Rh, Ir, and Ru Partitioning in the Cu-Poor IPGE Massive Ores, Talnakh Intrusion, Skalisty Mine, Russia

Pyrrhotite (or Cu-poor) massive ores of the Skalisty mine located in Siberia, Russia, are unique in terms of their geochemical features. These ores are Ni-rich with Ni/Cu ratios in the range 1.3–1.9 and contain up to 12.25 ppm Ir + Rh + Ru in bulk composition, one of the highest IPGE contents for the Norilsk-Talnakh ore camp. The reasons behind such significant IPGE Contents cannot simply be explained by the influence of discrete platinum-group minerals on the final bulk composition of IPGE because only inclusions of Pd minerals such as menshikovite, majakite, and mertieite II in Pd-maucherite were observed. According to LA-ICP-MS data obtained, base metal sulfides such as pyrrhotite, pentlandite, and pyrite contain IPGE as the trace elements. The most significant IPGE concentrator being Py, which occurs only in the least fractionated ores, and contains Os up to 4.8 ppm, Ir about 6.9 ppm, Ru about 38.3 ppm, Rh about 36 ppm, and Pt about 62.6 ppm. High IPGE contents in the sulfide melt may be due to high degrees of partial melting of the mantle, interaction with several low-grade IPGE impulses of magma, and (or) fractionation of the sulfide melt in the magma chamber.

Application of non-destructive neutron resonance capture analysis for investigation of women’s Old Believer cross dating back to the second half of the 17th century

Neutron Resonance Capture Analysis (NRCA) is presently being developed at the Frank Laboratory of Neutron Physics (FLNP) to determine the elemental composition of samples. The NRCA is a nondestructive method that allows measuring objects’ bulk composition. The procedure is based on detecting neutron resonances in radiative capture and the measurement of the yield of reaction products in these resonances. The experiments are carried out at the Intense REsonance Neutron source (IREN). In this study, we applied the NRCA to investigate an archaeological object provided by the Museum and Exhibition Complex (MVK) "Volokolamsk Kremlin". The object was a women’s Old Believer cross (second half of the 17th century) found in the Moscow region, Volokolamsk district, the village of Chubarovo.

Slater-Pauling-like Behavior of Spin Hall Conductivity in Pt-based Superlattices

The intrinsic spin Hall effect in the bulk systems of late transition metals (Os, Ir, Pt, and Au) as well as the Pt-based superlattices were investigated by using first-principle calculations. By comparing the computed spin Hall conductivities of Pt−M superlattices (M=Os, Ir, and Au) with different compositions and those obtained from atomic bulk composition, we saw that the spin Hall conductivities (SHCs) follow the behavior described by the Slater-Pauling curve, the maximum of which is at pure Pt bulk. From the examination of the band structures of the considered systems, we found that the origin of this behavior comes from the variation of the band structures as a direct consequence of the change of the number of electrons and hybridization effects.

Comparative Study of Sample-Preparation Techniques for Quantitative Analysis of the Mineral Composition of Humic Substances by Inductively Coupled Plasma Atomic Emission Spectroscopy

Five sample-preparation techniques were compared to quantify 31 elements in coal humic substances (HS) by ICP–AES from the viewpoints of complete isolation and speciation of elements. They include, for bulk composition, preparation of an aqueous colloidal HS solution followed by direct injection of the sample without decomposition and ashing followed by metaborate fusion; for element speciation, preparation of an aqueous colloidal HS solution followed by centrifugation and direct analysis without decomposition for water-soluble species; treatment with boiling nitric acid; and microwave-assisted treatment with nitric acid at 250 °C for acid-isolated species. The results of analysis significantly depend on the selected method of sample preparation due to specific features of HS, the simultaneous presence of many inorganic components in wide concentration ranges, and a significant fraction of the organic matrix; therefore, the total mineral composition of HS, both macro- and microcomponents, requires a combination of decomposition methods.

