Quantification of atmospheric oxygen levels during the Paleoproterozoic using paleosol compositions and iron oxidation kinetics

The increase in atmospheric oxygen during the Precambrian is a key to understand the co-evolution of life and environment and has remained as a debatable topic. Among various proxies for the estimation of atmospheric oxygen levels, paleosols, ancient weathering profiles, can provide a quantitative pattern of atmospheric oxygen increase during the Precambrian period of Earth history. We have re-evaluated the chemical compositions of paleosols, and presented a new method of applying Fe²⁺ oxidation kinetics to the Fe²⁺ and Fe³⁺ concentrations in paleosols to decipher the quantitative partial pressure of atmospheric oxygen (P_O2) between 2.5 and 2.0 Ga. We first estimated the compaction factor (CF, the fraction of original thickness) using the immobile elements such as Ti, Al and Zr on equal volume basis, which was then used to calculate retention fractions (M_R), a mass ratio of paleosol to parent rock, of redox-sensitive elements. The CF and Fe_R values were evaluated for factors such as homogeneity of immobile elements, erosion, and formation time of weathering. Fe_R increased gradually within the time window of ∼2.5-2.1 Ga and remained close to 1.0 since ∼2.1 Ga onwards. Mn_R also increased gradually similar to Fe_R but at a slower rate and near complete retention was observed ∼1.85 Ga, suggesting an almost continuous increase in the oxidation of Fe²⁺ and Mn²⁺ in paleosols ranging in age between ∼2.5 and 1.9 Ga.We have modeled P_O2 variations during the Paleoproterozoic by applying Fe²⁺ oxidation kinetics to the Fe²⁺ and Fe³⁺ concentrations in paleosols, which enabled us to derive an Fe²⁺ oxidation term referred to as ψ. Possible changes in temperature and P_CO2 during this time window and their effects on resulting models of P_O2 evolution have been also considered. We assumed four cases for the calculations of P_O2 variations between 2.5 and 2.0 Ga: no change in either temperature or P_CO2, long-term change in only P_CO2, long-term changes in both temperature and P_CO2, and short-term fluctuations of both temperature and P_CO2 during the possible, multiple global-scale glaciations. The calculations indicate that P_O2 increased gradually, linearly on the logarithmic scale, from <∼10⁻⁶ to >∼10⁻³ atm between 2.5 and 2.0 Ga. Our calculations show that the P_O2 levels would have fluctuated significantly, if intense, global glaciation(s) followed by period(s) of high temperature occurred during the Paleoproterozoic. This gradual rise model proposes a distinct, quantitative pattern for the first atmospheric oxygen rise with important implications for the evolution of life.     

Detrital zircon geochronology of the Speewah Group,Kimberley region,Western Australia: evidence for intracratonic development of the Paleoproterozoic Speewah Basin

Field observations integrated with new petrographic and sensitive high-resolution ion microprobe (SHRIMP) U–Pb age data for detrital zircons from the Paleoproterozoic Speewah Group of northern Western Australia provide evidence of depositional conditions, source of detritus, timing and evolution of the sedimentary rocks in the Speewah Basin. The Speewah Group is a 1.5 km-thick succession of poorly outcropping, predominantly siliciclastic rocks that preserve a fluviatile to marine, transgressive and regressive event. The Speewah Group unconformably overlies crystalline rocks of the Lamboo Province that were stabilised by the 1870–1850 Ma Hooper Orogeny, then accreted as the Kimberley region onto the North Australian Craton during the 1835–1810 Ma Halls Creek Orogeny. Unconformably overlying the Speewah Group is about 4 km of predominantly siliciclastic marine sedimentary rocks of the Kimberley Group in the Kimberley Basin. This study has detected a detrital zircon component within the Speewah Basin at 1814 ± 10 Ma, with a youngest zircon at 1803 ± 12 Ma (1σ) in fluviatile sandstones located beneath a volcaniclastic rock with magmatic zircons that have been dated at ca 1835 Ma. Previous studies proposed that the Speewah Basin developed as a retro-arc foreland basin during accretion of the North Australian Craton. We interpret the ca 1835 Ma zircons in the volcaniclastic rocks to be xenocrystic in origin. This new 20 million years younger maximum depositional age indicates that the Speewah Group in the Speewah Basin, similarly to the overlying Kimberley Group in the Kimberley Basin, developed in a post-orogenic setting on the North Australian Craton rather than in a syn-orogenic setting associated with the 1835–1810 Ma Halls Creek Orogeny.     

