppm. The concentrations of sulfur correlate positively with those of base metals, platinum group elements (PGE), and Au. Furthermore, sulfide grains commonly show exsolution textures. The evidence suggests a magmatic origin of the PGE mineralization where the PGE were concentrated in an immiscible sulfide melt in the parental magma. Bulk chemical compositions suggest that all mafic igneous rocks in the mineralized zones, except for late clinopyroxenite, are cogenetic. The hypothetical parental magmas have high MgO and low (~15× chondrite), unfractionated rare earth elements (REE) with (Ce/Yb)chondrite 35% of Pd in the deposit) on the eastern margin of the Roby zone have much higher concentrations of Pd than any other rocks and do not show correlations between sulfur and precious and base metals. Furthermore, the rocks are intensely and pervasively altered to actinolite, talc, anthophyllite, hornblende, chlorite, sericite, calcite, and quartz. These observations suggest subsolidus enrichment of Pd and mobility of S. The lack of apparent fluid pathways within the High-Grade zone and the distribution of the zone are consistent with the enrichment of Pd at high temperatures by fluids that originated from the mafic magmas. The textures of the Lac des Iles deposit are similar to those of contact-type PGE deposits, but there are fundamental differences between the two. The Lac des Iles deposit is not localized near the contact between the host intrusion and the country rocks and evidence of the assimilation of the host rocks is lacking. Instead, the mineralization at Lac des Iles has many features in common with layered intrusion-hosted deposits, in which pulses of primitive magma introduced the PGE. Unlike the quiescent magma chambers of most layered deposits, the magmas at Lac des Iles were intruded energetically, forming breccias and magma-mingling textures.

Interaction of base metal sulfides (pyrrhotite, pentlandite, and chalcopyrite) with aqueous fluids in the UG2 chromitite layer and the Merensky reef in the western Bushveld Complex has produced four common replacements: (1) replacement of sulfides and orthopyroxene by actinolite or tremolite, (2) replacement of sulfides and plagioclase by epidote, (3) replacement of sulfides by calcite, and (4) replacement of sulfides by magnetite. The first three replacements are directly related to the presence of sulfides in the rocks and occur at the grain scale; silicate minerals that are not in direct contact with sulfides are usually not affected. The replacement of sulfides by magnetite accompanies regional serpentinization superimposed on the Union section. Platinum group minerals, including Ru, Pt, and Pd sulfides, Pt and Pd tellurides, and Pd arsenides, occur in replacement aureoles around sulfide aggregates as well as within the aggregates, suggesting that the platinum group minerals are more resistant to hydrothermal alteration than the associated base metal sulfides. Redistribution of chalcopyrite, at least at the millimeter scale, variable losses of S and Ni, and perhaps decoupling of Pt and Pd at the centimeter scale took place during secondary hydrothermal alteration. These effects should be considered before models of primary mineralization processes can be meaningfully applied.

Optimal activities of amphibole are obtained by means of a new application of Gibbs’ method to the assemblage amphibole-epidote-chlorite-plagioclase-quartz-water in the system SiO2-Al2O3-Fe2O3-FeO-MgO-CaO-Na2O-H2O, and consequently T, P and X are derived from the amphibole chemistries via the differences relative to a set of the reference conditions. Amphibole solid solutions are modeled by the regular solution composed of seven end-members (tr-ts-ed-gln-mrb-fact-otr), and the optimal Margules parameters are obtained from hundreds of natural data sets of amphiboles in the Sanbagawa schists in the range 300–550 °C, 0.2–1.1 GPa. The temperatures obtained by Gibbs’ method are consistent with the temperatures by the hornblende-plagioclase thermometer with the absolute deviation of about 30 °C. The P-T conditions of calcic and subcalcic amphiboles are plotted in the stability fields of actinolite, hornblende, winchite, and barroisite of the greenschists and epidote-amphibolite facies conditions. Calculations for the representative zonings of amphiboles in the Sanbagawa schists suggest distinctive decompression P-T paths.

