Magma evolution and the formation of porphyry Cu–Au ore fluids: evidence from silicate and sulfide melt inclusions

Silicate and sulfide melt inclusions from the andesitic Farallón Negro Volcanic Complex in NW Argentina were analyzed by laser ablation ICPMS to track the behavior of Cu and Au during magma evolution, and to identify the processes in the source of fluids responsible for porphyry-Cu-Au mineralization at the 600 Mt Bajo de la Alumbrera deposit. The combination of silicate and sulfide melt inclusion data with previously published geological and geochemical information indicates that the source of ore metals and water was a mantle-derived mafic magma that contained approximately 6 wt.% H₂O and 200 ppm Cu. This magma and a rhyodacitic magma mixed in an upper-crustal magma chamber, feeding the volcanic systems and associated subvolcanic intrusions over 2.6 million years. Generation of the ore fluid from this magma occurred towards the end of this protracted evolution and probably involved six important steps: (1) Generation of a sulfide melt upon magma mixing in some parts of the magma chamber. (2) Partitioning of Cu and Au into the sulfide melt (enrichment factor of 10,000 for Cu) leading to Cu and Au concentrations of several wt.% or ppm, respectively. (3) A change in the tectonic regime from local extension to compression at the end of protracted volcanism. (4) Intrusion of a dacitic magma stock from the upper part of the layered magma chamber. (5) Volatile exsolution and resorption of the sulfide melt from the lower and more mafic parts of the magma chamber, generating a fluid with a Cu/Au ratio equal to that of the precursor sulfide. (6) Focused fluid transport and precipitation of the two metals in the porphyry, yielding an ore body containing Au and Cu in the proportions dictated by the magmatic fluid source. The Cu/S ratio in the sulfide melt inclusions requires that approximately 4,000 ppm sulfur is extracted from the andesitic magma upon mixing. This exceeds the solubility of sulfide or sulfate in either of the silicate melts and implies an additional source for S. The extra sulfur could be added in the form of anhydrite phenocrysts present in the rhyodacitic magma. It appears, thus, that unusually sulfur-rich, not Cu-rich magmas are the key to the formation of porphyry-type ore deposits. Our observations imply that dacitic intrusions hosting the porphyry–Cu–Au mineralization are not representative of the magma from which the ore-fluid exsolved. The source of the ore fluid is the underlying more mafic magma, and unaltered andesitic dikes emplaced immediately after ore formation are more likely to represent the magma from which the fluids were generated. At Alumbrera, these andesitic dikes carry relicts of the sulfide melt as inclusions in amphibole. Sulfide inclusions in similar dykes of other, less explored magmatic complexes may be used to predict the Au/Cu ratio of potential ore-forming fluids and the expected metal ratio in any undiscovered porphyry deposit.Editorial handling: B. Lehmann     

Pan-African Tectonism in the Western Maud Belt: P-T-t Path for High-grade Gneisses in the H.U. Sverdrupfjella, East Antarctica

Extensive high-grade polydeformed metamorphic provinces surroundingArchaean cratonic nuclei in the East Antarctic Shield recordtwo tectono-thermal episodes in late Mesoproterozoic and lateNeoproterozoic–Cambrian times. In Western Dronning MaudLand, the high-grade Mesoproterozoic Maud Belt is juxtaposedagainst the Archaean Grunehogna Province and has traditionallybeen interpreted as a Grenvillian mobile belt that was thermallyoverprinted during the Early Palaeozoic. Integration of newU–Pb sensitive high-resolution ion microprobe and conventionalsingle zircon and monazite age data, and Ar–Ar data onhornblende and biotite, with thermobarometric calculations onrocks from the H.U. Sverdrupfjella, northern Maud Belt, resultedin a more complex P–T–t evolution than previouslyassumed. A c. 540 Ma monazite, hosted by an upper ampibolite-faciesmineral assemblage defining a regionally dominant top-to-NWshear fabric, provides strong evidence for the penetrative deformationin the area being of Pan-African age and not of Grenvillianage as previously reported. Relics of an eclogite-facies garnet–omphaciteassemblage within strain-protected mafic boudins indicate thatthe peak metamorphic conditions recorded by most rocks in thearea (T = 687–758°C, P = 9·4–11·3kbar) were attained subsequent to decompression from P >12·9 kbar. By analogy with limited U–Pb singlezircon age data and on circumstantial textural grounds, thisearlier eclogite-facies metamorphism is ascribed to subductionand accretion around 565 Ma. Post-peak metamorphic K-metasomatismunder amphibolite-facies conditions is ascribed to the intrusionof post-orogenic granite at c. 480 Ma. The recognition of extensivePan-African tectonism in the Maud Belt casts doubts on previousRodinia reconstructions, in which this belt takes a pivotalposition between East Antarctica, the Kalahari Craton and Laurentia.Evidence of late Mesoproterozoic high-grade metamorphism duringthe formation of the Maud Belt exists in the form of c. 1035Ma zircon overgrowths that are probably related to relics ofgranulite-facies metamorphism recorded from other parts of theMaud Belt. The polymetamorphic rocks are largely derived froma c. 1140 Ma volcanic arc and 1072 ± 10 Ma granite. KEY WORDS: Maud Belt; Pan-African orogeny; geochronology; P–T–t path, East Antarctica     