Trace element and sulfur isotopic evidence for redox changes during formation of the Wallaby Gold Deposit,Western Australia

Wallaby is a major gold deposit of the St Ives Gold field of Western Australia, with an estimated resource of 8 million ounces of gold. It has a well-established paragenesis across five vein sets that displays macroscopic evidence of changing redox through time; from hematite to magnetite. Micro-analysis of pyrite from each vein generation shows a progressive and gradual change in redox conditions. The sulfur isotope composition has a δ³⁴S range of −7.7 to +9.8‰ using 3 μm spots on the Sensitive High Resolution Iron Micro Probe-Stable Isotope (SHRIMP-SI). Negative values indicative of an oxidized sulfur signature are found in the earliest generation of pyrite (which coexists with hematite) that also contains high concentrations of As, Ni, Zn, Ag, Sb, Cu and Pb. Conversely, positive values representative of reduced sulfur are found in later generations of pyrite, with lower concentrations of As, Ni, Sb, Cu, Zn and Pb. These later pyrite crystals display higher As/Ni, As/Sb, and As/Bi, and lower Cu/Te. These geochemical trends are the result of redox controlled transport and partitioning into pyrite of minor and trace elements now within the pyrite structure. Previous studies suggested a single orogenic event formed the Wallaby Deposit. This is not supported by the present study. Trace element ratios such as As/Ni clearly delineate the high Au generations and could be used as an exploration tool. It is suggested that pyrite from the Wallaby Gold Deposit formed via desulfidation and a gradual change in redox conditions within an evolving fluid and did not result from mixing of two separate fluids as previously advocated. Utilizing pyrite to link the entire fluid history of Wallaby demonstrates the general use of pyrite as a valuable mineral tracer in gold-bearing fluid systems.     

Invisible gold in arsenian pyrite and arsenopyrite from a multistage Archaean gold deposit: Sunrise Dam,Eastern Goldfields Province,Western Australia

The Sunrise Dam gold mine (11.1 Moz Au) is the largest deposit in the Archaean Laverton Greenstone Belt (Eastern Goldfields Province, Yilgarn Craton, Western Australia). The deposit is characterized by multiple events of fluid flow leading to repeated alteration and mineralization next to a major crustal-scale structure. The Au content of arsenian pyrite and arsenopyrite from four mineralizing stages (D₁, D₃, D_4a, and D_4b) and from different structural and lithostratigraphic environments was measured using in situ laser ablation inductively coupled plasma mass spectrometry. Pyrite contains up to 3,067 ppm Au (n = 224), whereas arsenopyrite contains up to 5,767 ppm (n = 19). Gold in arsenopyrite (D_4a stage) was coprecipitated and remained as “invisible gold” (nanoparticles and/or lattice-bound) during subsequent deformation events. In contrast, gold in pyrite is present not only as “invisible gold” but also as micrometer-size inclusions of native gold, electrum, and Au(Ag)–tellurides. Pristine D₁ and D₃ arsenian pyrite contains relatively low Au concentrations (≤26 ppm). The highest Au concentrations occur in D_4a arsenian-rich pyrite that has recrystallized from D₃ pyrite. Textures show that this recrystallization proceeded via a coupled dissolution–reprecipitation process, and this process may have contributed to upgrading Au grades during D_4a. In contrast, Au in D_4b pyrite shows grain-scale redistribution of “invisible” gold resulting in the formation of micrometer-scale inclusions of Au minerals. The speciation of Au at Sunrise Dam and the exceptional size of the deposit at province scale result from multiple fluid flow and multiple Au-precipitating mechanisms within a single plumbing system.     