Ridgeway is a high-grade gold-copper porphyry deposit (54 Mt at 2.5 g/t Au and 0.77% Cu), related to an alkalic intrusive complex of monzonitic composition. The deposit occurs within the Cadia district of New South Wales, Australia, which consists of a cluster of four Late Ordovician gold-copper porphyry deposits and two iron-copper-gold skarn deposits with a combined gold resource in excess of 574 metric tonnes (t). The deposits lie on a 7-km-long, northwest-oriented corridor of alteration and mineralization, transverse to the axis of the postulated volcanic arc. Alteration and mineralization at Ridgeway are zoned around a vertically attenuated intrusive complex of monzodioritic to quartz monzonitic composition. Distinct styles of veining and alteration are related to different intrusive phases of the monzonite complex, with the intensity of alteration and grade of mineralization decreasing from early- to late-mineral intrusions. Early-mineral intrusions are associated with intense actinolite- magnetite-biotite (calc-potassic) alteration and up to four stages of high-grade quartz-magnetite-sulfide veining. Bornite is the most abundant sulfide formed during early-stage alteration and correlates well with gold. Moderate- to weak-intensity orthoclase-biotite plus or minus magnetite (potassic) alteration accompanies the inter- and late-mineral intrusions, this alteration being associated with chalcopyrite- and pyrite-rich quartz-orthoclase veins. Propylitic and sodic (albite-pyrite) alteration assemblages are peripheral to, and locally overprint, the potassic alteration. Phyllic alteration is restricted to the margins of late-stage faults. The fluid inclusion assemblage comprises one and two salt-bearing brine inclusions, in addition to aqueous liquid-vapor inclusions of low to moderate salinity. No low-density, vapor-rich inclusions are present, indicating that the fluids from which the quartz veins precipitated did not enter the liquid-vapor field of the H2O-NaCl system. The brine inclusions undergo final homogenization to liquid via halite dissolution. This phenomenon, in addition to the absence of low-density vapor inclusions, suggests that the mineralizing fluids at Ridgeway were nonboiling hypersaline brines that exsolved directly from the crystallizing magma. The presence of mineralized aplitic vein dikes and comb quartz layering are interpreted to indicate that the early and transitional stages of mineralization at Ridgeway formed at the transition between magmatic and hydrothermal conditions.

The Jinchuan Ni–Cu sulfide deposit is hosted by an elongated, olivine-rich ultramafic body that is divided by subvertical strike-slip faults into three segments (central, eastern, and western). The central segment is characterized by concentric enrichments of cumulus olivine crystals and interstitial sulfides (pyrrhotite–pentlandite–chalcopyrite intergrowth), whereas the eastern and western segments are characterized by an increase of sulfides toward the lower contacts. In all segments sulfides are concentrated at the expense of intercumulus silicates. Olivine re-crystallization is found to be associated with actinolite alteration in some samples. The compositional variations of primary olivine from the sulfide-poor samples can be explained by a small degree of olivine crystallization ( 50 modal%) and sulfide (averaging ~5 wt%) in the rocks are consistent with the interpretation that the Jinchuan deposit was formed by olivine- and sulfide-laden magma successively ascending through a conduit to a higher, now-eroded, level. Sulfide enrichment toward the center in the central segment and toward the lower contact in the eastern and western segments may have, in part, resulted from flow differentiation and gravitational settling during magma ascent, respectively.

International audience; The behaviour of rare earth elements (REE) during fluid–rock interaction in mid-crustal shear zones has received little attention, despite their potential for mass balance calculation and isotopic tracing during deformation. In this study, several cases of large REE mobility during Alpine fluid-driven shear zone development in the pre-Alpine granitic basement of the Mont Blanc Massif are considered. On a regional scale, the undeformed granite compositions range within 5 wt% SiO2 (70.5–75.3 wt%) and magmatic chemical variations are of the order of 10–20%, ascribed to minor effects of crystal fractionation. Major and trace element mobility observed in shear zones largely exceeds these initial variations. Shear zones developed a range of mineral assemblages as a result of shearing at mid-crustal depths (at not, vert, similar0.5 GPa, 400°C). Five main shear zone assemblages involve muscovite, chlorite, epidote, actinolite and calcite, respectively, as major phases. In most cases, selective enrichments of light or heavy REE (and Y, Ta, Hf) are observed. REE mobility is unrelated to deformation style (cataclastic, mylonitic), the intensity of strain, and to the shear zone's major metamorphic mineral assemblages. Instead, the changes in REE concentrations are ascribed to the alteration of pre-existing magmatic REE-bearing minerals during deformation-related fluid–rock interaction and to the syntectonic precipitation of metamorphic REE-bearing minerals (mainly monazite, bastnäsite, aeschynite and tombarthite). Minor proportions (