Chemical composition and mixing state of BC-containing particles and the implications on light absorption enhancement

The radiative forcing of black carbon (BC) depends strongly on its mixing state in different chemical environments. Here, we analyzed the chemical composition and mixing state of BC-containing particles by using a single particle aerosol mass spectrometer and investigated their impacts on light absorption enhancement (Eabs) at an urban (Beijing) and a rural site (Gucheng) in North China Plain. While the BC was dominantly mixed with organic carbon (OC), nitrate and sulfate at both urban and rural sites, the rural site showed much higher fraction of BC coated with OC and nitrate (36 % vs. 15 – 20 %). Moreover, the BC mixing state evolved significantly as a function of relative humidity with largely increased coatings of OC-nitrate and nitrate at high RH levels. By linking with the bulk composition of organic aerosol (OA), we found that the OC coated on BC comprised dominantly secondary OA in Beijing, while primary and secondary OA were similarly important in Gucheng. Furthermore, Eabs was highly dependent on the secondary inorganic aerosol coated on BC at both sites, while the coated primary OC also resulted in an Eabs of ~1.2 for relatively fresh BC particles at the rural site. Positive matrix factorization analysis was performed to quantify the impact of different mixing state on Eabs. Our results showed the small Eabs (1.06 ~ 1.11) for BC particles from fresh primary emissions, while the Eabs increased significantly above 1.3 when BC was aged rapidly with increased coatings of OC-nitrate or nitrate, and it can reach above 1.4 as sulfate was involved in BC aging.

Metamorphism of metachert from the Southern Alps, New Zealand. A thermodynamic forward modelling study

<p>Scattered, scarce occurrences of garnet- and quartz-rich metamorphic rock, probably derived from Mn- and Fe-rich chert, occur within metamorphosed greywacke sequences worldwide. The metamorphism of such garnetiferous metacherts has not previously been investigated using modern thermodynamic forward modelling techniques due to the lack of appropriate, internally-consistent activity-composition (a–x) models for Mn-bearing minerals. The present study applies thermodynamic forward modelling using the recently-proposed a–x models of White et al. (2014) to investigate the metamorphism of garnetiferous metachert samples from the Southern Alps, New Zealand. Pressure-temperature (P–T) pseudosections are used in combination with results from petrography, element composition mapping using micro X-ray fluorescence (µXRF) and scanning electron microscope (SEM) methods, and garnet composition data from analytical transects by electron probe microanalysis (EPMA), to study metachert metamorphism. All the samples are compositionally layered, so the possibility exists that an input bulk rock composition might not match the effective bulk composition at the site of garnet growth. If a mineral assemblage stability field in a calculated P–T pseudosection matched the mineral assemblage in the rock, this was taken as an initial indication of a permissible input bulk rock composition. In that case, refined constraints on the P–T conditions were sought by comparing calculated and measured garnet compositions. The studied rocks include samples that are carbonate-bearing, which require consideration of the effects of fluid composition in mixed H₂O–CO₂ fluids, as well as a sample in which the garnet is strongly zoned, texturally-complex, and inferred to be of polymetamorphic origin. The effects of element fractionation by that garnet were investigated by recalculating the P–T pseudosection using a new bulk rock composition with the garnet core content removed. In none of the samples did the