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     

Hydrothermal Alteration, Fluid Inclusion and Stable Isotope Studies of the North Roby Zone, Lac des Iles PGE Mine, Ontario, Canada

The Archean mafic–ultramafic complex of Lac des Iles, Ontario, Canada, hosts economic platinum group elements (PGE)-Au-Cu-Ni mineralization in the Roby Zone. All lithologies in the North Roby Zone have been affected by hydrothermal alteration. The alteration products include talc (the most dominant mineral), anthophyllite, serpentine, actinolite, tremolite, chlorite, hornblende, zoisite, clinozoisite, epidote and sericite. In the altered rocks, light rare earth elements (La, Ce, Nd, Sm), Pb, Rb, Ba, Cs, S and possibly Y have been added by hydrothermal solution whereas Eu and heavy rare earth elements (Yb, Gd, Dy, Er) remained immobile. There are five types of fluid inclusions in the pegmatitic plagioclase with homogenization temperature and salinity ranging from 240°C to 445°C and 15.37 to 48.52 wt% equivalent NaCl, respectively. The δ¹⁸O and δD of talc range form 6.2‰ to 6.9‰ and −28‰ to −48‰, respectively. δ¹⁸O and δD water in equilibrium with talc during the hydrothermal alteration suggest a modified source for the hydrothermal solution. Microthermometry and stable isotope studies suggest that high temperature–high salinity fluid was diluted by, and mixed with, low temperature–low salinity meteoric solution. This mechanism precipitated the hydrothermal assemblage and redistributed trace elements during and after pegmatite formation in the North Ruby Zone.     

Stratiform platinum-group element mineralization in the layered Northern Ultramafic Center of the Lac des Iles Intrusive Complex,Ontario, Canada

The Northern Ultramafic Centre (NUC) of the Lac des Iles Complex, Northwest Ontario hosts several platinum group element (PGE) occurrences, including the Sutcliffe Zone, which consists of four subparallel, stratiform PGE-enriched intervals exposed within the cyclically layered eastern flank of the NUC. Field relationships, mineral paragenesis and lithogeochemistry allowed for the identification of 14 cyclic cumulate sequences of two distinct types – Cyclic unit type A (CUA) and Cyclic unit type B (CUB). CUA-type and CUB-type units are interpreted to have formed from a Si-enriched and Si-poor parent magmas, respectively. PGE-enriched intervals occur in four of the CUA-type cyclic units (CUA-5, -6, -8 and -11). PGE enriched intervals are commonly associated with websterite, olivine websterite and gabbronorite containing primary disseminated sulfide (0.2–2 vol%) which are dominated by pyrrhotite, chalcopyrite, and pentlandite with minor cubanite, and troilite. In hydrothermally altered rocks enriched in PGE, primary sulfides are locally partially replaced by secondary chalcopyrite, sphalerite, heazlewoodite, and chalcocite. Palladium occurs either in solid solution with primary pentlandite or is associated with platinum group minerals (PGM) such as Pd-plumbide, Pd-telluride, and Pt-bismuthotelluride. PGMs commonly occur within primary sulfides, at contacts between primary sulfide–silicate minerals, or in association with secondary serpentine and actinolite. Gold and silver typically occur as electrum that exhibits similar textural characteristics and mineralogical associations as the PGMs.Two different chemostratigraphic patterns of PGE, Cu and S enrichment can be recognized among the mineralized CUA cycles: The first (top-loaded) occurs near the top of CUA cycles (CUA-6, -8 and -11) in websterite and/or gabbronorite, just below the levels at which CUB magmas were emplaced. The second (middle-loaded), occurs midway through the lower cycle (CUA-5) in the olivine websterite, which is overlain by CUA-6. Within the four mineralized intervals, PGE tenors average 643 ppm Pd + Pt (in 100% sulfide), Pd/Pt and Pd/Ir ratios range from 0.9 to 3.5 and 35 to 537, respectively, and S/Se ratios range between 500 and 6000. The highest PGE tenors (4377 ppm Pd + Pt) are found in the lowermost interval in serpentinized olivine websterite and have an average Pd/Pt ratio of 3.5 and a S/Se ratio of approximately 2000.It is proposed that orthomagmatic processes of fractional crystallization and dynamic magma recharge were the dominant mineralization processes triggering sulfide-saturation and PGE concentration at the Sutcliffe Zone. Textural relationships between PGM, sulfide minerals, and primary and secondary hydrous silicates suggest that late magmatic to postcumulus hydrothermal fluid infiltration occurred locally during and after sulfide mineralization of the PGE-enriched intervals. However, these fluids had a minimal effect on the distribution of PGE in the Sutcliffe Zone. The Sutcliffe Zone shares many similarities with classic stratiform PGE deposits in terms of Pd/Pt ratio, high PGE tenors, low abundance of sulfide, and PGM assemblages. However, it is distinguished from most stratiform PGE deposits by its tectonic environment and lithostratigraphic position and by the intimate spatial association of the two parental magmas that are interpreted to have been responsible for the observed chemostratigraphy and PGE enrichment.     