The NICO Au-Co-Bi(±Cu±W) deposit is located in the Great Bear magmatic zone, NWT, Canada, where numerous polymetallic, iron oxide-dominated mineralized systems have been recognized. Petrographic, electron microprobe analysis (EMPA), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) studies of host-rock alteration and ore mineralogy, together with sulfarsenide geothermometry, have been carried out to constrain the nature of alteration and/or mineralization assemblages in this deposit. Metasedimentary rocks of the Treasure Lake Group host NICO and are pervasively altered to an assemblage of ferrohornblende I + actinolite I + biotite I + magnetite I ± orthoclase, which is cut by barren veins composed of quartz ± ferrohornblende-orthoclase-calcite (Set 1). These alteration events are overprinted by metasomatic prograde and retrograde mineralized assemblages and both brittle and ductile deformation accompanied the metasomatism. The prograde assemblage (>400°C) consists of cobaltite, Co-rich loellingite, and Co-rich arsenopyrite (stage I), magnetite II, ferrohornblende II, actinolite II, biotite II, pyrite, and minor scheelite and orthoclase. The earliest retrograde mineralization consists of arsenopyrite (stages II and III), which contains variable amounts of Co, together with native Bi (±bismuthinite) and Au, with lesser magnetite, marcasite, pyrite, hastingsite, and minor quartz. The preservation of solidified native Bi droplets suggests a temperature range of 270° to

The fibrillar growth habit and {100} twinning of fibrous amphiboles tend to produce anomalous optical properties. Commercial amosite and crocidolite always exhibit uniaxial-like optical properties including parallel extinction and two principal indices of refraction. Fibrous members of the actinolite series, however, exhibit a range in optical properties from normal to anomalous. The types of anomalous optical properties that can be displayed by asbestiform members of the actinolite series are described based on a study of twelve samples. One sample displays uniaxial-like properties, nine display partial development of uniaxial-like properties, and two contain fibers with both orthorhombic and monoclinic optical properties. “Byssolitic” samples of the actinolite series, a fibrous non-asbestiform habit, contain fibers that do not go to extinction in sections on or near (010), probably as a result of {100} twinning. Although anomalous optical properties may confound the identification of fibrous amphiboles, in most cases the refractive indices are predictable and can be used for identification. Because of the range in optical properties, especially extinction angle, reliance solely on parallel extinction to distinguish asbestos from non-asbestiform varieties is not recommended. The fibrillar structure, however, remains the hallmark of the asbestiform habit.

Fine structure in the principal OH-stretching bands of amphiboles of the tremolite-ferro-actinolite series have been examined. In samples with partly filled A sites, a broad (composite) band is observed at 3725∼3680 cm - 1 and is assigned to two types of configurations: (M1M1M3)-OH- A (Na,K): T 1 Si T 1 Al in which Al occurs at the T1 site, and (M1M1M3)-OH- A (Na,K)- O 3 (O 2 - ,F - ,Cl - ); the component of (M1M1M3)-OH- A (Na,K): T 1 Si T 1 Si configuration is small, because Na and K at the A site are locally associated with Al at an adjacent T1 site. In tremolite, manganoan tremolite, and Fe 2 + -poor actinolite, a weak shoulder on the principal A band at -3669 cm - 1 is assigned to the configuration M 4 Ca M 4 (Mg,Fe 2 + ,Mn 2 + ,Na):(MgMgMg)-OH- A □: T 1 Si T 1 Si (□ = vacancy). Fine structure in the principal bands B (B' and B") and C (C' and C") are also observed: the higher-frequency band B" is assigned to M 1 Fe 2 + M 1 Mg M 3 Mg-OH- A □, and the lower-frequency band B' to M 1 Mg M 1 Mg M 3 Fe 2 + -OH- A □; the higher-frequency band C' is assigned to M 1 Fe 2 + M 1 Fe 2 + M 3 Mg-OH- A □ and the lower-frequency band C" to M 1 Mg M 1 Fe 2 + M 3 Fe 2 + -OH- A □. Some broad OH-stretching bands attributed to (M1M1M3)-OH- A □: T 1 Si T 1 Al are observed at 3640∼3580 cm - 1 . In amphiboles of the tremolite-ferro-actinolite series that show a substantial B [(MgMgFe 2 + )-OH] band, a new OH-stretching band (at around 3641 cm - 1 ), E, appears near the principal C band (at around 3643 cm - 1 ) on heat treatment. The shape of band E is similar to that of the original band B, and its local configuration is O 2 - -(MgMgFe 3 + )-OH - . A weak and broad band A** appears at -3690 cm - 1 on heat treatment of some Na-bearing actinolites, and is ascribed to the (MgMgMg)-OH- A Na-O 2 configuration.