calculated and observed composition isopleths for the garnet cores match, suggesting that initial garnet nucleation in these Mn-rich rocks was locally controlled. For most samples in which the calculated and observed mineral assemblages matched, successful estimates of the peak metamorphic conditions were obtained. A garnet chert (A12E) from the mylonite zone of the Alpine Fault at Vine Creek, near Hokitika, gave a tight intersection of composition isopleths, indicating peak metamorphic conditions of 510 °C/5.5 kbar, after recalculation to correct for element fractionation by the strongly-zoned garnet. This tight, modern constraint is within error of previously-reported results from traditional geothermobarometry (420–600 °C/5.9–13 kbar) and Raman spectroscopy of carbonaceous material (RSCM T = 556 °C) from nearby sites. A peak metamorphic estimate of 520–550 °C/7–10 kbar was obtained from a dolomite-bearing sample from the garnet zone near Fox Glacier (J34), in good comparison with published temperatures from Raman spectroscopy of carbonaceous material in nearby metagreywacke samples (526–546 °C). The prograde metamorphic P–T path was probably steep, based on growth of the garnet core at ~475535 °C/5–9 kbar. The successful results for these garnet chert samples show that the new a-x models for Mn-bearing minerals extend the range of rock types that are amenable to pseudosection modelling. Results obtained in this study also serve to highlight several possible concerns: a) garnet nucleation and initial growth in very Mn-rich rocks may be subject to local compositional or kinetic controls; b) bulk rock compositions may not always mimic the effective bulk composition; c) the existing a–x models for Mn-bearing minerals and white micas may need refining; and d) some rocks may simply be ill-suited to thermodynamic forward modelling. Items a) and b) may be indicated by the common observation of a mismatch between predicted and measured garnet composition isopleths for garnet cores, and by a mismatch between garnet composition isopleths and the appropriate mineral assemblage field for sample AMS01, from the mylonite zone, Hari Hari, Southern Alps. For item c) every P–T pseudosection calculated using the new a–x models for Mn-bearing minerals showed garnet stable to very low temperatures below 300 °C. In addition, the P–T pseudosection for an oligoclase-zone metachporphyroblasts of Fe-Ti oxides (magnetitert (Sample J36) from Hari Mare stream, Franz Josef - Fox Glacier, indicated that the white mica margarite should be present instead of plagioclase (oligoclase), for a rock in which oligoclase is present and margarite is absent, a problem previously noted elsewhere. Item d) is exemplified by a very garnet-rich ferruginous metachert sample (J35, garnet zone, headwater region, Moeraki River, South Westland) which proved impossible to model successfully due to its complex mineral growth and deformation history. This sample contained multiple generations of carbonate with differing compositions, amphibole (not incorporated for modelling with the new a–x models for Mn-bearing minerals), large e associated with smaller, possibly later-formed ilmenite), and the garnet bands were offset by late deformation. The garnetiferous metachert samples studied here preserve in their textures and compositions clues to their growth mechanism and metamorphic history. The textures in at least two of the samples are consistent with the diffusion controlled nucleation and growth model for garnet. This research has successfully used state of the art thermodynamic modelling techniques in combination with the latest internally consistent a-x models on Mn-rich metachert, for the first time, extracting P–T conditions of the metamorphism of garnetiferous metachert from the Southern Alps.</p>