Lead isotope study of the late Archean Lac des Iles palladium deposit,Canada: enrichment of platinum group elements by ponded sulfide melt

Lead isotopic compositions of mineral separates are presented from the mineralized zones (Roby, Twilight, and High Grade zones) of the Lac des Iles palladium deposit (approximately 2.69 Ga) and tonalitic country rocks (approximately 2.727 to 2.775 Ga) in the Wabigoon subprovince of the western Superior Province of Canada. Plagioclase separates show Pb isotope ratios similar to those of the late Archean depleted mantle. Sulfide minerals coexisting with plagioclase have a more radiogenic Pb isotope composition, but very low concentrations of U (<0.2 ppb U) and Th (<0.01 ppb) compared to Pb (≫50 ppb). The isotope data are consistent with a model involving the incorporation of radiogenic Pb from country rocks to sulfide melt near the base of the magma chamber or along the conduit of the parental magmas. The proposed interpretation is also supported by decreasing Cu/Pd ratios from earlier barren to late fertile gabbro intrusions in the complex. The ponding sulfide melt became enriched in platinum group elements, as it was interacting with a large magma volume during the evolution of the Lac des Iles igneous complex.     

The isotope geochemistry of fracture calcites from the Chalk River area,Ontario, Canada

Calcite is a common fracture inflilling mineral in the Grenville gneisses of the Chalk River area, Ontario, Canada. It exhibits a variety of occurrences and textures which suggests calcite has precipitated under different hydrogeochemical conditions that may be identified through a detailed chemical and isotopic investigation of the calcite and associated infilling minerals.The δ¹⁸O of these calcites range over 20%. but the δ¹³C varies over a narrow range of 5%.. None of the calcites analyzed is in isotopic equilibrium with both the δ¹⁸O and δ¹³C of the present day ground water. The lightest δ¹⁸O calcites (near 0%. SMOW) are present in sealed fractures and are sometimes associated with laumontite. This suggests that these light calcites formed from hydrothermal solutions (at temperatures less than about 300°C) shortly after the period of metamorphism that formed the gneisses. This interpretation is supported by relatively unradiogenic⁸⁷Sr/⁸⁶Sr ratios near 0.709 and δ¹³C values of −5 to −6%..Most of the Chalk River calcites, however, are considerably heavier in¹⁸O and lighter in¹³C than the hydrothermal end member. This may be the result of low temperature recrystallization of the hydrothermal calcites by meteoric waters under variable water/rock ratios. The¹³C contents and⁸⁷Sr/⁸⁶Sr ratios of these younger, low temperature calcites appear to be partially buffered by the isotopic composition of the original hydrothermal calcite.Pyrite is often associated with the fracture calcites. These pyrites display a wide range in δ³⁴S values of about 70%., which suggests that sulphide precipitation occurred under semi-closed conditions. These data indicate that fracture permeability has been a major control on the isotopic composition of fracture minerals since formation of the gneiss.     

Hydrothermal alteration and oxygen and hydrogen isotope geochemistry of the D-68 zone Cu-Zn Massive Sulfide Deposit,Noranda District,Quebec, Canada