Mid-Mesozoic to Tertiary igneous activity reflects arc evolution along the Sierra + White-Inyo sector of the continental margin. The Ca-amphibole + biotite ± augite-bearing Middle Jurassic Barcroft pluton consists of intergradational, quartzose gabbro-diorite, metadiorite, voluminous mafic-to-felsic granodiorite, and rare alaskite-aplite. It was emplaced along the Barcroft structural break—a major ENE-striking suture juxtaposing mid-Mesozoic bimodal metavolcanics on the north against metamorphosed Lower Cambrian platform strata on the south. The Cretaceous, two-mica McAfee Creek Granite intruded both wall rocks and the Barcroft granodioritic pluton on the east. Geologic mapping and petrochemical studies have documented the structure and metaluminous geochemistry of the Barcroft body. Analyses of Ca-clinoamphiboles from 16 Barcroft rocks allow the assignment of P-T conditions of crystallization/recrystallization based on experimentally determined and calculated clinoamphibole thermobarometers. Combined with earlier studies of country-rock metamorphism, and oxygen isotopic investigations of mineral assemblages in both plutons and wall rocks, four stages in the P-T evolution of the Barcroft pluton have been identified: Stage 1, partial melting of a mafic protolith at ~25 km or greater depth, then onset of crystallization of refractory hornblende and other ferromagnesian phases at ~915 ± 25 °C attending magma ascent. Stages 2 → 3, crystallization of progressively more actinolitic hornblende during decompression cooling and stalling of the pluton at a depth of 10–12 km, as temperature declined over the interval ~760–650 °C. Stage 4, subsolidus recrystallization/exsolution of nearly stoichiometric actinolite ± grunerite attending deuteric alteration over the range ~395–545 °C at a depth of 4–5 km. Mineral assemblages of stages 1 → 4 are disposed progressively inward, indicating that the Barcroft pluton lost heat along intrusive contacts with the wall rocks, cooling, annealing, and re-equilibrating in the process. The Cretaceous McAfee Creek Granite transected this ENE-trending thermal zonation, but exerted little effect on Ti + Al contents (and δ18O values) of Barcroft amphiboles.

Retrograde eclogites and serpentinites from the Hochgrossen massif, Styria, are parts of the Speik complex in the Austroalpine basement nappes of the Eastern Alps. They are in tectonic contact with pre-Alpine gneisses, amphibolites, and Permo-Triassic quartz phyllites (Rannach Series). The eclogites are derived from ocean-floor basalts with affinities to mid-ocean ridge and back-arc basin basalts. Fresh eclogites are rare and contain omphacite with a maximum of 39 mol% jadeite content, garnet (Py15–19) and amphibole. Retrograde eclogites consist of amphibole and symplectites of Na-poor clinopyroxene (5–8 mol% Jd) + albite ± amphibole. Amphiboles are classified as edenite, pargasite, tschermakite, magnesiohornblende and actinolite. In relatively fresh eclogite, edenite is a common amphibole and texturally coexists with omphacite and garnet. An average temperature of 700 °C was obtained for eclogite facies metamorphism using garnet-pyroxene thermometry. A minimum pressure of 1.5 GPa is indicated by the maximum jadeite content in omphacite. Thermobarometric calculations using the TWEEQ program for amphibole in textural equilibrium with omphacite and garnet give pressures of 1.8–2.2 GPa at 700 °C. The equilibrium assemblage of Na-poor clinopyroxene, albite, amphibole and zoisite in the symplectites gives a pressure of about 0.6–0.8 GPa at 590–640 °C. 40Ar/39Ar radiometric dating of edenitic amphibole in textural equilibrium with omphacite gave a plateau age of 397.3 ± 7.8 Ma, and probably indicates retrograde cooling through the closure temperature for amphibole (∼500 °C). The age of the high-pressure metamorphism thus must be pre-Variscan and points to one of the earliest metamorphic events in the Austroalpine nappes known to date.

