Magmatic mineralization and hydrothermal enrichment of the High Grade Zone at the Lac des Iles palladium mine, northern Ontario, Canada

The economic mineralization of Pd at the Lac des Iles mine occurs in the gabbroic rocks of the Mine Block Intrusion in the 2.69 Ga Lac des Iles Intrusive Complex. The complex intruded the tonalitic rocks of the Lac des Iles greenstone belt in the Wabigoon Subprovince of the Superior Province of Canada. We conducted a detailed study on the Pd mineralization in the southern Roby Zone and the Twilight Zone. Sulphide minerals commonly display exsolution textures where pentlandite and chalcopyrite are exsolved from pyrrhotite. Sulphur contents from these zones display positive correlations with the contents of platinum group elements (PGE), Se, and Te, suggesting a magmatic origin of the mineralization where PGE were concentrated in immiscible sulphide melt in the parental magmas. The average ratios of Se/S (703±192×10^–6) and Te/S (192±104×10^–6) in the two zones are higher than the primitive mantle values of ~300×10^–6 and ~48×10^–6, respectively. The high ratios are consistent with the derivation of their parental magmas from a depleted mantle source. The High Grade Zone forms a narrow northwest-trending zone in the margin of the Roby Zone, and is hosted by an intensely altered clinopyroxenite/melanogabbroic unit. It contains two mineral assemblages; millerite + siegenite ± chalcopyrite ± pyrite co-existing with hornblende + plagioclase ± quartz ± carbonate, and pyrite ± chalcopyrite with chlorite + actinolite ± albite ± quartz ± carbonate. The ore is high in Pd (mean Pd/Pt ratio of 16.5; up to 25) compared to the southern Roby Zone and Twilight Zone where the Pd/Pt ratios are ~8. It shows positive correlations between Se and Te and between Se and immobile metals, such as Ni and Co. The data suggest a primary magmatic origin of mineralization of the High Grade Zone, but there is substantial scatter on diagrams involving S, such as the plot between S and Se. The evidence suggests that the primary magmatic mineralization was followed by hydrothermal transport of mobile elements. Using the relationships between Se and metals, the ore most likely had 0.8–2 ppm Pt and 8–21 ppm Pd during the primary mineralization. The subsequent hydrothermal activity resulted in the enrichment of Pd by up to 40 ppm. The lack of fluid pathways in the High Grade Zone and the distribution of the zone are consistent with magmatic-hydrothermal activity by aqueous fluids exsolved from the parental magmas of the Roby Zone and High Grade Zone. Sulphide minerals from the southern Roby Zone, Twilight Zone, and High Grade Zone have similar ³⁴S values, ranging from 0.0 to +1.5. The data are consistent with the derivation of S from the mantle. In individual samples from the southern Roby Zone and High Grade Zone, pyrite shows lower ³⁴S than chalcopyrite, suggesting isotopic disequilibrium of S. This likely reflects the crystallization and re-crystallization of sulphide minerals over a wide range of temperatures.Editorial handling: B. Lehmann     

Light utilization efficiency of phytoplankton in the Western Subarctic Gyre of the North Pacific during summer

We investigated the water-column light utilization efficiency (Ψ) of phytoplankton photosynthesis in the Western Subarctic Gyre (WSG) of the North Pacific during summer 2008. The Ψ values (0.64–1.86 g C [g Chl a]^?1 [mol photon]^?1 m²) obtained were observed to increase significantly with decreasing daily photosynthetic available radiation (PAR) and were generally higher than those of previous studies, not only from the subarctic Pacific but also from the world’s oceans. To examine the effect of iron availability on Ψ in the WSG, Ψ values were estimated from the data of two in situ iron fertilization experiments: the Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study I (SEEDS-I) and II (SEEDS-II). We found that iron availability did not affect Ψ values. Overall, this study revealed that Ψ values changed remarkably in the WSG during the summer, and that higher values were found at the stations where moderate PAR levels (ca. 10–30 mol photons m^?2 day^?1) were observed and where autotrophic flagellates predominated in the phytoplankton assemblages.     

An index for tropical temperate troughs over southern Africa

Strong cases of the tropical temperate troughs (TTT) that are responsible for the most of the summer rainfall over subtropical southern Africa are analyzed. An index for identifying the TTT is introduced for the first time using anomalies of outgoing longwave radiation (OLR) and the wind. The TTT is associated with a ridge-trough-ridge wave-like structure in the lower troposphere over southern Africa and the adjoining Indian Ocean. Therefore, the index considers physical processes that occur over southern Africa, adjoining the Atlantic and Indian Oceans to depict the variability of the TTT events. Unusually strong TTT events are identified when the standard deviations of the TTT indices defined by the OLR and wind anomalies in the selected regions are above 1.5 and 0.5 respectively. After applying this criterion and filtering out consecutive events, 55 TTT events are identified during the study period of December–January–February seasons from 1980–1981 to 2009–2010. From the composite analyses of those 55 events, it is found that the TTTs evolve with suppressed (enhanced) convection over the southwest Indian Ocean adjacent to Madagascar (southern Africa). The suppressed convection is, in turn, found to be associated with the enhanced convection around Sumatra in the southeast tropical Indian Ocean. This may explain why more TTT events occur in La Niña years as compared to El Niño years. Time evolution of the canonical TTT event shows that it starts 3 days prior to the mature phase of the event, suggesting possible predictability. After reaching a matured state, the system moves east toward the Indian Ocean and decays within the subsequent couple of days. In addition, the intertropical convergence zone (ITCZ) structure changes over Southern Africa/Madagascar during the TTT event and remains similar to climatology over other regions. The results indicate that the continental part of the ITCZ intensifies prior to the TTT event and then spreads southward following the mid-latitude influence during and after the event.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).     