Summary Pervasive hydrothermal alteration zones in quartz-feldspar porphyry domes underly all massive sulfide lenses in the D-68 Zone Cu-Zn deposit, Noranda. Alteration pipes are mineralogically zoned and contain chloritic cores consisting of stringer sulfides, enveloped by sericitic haloes. Silicified rocks are found locally.Alteration took place at nearly constant volume. Na depletion, and K enrichment relative to the least altered rocks, are found in all alteration zones. Fe and Mg have been added to the chloritic zone and subtracted in the sericitic and silicic zones. Ca and Si are enriched mainly in the silicic zone. Al, Ti and Zr were the least mobile of the elements studied.Whole-rock ¹⁸O values vary from +5.6 to +6.2 per mil in chloritized rocks, +5.8 to + 7.3 per mil in sericitized rocks and + 7.2 to + 8.3 per mil in silicified rocks. D values for two chloritized samples are – 63 and – 70 per mil whereas in two sericitized samples they are close to –62 per mil. Quartz from the chlorite alteration zone is isotopically heavier (¹⁸O = 8.6 per mil) than that from the sericite alteration zone (¹⁸O = 6.4 per mil), suggesting equilibration with different hydrothermal fluid or different temperature of alteration. Assuming an alteration temperature of 300° + 50°C the fluid in equilibrium with quartz and chlorite had ¹⁸O and D values of about 1.5 ± 2.0 per mil and –23 ± 5 per mil, respectively. The fluid in equilibrium with quartz and sericite had ¹⁸O and D values of about –0.5 ± 2 per mil and –30 ± 5 per mil, respectively. On the basis of isotopic data, seawater was probably the major constituent of the hydrothermal fluids.

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Hydrothermale Umwandlung und Sauerstoff-Wasserstoff-Isotopengeochemie der Zone D-68 Cu-Zn Derberz Sulfidlagerstätte, Noranda District, Quebec, Canada

Zusammenfassung Hydrothermale Umwandlungszonen in porphyrischen Quarz-Feldspat Gesteinskörpern liegen unterhalb von Derberz Sulfidlinsen in der D-68 Zone Cu-Zn Lagerstätte, Noranda. Umgewandelte pipes sind mineralogisch zoniert; sie enthalten aus Sulfiden bestehende chloritische Kerne, die von sericitischen Höfen umhüllt werden. Lokal treten silicifizierte Gesteine auf.Die Umwandlung ging bei annähernd konstantem Volumen vor sich. Na-Verarmung und K-Anreicherung, bezogen auf die am wenigsten umgewandelten Gesteine, liegen in allen Umwandlungszonen vor. Fe und Mg wurden der Chloritzone zugeführt, in den Sericit- und Si-Zonen abgeführt. Ca und Si sind vor allem in der Si-Zone angereichert. Al, Ti und Zr waren von den untersuchten Elementen am wenigsten mobil.Gesamtgesteins-¹⁸O Werte variieren von +5,6 bis +6,2 in den chloritisierten Gesteinen, von +5,8 bis 7,3 in sericitisierten Gesteinen und von +7,2 bis +8,3 in den silicifizierten Gesteinen. Die D Werte für zwei chloritisierte Proben betragen –63 und –70, in zwei sericitisierten Proben liegen sie hingegen nahe bei –62. Quarz von der Chlorit-Umwandlungszone ist isotopisch schwerer (¹⁸O = 8,6) als von der Sericit-Umwandlungszone (¹⁸O = 6.4), was eine Gleichgewichtseinstellung mit verschiedenen hydrothermalen Lösungen oder eine verschiedene Umwandlungstemperatur nahelegt. Bei einer angenommenen Umwandlungstemperatur von 300 ± 50°C, hatte die im Gleichgewicht mit Quarz und Chlorit stehende Lösung ¹⁸O und D Werte von etwa 1,5 ± 2 bzw. –23 + 5. Die im Gleichgewicht mit Quarz und Sericit befindliche Lösung hatte ¹⁸O und D Werte von etwa –0,5 ± 2%o bzw. –30 ± 5. Aufgrund der Isotopendaten war wahrscheinlich Meerwasser der Hauptbestandteil der hydrothermalen Lösungen.

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With 7 Figures     

Differences in paleomagnetic interpretations due to the choice of statistical, demagnetization and correction techniques: Kapuskasing Structural Zone, northern Ontario, Canada