Metamorphism of metachert from the Southern Alps, New Zealand. A thermodynamic forward modelling study

<p>Scattered, scarce occurrences of garnet- and quartz-rich metamorphic rock, probably derived from Mn- and Fe-rich chert, occur within metamorphosed greywacke sequences worldwide. The metamorphism of such garnetiferous metacherts has not previously been investigated using modern thermodynamic forward modelling techniques due to the lack of appropriate, internally-consistent activity-composition (a–x) models for Mn-bearing minerals. The present study applies thermodynamic forward modelling using the recently-proposed a–x models of White et al. (2014) to investigate the metamorphism of garnetiferous metachert samples from the Southern Alps, New Zealand. Pressure-temperature (P–T) pseudosections are used in combination with results from petrography, element composition mapping using micro X-ray fluorescence (µXRF) and scanning electron microscope (SEM) methods, and garnet composition data from analytical transects by electron probe microanalysis (EPMA), to study metachert metamorphism. All the samples are compositionally layered, so the possibility exists that an input bulk rock composition might not match the effective bulk composition at the site of garnet growth. If a mineral assemblage stability field in a calculated P–T pseudosection matched the mineral assemblage in the rock, this was taken as an initial indication of a permissible input bulk rock composition. In that case, refined constraints on the P–T conditions were sought by comparing calculated and measured garnet compositions. The studied rocks include samples that are carbonate-bearing, which require consideration of the effects of fluid composition in mixed H₂O–CO₂ fluids, as well as a sample in which the garnet is strongly zoned, texturally-complex, and inferred to be of polymetamorphic origin. The effects of element fractionation by that garnet were investigated by recalculating the P–T pseudosection using a new bulk rock composition with the garnet core content removed. In none of the samples did the calculated and observed composition isopleths for the garnet cores match, suggesting that initial garnet nucleation in these Mn-rich rocks was locally controlled. For most samples in which the calculated and observed mineral assemblages matched, successful estimates of the peak metamorphic conditions were obtained. A garnet chert (A12E) from the mylonite zone of the Alpine Fault at Vine Creek, near Hokitika, gave a tight intersection of composition isopleths, indicating peak metamorphic conditions of 510 °C/5.5 kbar, after recalculation to correct for element fractionation by the strongly-zoned garnet. This tight, modern constraint is within error of previously-reported results from traditional geothermobarometry (420–600 °C/5.9–13 kbar) and Raman spectroscopy of carbonaceous material (RSCM T = 556 °C) from nearby sites. A peak metamorphic estimate of 520–550 °C/7–10 kbar was obtained from a dolomite-bearing sample from the garnet zone near Fox Glacier (J34), in good comparison with published temperatures from Raman spectroscopy of carbonaceous material in nearby metagreywacke samples (526–546 °C). The prograde metamorphic P–T path was probably steep, based on growth of the garnet core at ~475535 °C/5–9 kbar. The successful results for these garnet chert samples show that the new a-x models for Mn-bearing minerals extend the range of rock types that are amenable to pseudosection modelling. Results obtained in this study also serve to highlight several possible concerns: a) garnet nucleation and initial growth in very Mn-rich rocks may be subject to local compositional or kinetic controls; b) bulk rock compositions may not always mimic the effective bulk composition; c) the existing a–x models for Mn-bearing minerals and white micas may need refining; and d) some rocks may simply be ill-suited to thermodynamic forward modelling. Items a) and b) may be indicated by the common observation of a mismatch between predicted and measured garnet composition isopleths for garnet cores, and by a mismatch between garnet composition isopleths and the appropriate mineral assemblage field for sample AMS01, from the mylonite zone, Hari Hari, Southern Alps. For item c) every P–T pseudosection calculated using the new a–x models for Mn-bearing minerals showed garnet stable to very low temperatures below 300 °C. In addition, the P–T pseudosection for an oligoclase-zone metachporphyroblasts of Fe-Ti oxides (magnetitert (Sample J36) from Hari Mare stream, Franz Josef - Fox Glacier, indicated that the white mica margarite should be present instead of plagioclase (oligoclase), for a rock in which oligoclase is present and margarite is absent, a problem previously noted elsewhere. Item d) is exemplified by a very garnet-rich ferruginous metachert sample (J35, garnet zone, headwater region, Moeraki River, South Westland) which proved impossible to model successfully due to its complex mineral growth and deformation history. This sample contained multiple generations of carbonate with differing compositions, amphibole (not incorporated for modelling with the new a–x models for Mn-bearing minerals), large e associated with smaller, possibly later-formed ilmenite), and the garnet bands were offset by late deformation. The garnetiferous metachert samples studied here preserve in their textures and compositions clues to their growth mechanism and metamorphic history. The textures in at least two of the samples are consistent with the diffusion controlled nucleation and growth model for garnet. This research has successfully used state of the art thermodynamic modelling techniques in combination with the latest internally consistent a-x models on Mn-rich metachert, for the first time, extracting P–T conditions of the metamorphism of garnetiferous metachert from the Southern Alps.</p>

Garnet major-element composition as an indicator of host-rock type: a machine learning approach using the random forest classifier

The major-element chemical composition of garnet provides valuable petrogenetic information, particularly in metamorphic rocks. When facing detrital garnet, information about the bulk-rock composition and mineral paragenesis of the initial garnet-bearing host-rock is absent. This prevents the application of chemical thermo-barometric techniques and calls for quantitative empirical approaches. Here we present a garnet host-rock discrimination scheme that is based on a random forest machine-learning algorithm trained on a large dataset of 13,615 chemical analyses of garnet that covers a wide variety of garnet-bearing lithologies. Considering the out-of-bag error, the scheme correctly predicts the original garnet host-rock in (i) > 95% concerning the setting, that is either mantle, metamorphic, igneous, or metasomatic; (ii) > 84% concerning the metamorphic facies, that is either blueschist/greenschist, amphibolite, granulite, or eclogite/ultrahigh-pressure; and (iii) > 93% concerning the host-rock bulk composition, that is either intermediate–felsic/metasedimentary, mafic, ultramafic, alkaline, or calc–silicate. The wide coverage of potential host rocks, the detailed prediction classes, the high discrimination rates, and the successfully tested real-case applications demonstrate that the introduced scheme overcomes many issues related to previous schemes. This highlights the potential of transferring the applied discrimination strategy to the broad range of detrital minerals beyond garnet. For easy and quick usage, a freely accessible web app is provided that guides the user in five steps from garnet composition to prediction results including data visualization.