Syn-eruptive breakdown of pyrrhotite: a record of magma fragmentation,air entrainment,and oxidation

Air entrainment in fragmented magmas controls the dynamics of volcanic eruptions. Pyroclast oxidation kinetics may be applied to quantify the degree of magma–air interaction. Pyrrhotite (Po) in volcanic rocks is often oxidized to form magnetite (Mt) and hematite (Hm), and its reaction mechanisms are well constrained. To test utilizing Po oxidation as a marker for magma–air interactions, we compared the occurrence of Po oxidation products from three different eruption styles during the Sakurajima 1914–1915 eruption. Pumices from the Plinian eruption include columnar-type Fe oxides (Mt with subordinate width of Hm) often accompanied by relict Po. This columnar type is also found in clastogenic lava, where it is almost completely oxidized to Hm. The effusive lava contains framboidal aggregates of subhedral to anhedral Mt crystals without Hm. The formation mechanisms of columnar and framboidal Fe oxides were estimated. The columnar type Fe oxides were formed syn-eruptively through gaseous reactions, as opposed to the melt in a magma chamber, as demonstrated by the Ti-free nature of the columnar Mt and its synchronous oxidation to Hm. By contrast, the framboidal type was formed in a melt with decreasing fS₂. The calculation of Hm growth in a conductively cooling pumice clast constrains the surface temperature of pumice in the eruption column. The paragenesis and oxidation degree of Po and Fe oxides are consistent with the eruption processes in terms of magma fragmentation, air entrainment, and welding, and can, therefore, be a responsive marker for the magma–air interaction.     

Mineral Inclusions in Chromite from the Chromite Deposit in the Kudi Ophiolite, Tibet, Proto-Tethys

High-Al chromite from the Kudi chromitites contains a wide range of mineral inclusions. They include clinopyroxene, amphibole, phlogopite, olivine, orthopyroxene, apatite, base-metal sulfides, calcite and brucite. The modal abundance of inclusions vary greatly among different grains of chromite. The common inclusions are clinopyroxene and amphibole, which occur as monomineral or polymineral associated with other minerals. The shapes of these inclusions tend to follow the growth plane of host chromite. Mineral assemblages and textures demonstrate that some inclusions(olivine, clinopyroxene) are trapped during magmatic stage, and most of the inclusions(e.g., amphibole, phlogopite) are trapped during recrystallization of chromite. Sulfide inclusions are pentlandite, chalcopyrite and cubanite. They occur either as isolated grains or together with silicate minerals, and formed from the separation of sulfide-bearing liquid from silicate magma. The parental magma of chromitites contains Al_2O_3 15.0wt%–16.5wt%, TiO_20.30wt%–1.05wt% based on calculation with the composition of chromite, similar to parental magma of high-Al chromitites from elsewhere and the estimated melt composition is comparable with that of MORB. Considering the high-Mg olivine in disseminated chromitite and abundant hydrous inclusions, we propose that Kudi chromitites formed beneath a volcanic front during the subduction initiation of Proto-Tethys.     

Tethyan and Indian subduction viewed from the Himalayan high- to ultrahigh-pressure metamorphic rocks

The Himalayan range is one of the best documented continent-collisional belts and provides a natural laboratory for studying subduction processes. High-pressure and ultrahigh-pressure rocks with origins in a variety of protoliths occur in various settings: accretionary wedge, oceanic subduction zone, subducted continental margin and continental collisional zone. Ages and locations of these high-pressure and ultrahigh-pressure rocks along the Himalayan belt allow us to evaluate the evolution of this major convergent zone.

(1) Cretaceous (80–100 Ma) blueschists and possibly amphibolites in the Indus Tsangpo Suture zone represent an accretionary wedge developed during the northward subduction of the Tethys Ocean beneath the Asian margin. Their exhumation occurred during the subduction of the Tethys prior to the collision between the Indian and Asian continents.

(2) Eclogitic rocks with unknown age are reported at one location in the Indus Tsangpo Suture zone, east of the Nanga Parbat syntaxis. They may represent subducted Tethyan oceanic lithosphere.

(3) Ultrahigh-pressure rocks on both sides of the western syntaxis (Kaghan and Tso Morari massifs) formed during the early stage of subduction/exhumation of the Indian northern margin at the time of the Paleocene–Eocene boundary.

(4) Granulitized eclogites in the Lesser Himalaya Sequence in southern Tibet formed during the Paleogene underthrusting of the Indian margin beneath southern Tibet, and were exhumed in the Miocene.

These metamorphic rocks provide important constraints on the geometry and evolution of the India–Asia convergent zone during the closure of the Tethys Ocean. The timing of the ultrahigh-pressure metamorphism in the Tso Morari massif indicates that the initial contact between the Indian and Asian continents likely occurred in the western syntaxis at 57 ± 1 Ma. West of the western syntaxis, the Higher Himalayan Crystallines were thinned. Rocks equivalent to the Lesser Himalayan Sequence are present north of the Main Central Thrust. Moreover, the pressure metamorphism in the Kaghan massif in the western part of the syntaxis took place later, 7 m.y. after the metamorphism in the eastern part, suggesting that the geometry of the initial contact between the Indian and Asian continents was not linear. The northern edge of the Indian continent in the western part was 300 to 350 km farther south than the area east of the Nanga Parbat syntaxis. Such “en baionnette” geometry is probably produced by north-trending transform faults that initially formed during the Late Paleozoic to Cretaceous Gondwana rifting. Farther east in the southern Tibet, the collision occurred before 50.6 ± 0.2 Ma. Finally, high-pressure to ultrahigh-pressure rocks in the western Himalaya formed and exhumed in steep subduction compared to what is now shown in tomographic images and seismologic data.     

Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.