Two spatial scales of fluid–rock interaction in an ophiolite suite are revealed by oxygen isotope and hydrogen isotope studies of metagabbros on the island of Tinos (Cyclades, Greece). Sequentially formed mineral generations in the metagabbros include relict igneous augite, hornblende of sub-seafloor hydrothermal origin, and actinolite and albite formed by regional greenschist-facies metamorphism during orogenesis. With the exception of augite (δ 18 O=4.4–5.6‰), the metagabbros are characterized by unusually high δ 18 O values: hornblende (5.8–7.4‰), actinolite (6.5–10.2‰), feldspar (14.6–14.9‰) and whole rocks (7.0–10.5‰). Hornblende δ D values range from −57 to −66‰. The high δ 18 O values and the δ D range of the hornblendes are compatible with interaction of oceanic gabbro with seawater that had previously been enriched in 18 O/ 16 O (δ 18 O=6.5–8‰) by isotopic exchange at moderate to high temperatures. The high degree of oceanic alteration in the layered gabbros, mass balance calculations of isotopic exchange, and field evidence for early oceanic thrusting suggest that seawater could have penetrated deeply into the ocean crust, becoming 18 O/ 16 O-enriched through isotopic exchange with gabbros at progressively increasing temperature. Upward, down-temperature flow of the high-δ 18 O water would be very effective in elevating the δ 18 O values of gabbros. The regional greenschist metamorphic overprint of the ophiolite, possibly the result of continued thrusting and piling up of nappes during obduction, is characterized by localized fluid–rock exchange. Actinolite in massive gabbroic layers has δ 18 O values (6.5–7.2‰) close to those of the hornblende, whereas in deformed meter-sized gabbroic blocks the amphiboles have significantly higher values (8.4–10.2‰). Likewise, albite in the gabbroic blocks has high δ 18 O values of ca. 15‰ that are ascribed to meter-scale exchange with 18 O-rich fluids derived from dehydration reactions in low-temperature hydrothermally altered basaltic host rock enclosing the blocks. Deformation-enhanced permeability facilitated fluid infiltration in gabbroic blocks, whereas the relatively undeformed, and therefore less permeable, massive gabbros experienced minor interaction with fluids. The orogenic fluid–rock interaction thus represents local-scale redistribution of hydrous mineral components introduced during seafloor hydrothermal exchange.