The Kapuskasing Structural Zone (KSZ) reveals a section through the Archean lower crustal granoblastic gneisses. Our new paleomagnetic data largely agree with previous work but we show that interpretations vary according to the choices of statistical, demagnetization and field-correction techniques. First, where the orientation distribution of characteristic remanence directions on the sphere is not symmetrically circular, the commonly used statistical model is invalid [Fisher, R.A., Proc. R. Soc. A217 (1953) 295]. Any tendency to form an elliptical distribution indicates that the sample is drawn from a Bingham-type population [Bingham, C., 1964. Distributions on the sphere and on the projective plane. PhD thesis, Yale University]. Fisher and Bingham statistics produce different confidence estimates from the same data and the traditionally defined mean vector may differ from the maximum eigenvector of an orthorhombic Bingham distribution. It seems prudent to apply both models wherever a non-Fisher population is suspected and that may be appropriate in any tectonized rocks. Non-Fisher populations require larger sample sizes so that focussing on individual sites may not be the most effective policy in tectonized rocks. More dispersed sampling across tectonic structures may be more productive. Second, from the same specimens, mean vectors isolated by thermal and alternating field (AF) demagnetization differ. Which treatment gives more meaningful results is difficult to decipher, especially in metamorphic rocks where the history of the magnetic minerals is not easily related to the ages of tectonic and petrological events. In this study, thermal demagnetization gave lower inclinations for paleomagnetic vectors and thus more distant paleopoles. Third, of more parochial significance, tilt corrections may be unnecessary in the KSZ because magnetic fabrics and thrust ramp are constant in orientation to the depth at which they level off, at approximately 15-km depth. With Archean geothermal gradients, primary remanences were blocked after the foliation was tilted to rise on the thrust ramp. Therefore, the rocks were probably magnetized in their present orientation; tilting largely or entirely predates magnetization.     

The role of buried bedrock valleys on the development of karstic aquifers in flat-lying carbonate bedrock: insights from Guelph, Ontario, Canada

A spatial relationship between high capacity municipal production wells (>5,000 m³/day), completed in a deep bedrock aquifer, and a buried bedrock valley was recognized in the city of Guelph, southwestern Ontario, Canada. Most production wells are completed in a discrete zone, ～60 m below ground surface, within flat-lying dolostones of the Silurian Amabel Formation. Thick overburden and limited subsurface data make characterization of the karstic aquifer difficult. This study integrates hydrogeologic data with models of karst formation, deriving a conceptual model of porosity development as it relates to valley incision. Bedrock valley incision likely occurred prior to the early Wisconsinan age (>60–75 ka). Incision created steep hydraulic gradients within the flat-lying bedrock, and provided the driving force required to integrate regional groundwater flow into karst conduits that drained at the base of the valley. Dissolution in production zone dolostones was favoured over dissolution in shallower bedrock due to abundant bedding plane partings and fossiliferous facies with high intercrystalline porosity. Burial of the valley during subsequent ice advances reduced the valley’s hydraulic influence and the efficacy of the flow system to cause dissolution. The high capacity municipal wells near the buried bedrock valley tap into the now dormant karst aquifer system.     

Thermodynamics of Arsenates,Selenites, and Sulfates in the Oxidation Zone of Sulfide Ores. XIV. Selenium Minerals in the Oxidation Zone of the Yubileynoe Massive Sulfide Deposit,the South Urals

Selenium is one of the most important minor elements in massive sulfide ores. This study focuses on selenium minerals present in the oxidation zone of the Yubeleinoe massive sulfide deposit, the South Urals, Russia: clausthalite (PbSe), tiemannite (HgSe), and naumannite (Ag₂Se). These minerals are associated with goethite and siderite. Thermodynamic modeling was used to estimate the physicochemical parameters of selenide stability and the possible formation of Pb, Hg, and Ag selenites as a result of sulfide ore oxidation. The Eh–pH diagrams for the Fe–S–CO₂–H₂O and Fe–Se–CO₂–H₂O systems were calculated to estimate the physicochemical formation conditions of the Yubileinoe oxidation zone, as well as for the M–Se–Н₂О and M–S–H₂O (M = Hg, Pb, Ag) systems. The physicochemical parameters of clausthalite, naumannite, and tiemannite stability are consistent with these conditions. Only the formation of PbSeO3 is theoretically possible among Pb, Ag, and Hg selenites.

     

The relationship between length and width of plutons within the crustal-scale Cobequid Shear Zone, northern Appalachians, Canada

The lengths and widths have been measured for 69 component bodies of composite plutons along the Cobequid Shear Zone. Plutons on major fault strands, those with mylonite zones >0.1 km wide, exhibit evidence of multiple intrusion of magma batches. Small plutons along short faults in stepover zones appear related to rapid emplacement of magma in bodies 1.5–4 km long by 0.1–2 km wide. Such small plutons show low enrichment in incompatible elements in older component bodies, but increasing amounts in younger bodies as a result of progressive magma expulsion from crystal mush during crystallization and shear-enhanced compaction in fault zones. Wider plutons generally occur along longer fault strands accommodating more strain and penetrating deeper into the crust and show enrichment in incompatible elements. The width of the mylonitic fault zone is about 15% of the width of these plutons. The length-to-width ratio of component bodies and composite plutons varies between 2 and 11. The best-fit line describing these data has a slope of 1.056, which implies scaling behavior between plutonism and tectonic processes. Scalar properties of plutonic bodies are similar to those of faults, but scalar relationships observed in component bodies do not apply to composite plutons.     