Use of in situ-produced Be in carbonate-rich environments: A first attempt

We have determined the production rate of in situ-produced ¹⁰Be in calcite through measurements of ¹⁰Be and ³⁶Cl concentrations in the same calcite samples and of ¹⁰Be concentrations in depth profiles of flint from the same erosional surface. This yields a ¹⁰Be production rate in calcite of 37.9 ± 6.0 at/g/yr at sea level and high latitude, approximately sixfold higher than production in the coexisting flint. We propose that this higher rate of production may be due to high production cross sections for C spallation by cosmic rays with energies below 50 MeV. These results also open the possibility of dating burial events in carbonate-rich environments by differential radioactive decay of ¹⁰Be and ³⁶Cl.     

Chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100°C to 550°C: Case study in the Liassic black shale formation of Central Swiss Alps

Hydrocarbon distributions and stable isotope ratios of carbonates (δ¹³C_car, δ¹⁸O_car), kerogen (δ¹³C_ker), extractable organic matter (δ¹³C_EOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C_<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C₁₂ and C₁₃n-alkanes, C₁₄, C₁₆ and C₁₈n-alkylcyclopentanes and to a lesser extend C₁₅, C₁₇ and C₂₁n-alkylcyclohexanes. The progressive ¹³C-enrichment (up to 3.9‰) with metamorphism of the C_>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6‰) C_<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C₁ and C₂ radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C_>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C₂₉ to C₃₁ range and 5α(H),14α(H),17α(H)-20R C₂₇, C₂₉ steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C₂₉Ts) vs. 17α(H),21β(H)-30-norhopane [C₂₉Ts/(C₂₉Ts + C₂₉)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.     

Hydrogen isotopic composition of water from fossil micrometeorites in howardites

We have measured the hydrogen isotopic composition (D/H ratios) of the water from 13 carbonaceous chondritic microclasts (CCMs, size <1 mm) trapped in two howardites (Kapoeta and Yamato-793497) early in the evolution of Solar System. The division into tochilinite-rich; magnetite-rich, olivine-poor; magnetite-rich, olivine-rich CCM types is corroborated by the hydrogen isotopic compositions. Both mineralogy and hydrogen isotopic compositions demonstrate that tochilinite-rich CCMs represent CM2 chondritic matter. In contrast, there is no good match between the isotopic and mineralogical properties of the magnetite-rich CCMs and the known groups of carbonaceous chondrites, suggesting that magnetite-rich CCMs represent a new kind of chondritic matter, not yet sampled in meteorite collections. This demonstrates that the view of the asteroid belt revealed by the collection of meteorites is incomplete. The study of (micro)clasts offers a unique opportunity to better decipher the nature and relative abundance of asteroids.The average hydrogen isotopic composition of water belonging to CCMs, D/H = (152.0 ± 4.8) × 10⁻⁶ (1σ_m), is similar to that of Antarctic micrometeorites (AMMs), D/H = (161.2 ± 3.8) × 10⁻⁶ (1σ_m). The similarity, in terms of mineralogy and hydrogen isotopic composition, between CCMs and AMMs demonstrates that the composition of the micrometeorites has not been modified over the whole history of the Solar System. It indicates that the composition of the micrometeorite flux onto Earth has been, and is, dominated by a mixture of CM2-like; magnetite-rich, olivine-poor; magnetite-rich, olivine-rich carbonaceous chondritic matter exemplified by CCMs found in howardites. Because CCMs have not suffered atmospheric entry, they provide an abundant source of pristine micrometeorites.The average D/H ratio of the whole population of CCMs is identical within errors to that of the Earth (149 ± 3 × 10⁻⁶). The match between the CCMs D/H ratio and that of the Earth is especially remarkable because 1) three different populations of CCMs are needed to make the D/H ratio of the Earth; 2) there is no single carbonaceous chondrite group for which a similar match exists. This observation suggests that CCMs population might be representative of the late veneer agent(s) that delivered water to the Earth.     