The Pena Colorada iron skarn is located in the southern part of the Guerrero terrane. It contains 150 million metric tons (Mt) with a grade of 36 percent magnetite. The deposit occurs at the contact of a 68 Ma equigranular diorite with mid-Cretaceous volcano-sedimentary rocks of the Tepalcatepec Formation. Volcanic units within this formation have tholeiitic affinity and REE patterns that are compatible with a primitive arc setting. The Pena Colorada diorite and associated voluminous aplitic phases are part of a Late Cretaceous calc-alkaline continental arc that subsequently intruded this basin. Northeast-vergent deformation affected the region in the Late Cretaceous. North-south and east-west reverse, and northwest and northeast strike-slip faults localize the mineralization. The alteration halo around the diorite intrusion is 500 m wide. Within an inner 200-m halo, the volcano-sedimentary section was affected by an early metamorphic event, with discontinuous bands of pyroxene (Di 68 Hd 29 Jo 3 ) hornfels and garnet (Gr 61 Am 36 Ad 3 ) disseminations. Metasomatic pyroxene, garnet, and plagioclase cut the early metamorphic event preferentially replacing carbonate and volcanic units up to and including a 35-m-thick marl located 200 m above the intrusion. Metasomatic pyroxene and garnet have average compositions of Di 77 Hd 21 Jo 2 and Ad 76 Gr 20 Am 2 Sp 1 Py 1 , respectively. Pyroxene compositions reach Di 94 Hd 5 Jo 1 , whereas garnet exhibits intragrain compositional zoning from Ad 49 Gr 46 in the core to Ad 100 Gr 0 in the rim. Albitization of preexisting protoliths modified igneous plagioclase compositions from Ab 67 An 32 Or 1 up to Ab 96 An 3 Or 1 . Albitization is followed by abundant fracture-controlled Fe-epidote and Cl-bearing chlorite (Cha 84 Cli 14 Pen 2 ) that extend from the marl unit outward some 300 m. This association is cut by a later assemblage of epidote-chlorite-prehnite that affects the entire 500-m width of the alteration halo and part of the intrusion. Chlorite (Cha 54 Cli 45 Pen 1 ) from this later event is richer in Mg than that from the previous association. Igneous hornblende in the intrusion is altered to actinolite. A potassic alteration event related to a hydrothermal breccia and aplitic dikes overprints the pre-existing calc-silicate associations. Alteration minerals in the breccia and the 200-m potassic halo around it, evolve from early K feldspar-(biotite)-quartz, to late jasperoid-fluorapatite-calcite veins. Mg-rich biotite (Phl 77 Ann 23 ) and REE-rich apatite contain F/Cl/OH ratios of 1/0/3 and 1/0/0, respectively. Massive magnetite (36‰)-specular hematite (7‰)-sulfide ( O, C, S, and H stable isotope determinations on minerals from the calc-silicate association are consistent with an igneous source for the initial fluids, which mixed outward with an increasing component of trapped seawater or evaporite. However, water in equilibrium with magnetite exhibits unusually enriched δ 18 O values relative to other coexisting mineral-derived fluids. A solution that equilibrated with limestone at relatively high temperature is required to explain these heavy values.

Diopside-rich, skarn-hosted, copper–gold ore derived primarily from carbonaceous metapelites at Mount Elliott forms a distinctive member of the spectrum of Cu–Au–(Fe oxide) deposit styles in the Cloncurry district of the Paleoproterozoic to Mesoproterozoic Mount Isa Block. The mine sequence is a package of carbonaceous metapelites and metagreywackes containing amphibolites derived from tholeiitic basic rocks. A 40Ar–39Ar age spectrum with an extensive plateau-like segment at 1,510 ± 3 Ma from an actinolite associated with sulfides is taken to represent the age of mineralization and is identical within error to the ages of most of the nearby batholithic granitoids. The mine sequence is locally intruded by 1- to 10-m-thick late- to post-tectonic trachyandesite dykes, which were emplaced during the hydrothermal activity that created the orebodies and have affinities with the regional high potassium “Eureka” supersuite granitoids. Stable isotope data are consistent with dominantly magmatic fluids during mineralization and the regionally distinctive skarn (Ca–Mg) and Cu–Au–Ni–Co–Te–Se (low Pb–Zn–Ag–Sb) chalcophile element associations may reflect a primitive magmatic fluid source and/or leaching of these elements from country rocks. Mount Elliott is an unusual skarn deposit characterized by pronounced early albitization (K–Fe–Mg depletion) of the host rocks succeeded by predominantly open-space deposition of sodic diopside ± actinolite ± scapolite ± andradite ± magnetite ± sulfides ± apatite ± allanite ± tourmaline ± calcite. The Ca–Fe–Mg(–Na)-rich (manganese-poor) chemistry was imposed from the fluid phase in the absence of carbonate-rich protoliths. Immobile trace element (Ti, Zr, Nb) geochemistry shows that Mount Elliott skarns formed in both metasedimentary and mafic metavolcanic host rocks, but the former are the main hosts of ore in upper and lower ore zones that represent most of the resource. Banded skarns derived from a distinct calc-silicate/marble package at the nearby SWAN prospect have higher Nb/TiO2 and Zr/TiO2 ratios than the Mount Elliott metasediment-derived skarns, consistent with different provenance of the detrital components in the two sequences. Medium- to coarse-grained massive skarn and skarn breccia in the Mount Elliott lower ore zone formed in pelites and the trachyandesite dykes are the only intrusive rocks that could be genetically related to the mineralization in the immediate vicinity of the orebodies.