Systematics of the isotopic composition of sulfur in the oceans during the Phanerozoic and its implications for atmospheric oxygen

Past treatments of the variation of δS³⁴ in marine evaporites have either assumed a steady-state ocean or have invoked rather simplified ocean input-output models. This paper derives more completely the relationships between the parameters that influence the time variation of δS³⁴ in ocean water and the relationship between δS³⁴ in ocean water and net gains and losses of atmospheric oxygen due to the operation of the sulfur cycle. The lower and mid-Paleozoic are shown to have been periods of net gain of atmospheric oxygen by the operation of the sulfur cycle; the upper Paleozoic, particularly the Permian, a period of oxygen loss. It is difficult to relate these oxygen gains and losses to variations in the oxygen content of the atmosphere, because the oxygen flux due to the operation of the carbon cycle is approximately twice as large as the flux due to the operation of the sulfur cycle. Data for the organic carbon and sulfide content of sedimentary rocks of the Russian Platform suggest that a decrease in sulfide from the Paleozoic to the Mesozoic and Cenozoic Era was roughly balanced by an increase in the proportion of organic carbon; however, such data are insufficient to define the abundance of atmospheric oxygen during the Phanerozoic. Biologic data and a better understanding of controls on atmospheric P_o2 are more likely to produce convincing evidence regarding variations of atmospheric oxygen in the past.     

Carbon, oxygen, and sulfur isotope compositions of carbonate and sulfate rocks from the Famennian potassium-bearing subformation of the Pripyat trough

Peculiar features of evaporitic process at the stage of potassium accumulation are considered on the basis of carbon and oxygen isotope data on carbonate rocks and sulfur isotope data on anhydrite from the Famennian potassium-bearing subformation of the Starobin potassic salt deposit in the Pripyat trough. It was found that potassium accumulation was accompanied by the influx of continental waters and highly concentrated brines, while the formation of thick salt-free units was related to the replenishment of fresh seawater to the basin.     

Decoupling of the Sm-Nd and Re-Os Isotopic Systems in Sulphide-Saturated Magmas in the Halls Creek Orogen, Western Australia

We have observed apparent decoupling of the Re–Os andSm–Nd isotopic systems in sulphide-saturated magmas thatsuggests that bulk two-component or assimilation–fractionalcrystallization (AFC) mixing modelling, based on Re–Osisotopic data, is inappropriate for chalcophile isotopic systemsin turbulent sulphide-saturated magmas. This behaviour is observedin three Palaeoproterozic layered mafic–ultramafic intrusionsin the Halls Creek Orogen of Western Australia. All intrusionsclearly have a basaltic parental magma based on primitive olivineand spinel compositions. The intrusions are light rare earthelement enriched and define a narrow range of initial Nd-isotopicsignatures (     

Development and use of in situ laser sulfur isotope analyses for pyrite-anhydrite geothermometry: An example from the pyrite deposits of the Cameros Basin,NE Spain

We describe a system for the in situ sulfur isotope analysis of small (>100 μm) anhydrite crystals and investigate its application to anhydrite-pyrite geothermometry. Anhydrite inclusions (<1 mm) have been analyzed in spectacular, museum quality pyrite crystals from the Mesozoic Cameros Basin in NE Spain. Some of the data yield isotopic equilibrium temperatures (367 ± 6°C) consistent with other geothermometric estimates of metamorphic temperature. This suggests that isotopic equilibrium was established between the host pyrite and anhydrite inclusions and was not affected by re-equilibration. However, other data points yield anhydrite compositions consistently too ³⁴S-depleted, resulting in a geologically unrealistic temperature (610 ± 20°C). Experiments show that where pyrite becomes overheated by the laser during anhydrite decomposition, solid phase reaction can incorporate pyrite-sulfur into the sampled gas in a stoichiometric fashion, therefore, the consistency of the erroneous temperature estimates from this group. Successful analyses are only obtained when overheating of the pyrite is avoided during laser decomposition of anhydrite inclusions. The laser system allows isotopic measurement of anhydrite inclusions too small to be analyzed conventionally.     