The geochemistry,geochronology and paleomagnetism of dikes and sills associated with the Mesoproterozoic Midcontinent Rift near Thunder Bay,Ontario, Canada

The Midcontinent Rift (MCR) of North America comprises a series of basaltic sheets, flows and intrusive rocks emplaced in the Lake Superior region during the Mesoproterozoic. The mafic rocks preserved on the northern flank of Lake Superior represent the older portions of the rift sequence and offer insights into the early development of the rift. New geochronological, geochemical and paleomagnetic data are presented for the dikes and sills located in and south of Thunder Bay, Ontario. Three sill suites are recognized within the study area; an earlier, spatially restricted ultramafic unit termed the Riverdale sill, the predominant Logan sills and Nipigon sills in the north of the study area. In addition three dike sets are recognized, the north-east trending Pigeon River swarm, the north-west trending Cloud River dikes and the Mt. Mollie dike. The geochemical data demonstrate that the majority of sills south of Thunder Bay are of Logan affinity and distinct from those of broadly similar age in the Nipigon Embayment to the north. The Pigeon River dikes that intrude the sills are geochemically coherent but distinct from the Logan sills and could not be feeders to the sills. The new age of 1109.2 ± 4.2 Ma for the Cloud River dike and its R polarity are consistent with published magnetostratigraphy. The Mt. Mollie dike age (1109.3 ± 6.3 Ma) indicates that it is not coeval with the spatially associated Crystal Lake gabbro as previously thought. The complexity of the dike and sill suites on the northern flank of suggests that the early phases of rifting occurred in distinct and changing stress fields prior to the main extensional rifting preserved in younger rocks to the south. The geochemistry and geochronology of the intrusions suggest a long-lived and complex magmatic history for the Midcontinent Rift.     

The effect of metasomatism on the Cr-PGE mineralization in the Finero Complex, Ivrea Zone, Southern Alps

The magmatic metasomatism that was responsible for producing chromitite–dunite bodies in the unusual phlogopite peridotite of the Finero Complex in Permian to Triassic times also influenced the Cr-platinum group elements (PGE) mineralization. At least the end stages of this metasomatism are recorded in compositional zoning of chromite grains in the podiform chromitite. Metasomatic melt, with or without vapor, reacted with chromite to produce core-to-rim Cr enrichment of extant chromite grains and was concurrent with pyroxene crystallization. Under conditions of lower melt/rock ratio, metasomatism resulted in core-to-rim Al enrichment in chromite and crystallization of amphibole between chromite and clinopyroxene. This early, high-temperature metasomatism is unrelated to the later and pervasive K-metasomatism that crystallized phlogopite and was associated with the intrusion of clinopyroxenite dikes that cut the peridotite. Much later, serpentinization of olivine locally depleted chromite in Al and enriched it in Fe and formed minor amounts of magnetite.The PGE, which are present mainly as laurite inclusions in chromite, were remobilized by the early metasomatism. This resulted in substantial variation in the PGE contents of chromitites and imposed a characteristic PGE pattern in which chondrite-normalized Os, Ir, Ru and Rh contents are high but Pt and Pd contents are low. The slopes of PGE chondrite-normalized concentration patterns are systematically related to absolute PGE abundance and to rock mode. Chromitites with low modal orthopyroxene, clinopyroxene, and amphibole exhibit negative PGE slopes and contain relatively high PGE concentrations, whereas chromitites rich in these silicate minerals have positive slopes and low PGE contents.     

吐哈盆地大南湖地区层间氧化带特征及铀找矿前景

利用前人钻孔资料并结合野外调查,研究了找矿目的层西山窑组沉积环境、岩相古地理特征、砂体厚度及空间展布;对比各岩层的后生氧化程度,确定了层间氧化带的分布范围和空间展布形态。通过对目的层砂岩岩石学和岩石化学特征的研究,初步查明了本区砂岩孔隙度、密度与其结构构造密切相关,以及氧化带中次生矿物变化和化学元素如Fe、CO2、C有、S、U、Th、Se、Mo、V等含量变化与地下水的氧化作用有关,符合水成铀矿床的变化规律。在此基础上,圈定出氧化砂体,其底板埋深小于300m、厚度达50-100m、氧化带前锋长达60km。并在氧化带前锋发现铀矿化、硒矿化多处,初步显示该区具有良好的找矿前景。