Iron-oxide–Cu–Au deposits, particularly those formed in deeper level (plutonic) environments, are commonly characterized by regional scale sodic(–calcic) alteration, which typically formed pre- or syn-Cu–Au mineralization. The sodic(–calcic) assemblages include albite, scapolite, pyroxene, actinolite, apatite, titanite, epidote and calcite. The consistent presence of coexisting hypersaline aqueous and CO2-rich fluids in minerals from sodic(–calcic) alteration and associated Fe-oxide–Cu–Au deposits is the result of unmixing of H2O–CO2–NaCl ± CaCl2–KCl magmatic fluids. Experimental evidence indicates that the Na/(Na + K) ratio of fluids in equilibrium with two alkali feldspars in CO3 2−-bearing parent fluids would be significantly higher than in unmixed chloride-bearing aqueous fluids. Therefore, fluid unmixing caused by decreases in temperature and/or pressure, will result in albitization of wall rocks, as is observed in most deeper level Fe-oxide–Cu–Au deposits. This alteration style may be succeeded by K-feldspathization with decreasing temperature because of the increase in equilibrium Na/(Na + K) in chloride-bearing fluids buffered by alkali feldspars.

The metasediment-hosted distal scheelite skarns from the Riba de Alva mine, Barca de Alva-Escalhao region, northeastern Portugal, consist of three main levels of strata-bound, boudin-shaped, 0.5- to 4-m-thick bodies, having a total resource of 380,000 tons (t) with an average grade of 0.51 percent WO3. The boudinage of the Cambrian metasedimentary rocks of the Slate Greywacke Complex occurred early during the Hercynian orogeny, prior to the Granitic Complex intrusion and the skarn-forming process. The Granitic Complex corresponds to reduced, highly evolved, and metallogenically specialized S-type leucogranites, comparable to those commonly associated with Mo-poor W-F skarns. Four different skarn types were recognized: pyroxene skarn with Fe diopside± anorthite; amphibole-epidote skarns with actinolite + clinozoisite ± bytownite ± phlogopite; ore skarn with clinozoisite + scheelite + fluorite + calcite ± labradorite ± apatite ± Fe axinite ± armenite ± scapolite; and late-stage veins with quartz (or fluorite or calcite) ± clinozoisite ± andesine (or albite) ± adularia. Clinopyroxene ranges from Di80Hd20 to Di60Hd40. Amphibole compositions range from actinolite to Mg hornblende and are F rich (0.5–1.9 wt %). Clinozoisite, often zoned with Fe-poor cores, shows little compositional variation in the skarn types, having a low pistacitic component (5–13% Ps). Plagioclase compositions grade from anorthite in pyroxene skarn through andesine and albite in late-stage veins. Phlogopite, as amphibole, is F rich (2.45–4.70 wt %). An extremely pure Mo-free scheelite, the only ore mineral present, is restricted to the ore skarn type. The Riba de Alva skarns were formed, after intrusion of the Hercynian Granitic Complex, by selective infiltrative metasomatic alteration of argillaceous dolomitic limestone. An early stage of prograde alteration led to the formation of the pyroxene skarn, through reaction with an Si-rich and Fe-bearing fluid. Scheelite mineralization occurred during retrograde alteration, which was mainly fracture controlled and is characterized by a pervasive infiltration metasomatism with minor diffusion in the skarn walls. This alteration started with hydration reactions to form amphibole-epidote skarns, probably under lower XCO2 conditions. Ore skarn formation, with scheelite deposition, took place later during this retrograde stage, mainly along veins within the strata-bound boudins, as the result of a decrease in temperature and/or significant changes in the activity of some fluid components such as W, F, Na, Mn, P, and B, and particularly an increase in aCa. Monomineralic late-stage veins represent the waning stage of the skarn-forming process.