华北克拉通大青山-集宁地区古元古代变质沉积岩的锆石氧同位素组成:SHRIMP微区原位分析

在已获得锆石U-Pb年龄基础上,我们首次对孔兹岩带典型出露区大青山和集宁土贵乌拉地区古元古代变质沉积岩进行了锆石SHRIMP氧同位素研究。锆石具有复杂的内部结构和年龄分布。大青山地区古元古代早期变质沉积岩4个样品碎屑锆石的δ18O为5.52‰~7.11‰,部分重结晶锆石的δ18O为7.22‰~7.90‰,变质新生锆石的δ18O为6.37‰~8.31‰。大青山地区古元古代晚期变质沉积岩2个样品的锆石O同位素组成特征与古元古代早期的类似,另外2个样品的锆石O同位素组成与之不同,碎屑锆石、部分重结晶锆石和变质新生锆石的δ18O分别为6.26‰~10.80‰、9.00‰~11.20‰和9.66‰~11.90‰。集宁土贵乌拉地区古元古代晚期超高温变质沉积岩4个样品不存在碎屑锆石,变质锆石的δ18O变化范围为11.41‰~13.57‰。主要认识如下:1)大青山地区碎屑沉积物主要来自新太古代晚期-古元古代早期成熟度不高的TTG花岗质岩石物源区,与之相比,集宁土贵乌拉地区古元古代晚期超高温岩石的变质原岩成熟度更高;2)不同类型变质沉积岩变质新生锆石的δ18O和变质新生锆石与碎屑锆石的Δ18O存在明显区别,主要反映了岩石体系和变质流体的O同位素组成不同;3)大青山地区高角闪岩相-麻粒岩相变质沉积岩,重结晶锆石的O同位素完全重置,但U-Th-Pb体系未完全重置,集宁土贵乌拉地区超高温变质沉积岩的重结晶锆石O和U-Th-Pb同位素体系都完全重置。变质作用强度不同是主要原因。     

Metamorphic grade and gradient from white K-micas of Na-mica bearing sedimentary rocks in the Mosquito Creek Basin,East Pilbara Craton,Western Australia

Shales and phyllites from the turbidite sequences of the 2.9 Ga Mosquito Creek Formation of the East Pilbara, Western Australia contain varying amounts of paragonite and mixed Na–K micas (MNKMs), the 0 0 l X-ray diffraction reflections of which are unresolved from the 10-Å reflections, and only partly resolved from the 5-Å reflections of white K-mica (WKM). The Kübler index (‘crystallinity’), the full width at half maximum (FWHM) of the WKM, obtained from these composite reflections by applying a three-peak deconvolution procedure, reveals a metamorphic zoning of the Mosquito Creek Formation. The highest, “epimetamorphic”, grade occurs in the — largely Na-mica free — southern part, with lower, medium- to high-anchimetamorphic, grades in the central part, notably in a WSW-ENE anticlinal zone extending from Nullagine to the Blue Spec Mine. The Na-mica free metasediments of the Glen Herring Shale of the Fortescue Group, overlying the Mosquito Creek Formation to the W, show only a slightly lower metamorphic grade. The low b₀ lattice parameter of the WKMs indicates a very low metamorphic P/T gradient. The Na-mica bearing metasediments of the Mosquito Creek Formation correspond to a kaolinite-bearing protolith, strongly Al-enriched and K-depleted with respect to the presumably granitic-tonalitic source rock.     