Geology and Petrology of Ruapehu Volcano and Related Vents

<p>Ruapehu Volcano is an active, multiple-vent, andesite composite volcano at the southern terminus of the Taupo Volcanic Zone, central North Island, New Zealand. The present-day volume of Ruapehu is estimated at 110 km3, and construction of the massif probably occurred during the past 0.5 m.y. Geologic mapping and stratigraphic studies have led to the recognition of four periods of cone construction, each occurring over 104-105 year time intervals. On the basis of lithologic/petrographic differences, and conspicuous unconformities which separate the deposits of each cone-building period, four new formations are defined, comprises the Ruapehu Group. Te Herenga formation (new formation name) comprises the oldest deposits of Ruapehu (upper lavas ca. 0.23 Ma) and is exposed as planeze surfaces and aretes on N and NW Ruapehu. The formation includes lava flows, tuff breccias, and small intrusive bodies surrounded by zones of hydrothermal alteration. There is little petrographic and compositional diversity; most lavas are porphyritic titanomagnetite- augite- hypersthene- plagioclase basic andesites. Wahiance Formation (new formation name) is younger than Te Herenga Fm,. but of unknown age. It is well exposed on SE Ruapehu, and comprises mostly lava flows and tuff breccias. The lavas comprise acid and basic andesites. Mangewhero Formation (new formation name) is well exposed everywhere except SE Ruapehu, and the upper lavas and pyroclastics (ca. 0.02 Ma) form the present high peeks and main cone of Ruapehu. The lavas are petrographically and geochemically diverse, ranging from basalt to decite in bulk composition. Some of the lower lavas are olivine-beering andesites of hybrid orgin. Whakapapa Formation (new formation name; ca 15,000 years to present) comprises conspicuously young lava flows, tuff breccias, airfall pyroclastics and minor pyroclastic flows of acid- and basic andesite. The deposits of these post-glacial summit and flank eruptions are subdivided into the lwikau, Rangataua, Tama and Crater Lake Members. 'Related vents' produced Heuhungatahi Andesite Fm. (> 0.5 Ma?), and Holocene deposits of basalt and basic andesite at isolated, monogenetic centres comprising Ohakune Andesite Fm., Pukeonake Andesite Fm., and Waimarino Basalt Fm. (new formation name). Most Ruapehu lavas are medium-K acid and basic andesites (mean of 144 bulk rock analyses is 57.8 wt % SiO2), but rare basalt and minor decite are present. Nearly all lavas are porphyritic in plagioclase, augite and hypersthene [plus or minus] olivine, with titanomagnetite micro- phenocrysts, and contain abundant metamorphic and igneous rock inclusions. Petrography, mineral chemistry and bulk rock chemistry indicate fractional crystallization series from parental basalts (52-53 % SiO2, Q-normative, low-alumina) to medium-K basic- and acid andesites (58-59 % SiO2). Early fractionating minerals are olivine and clinopyroxene with minor chrome spinel and plagioclase, followed by plagioclase, orthopyroxene, clinopyroxene and minor titanomagnetite in later stages of differentiation. Thus, basalt differentiation to produce andesites involves 'POAM-type' (Gill, 1981) fractional crystallization. Three second-order differentiation processes operate concurrently with frational crystallization: (1) Crystal accumulation involves addition of co-genetic plutonic rock fragments and crystals derived from them. These inclusions are common and few rocks represent liquid compositions. (2) Magma mixing involves mingling of magmas in repeatedly-occupied conduits. End members are as diverse as basalt and decite, yielding petrogaphically and chemically distinctive high-Mg andesites of the upper cone complex and parasitic centres. (3) Selective crustal assimilation is suggested by partially fused metamorphic inclusions, positive correlation of 87Sr/86Sr with SiO2, and failure of simple 'POAM' fractionation to explain decites (63-65 % SiO2). Petrogenesis of Ruapehu andesites takes place under open-system condition, involving production of parental Q-normative basalts in the mantle wedge, concurrent fractional crystallization and crustal contamination, entrainment of co-genetic plutonic rocks, and mixing of magmas in common conduits.</p>