Planetesimal sulfate and aqueous alteration in CM and CI carbonaceous chondrites

Water-soluble sulfate salts extracted from six CM chondrites have oxygen isotope compositions that are consistent with an extraterrestrial origin. The Δ¹⁷O of sulfate are correlated with previously reported whole rock δ¹⁸O and with an index of meteorite alteration, and may display a correlation with the date of the fall. The enrichments and depletions for Δ¹⁷O of water-soluble sulfate from the CM chondrites relative to the terrestrial mass dependent fractionation line are consistent with sulfate formation in a rock dominated asteroidal environment, and from aqueous fluids that had undergone relatively low amounts of oxygen isotope exchange and little reaction with anhydrous components of the meteorites. It is unresolved how the oxidation of sulfide to sulfate can be reconciled with the inferred low oxidation state during the extraterrestrial alteration process. Oxygen isotope data for two CI chondrites, Orgueil and Ivuna, as well as the ungrouped C2 chondrite Essebi are indistinguishable from sulfate of terrestrial origin and may be terrestrial weathering products, consistent with previous assertions. Our oxygen isotope data, however, can not rule out a preterrestrial origin either.     

Jadeitites, albitites and related rocks from the Motagua Fault Zone, Guatemala

Jadeitites from Guatemala are found as weathered blocks in tectonized serpentinite in a 15-km zone north of the Motagua Fault Zone. Rock types found with jadeitite include albitites, albite-mica rocks, omphacite/taramitic amphibole-bearing metabasites, chlorite-actinolite schists, talc-carbonate rocks and antigorite schists. In addition to the predominant jadeitic (Jd₉₃_₁₀₀) pyroxene, common phases in jadeitite include micas (paragonite and/or phengite ± rarer phlogopite), omphacite, albite, titanite /Pm zircon, apatite and graphite. Conditions of jadeitite formation are 100-400d? C, 5-11 kbar with 0.0 > log₁₀a_sio2≥= 0.7. Fluid inclusions, coarse textures, vein structures, and rhythmic zoning of pyroxene indicate an aqueuos fluid was involved. Jadeitites are either (1) metasomatic modifications of former felsic-to-pelitic inclusions that have undergone silica depletion plus efficient soda exchange and enrichment, or (2) solution precipitations derived from such a source. The close spatial relationship of faults and shear zones, serpentinites, and jadeitites suggests jadeitites form in a relatively high-P/T setting with substantial flow of sodic fluid in a tectonized zone. Most Guatemalan jadeitites are extensively altered to analcime, albite, taramitic amphibole, (clino)zoisite ± nepheline and preiswerkite. This alteration reflects depressurization /Pm heating to below the jadeite + fluid = analcime reaction at high a_Na. With progressive alteration, analcime and nepheline are replaced by albite; the increase in silica content may result from fluid flowing up a tectonized zone reaching saturation with an albite assemblage. Albitite phases, albite, actinolite, zoisite, /Pm chlorite, phengite, K-feldspar and quartz, record conditions of c. 3-8 kbar at T < 400d? C, indicating a clockwise P-T trajectory of the blocks. Barium aluminosilicates—banalsite, celsian, cymrite and hyalophane—are common minor late-stage phases in jadeitites and albite-rich rocks. Barian phengite is common in albite-mica rocks.