Climate Changes and Cyclic Sedimentation in the Mid-Late Permian: Kennedy Group, Carnarvon Basin, Western Australia

Climate has an important direct and indirect influence of sedimentation, and especially on the development of cyclic sedimentation. Climate influences both accommodation and supply, the major controls on the architecture of sedimentary sequences. The Permian paleoclimate is the subject of increasing controversy, giving rise to numerous differing models developed and an expanding database of fossil evidence for climatic conditions.Western Australian basins, in particular the Carnarvon Basin, are unique among nearby Gondwanan basins in that they do not have extensive coal measures within their Permian successions. The Kennedy Group, the uppermost unit in the onshore Carnarvon Basin Permian succession, has a detrital composition indicative of arid weathering conditions. Within the Kennedy Group, even lagoonal and very nearshore sediments are devoid of plant debris or indications of the nearby presence of extensive flora. Presumed surfaces of subaerial exposure do not show paleosol development or root-traces. There has been little development of clay and chemical grain degradation is almost entirely related to diagenetic cementation and dissolution phases, rather than transport and source weathering. Nearby basins, at similar latitudes, in India and East Australia contain coal measures, consistent with the humid climates that are predicted for this latitude. It is suggested therefore that the inferred aridity in the climate of the Carnarvon Basin and other Western Australian Basins is due to local climatic effects, probably related to an interruption in atmospheric circulation caused by tectonic rifting and uplift to the west.Cyclicity in the Kennedy Group indicates regular Late Permian, Milankovitch scale eustatic sea-level change, and may signify the presence of some ice at the poles. The development of cycles may have been enhanced by shifting climate belts controlled by Milankovitch cyclicity.     

Tectonic setting, evolution and orogenic gold potential of the late Mesoarchaean Mosquito Creek Basin, North Pilbara Craton, Western Australia

The geology, evolution, and metallogenic potential of the Mesoarchaean Mosquito Creek Basin remains poorly understood, despite the presence of several orogenic gold deposits. The basin is dominated by medium- to coarse-grained, poorly sorted and chemically immature sandstone and conglomerates, characterised by very high Cr/Th, high Th/Sc, and low Zr/Sc relative to average continental crust. These features are consistent with the presence of significant mafic rocks in the source terrain(s), a limited role for sediment recycling, and deposition in an increasingly distal passive margin setting on the southeastern edge of the Palaeo- to Mesoarchaean East Pilbara Terrane.New U–Pb SHRIMP data on 358 detrital zircons indicate a conservative maximum depositional age of 2972 + 14/−37 Ma (robust median; 96.1% confidence). Zircon provenance spectra from conglomeratic rocks near the base of the unit are consistent with substantial derivation from the East Pilbara Terrane, but finer-grained sandstones higher in the stratigraphy appear to have been sourced elsewhere, as their zircon age spectra are not well matched by any of the exposed Pilbara terranes.The Mosquito Creek Basin was deformed before and during collision with the northern edge of the Mesoarchaean Kurrana Terrane, which resulted in the development of macroscopic north-verging folds, thrust faulting, and widespread sub-greenschist to greenschist facies metamorphism. This collisional event probably took place at ca. 2900 Ma, based on two identical Pb–Pb model ages of 2905 ± 9 Ma from epigenetic galena associated with vein-hosted gold–antimony mineralization. The metallogenic potential of the Mosquito Creek Basin remains largely unevaluated; however, the possibility of a passive margin setting and continental basement points to relatively limited potential for the formation of major orogenic gold deposits.     

Magmatic history of the Eastern Creek Volcanics,Mt Isa,Australia: insights from trace-element and platinum-group-element geochemistry

The Paleoproterozoic basalts of the Eastern Creek Volcanics are a series of continental flood basalts that form a significant part of the Western Fold Belt of the Mt Isa Inlier, Queensland. New trace-element geochemical data, including the platinum-group elements (PGE), have allowed the delineation of the magmatic history of these volcanic rocks. The two members of the Eastern Creek Volcanics, the Cromwell and Pickwick Metabasalt Members, are formed from the same parental magma. The initial magma was contaminated by continental crust and erupted to form the lower Cromwell Metabasalt Member. The staging chamber was continuously replenished by parental material resulting in the gradual return of the magma composition to more primitive trends in the upper Cromwell Metabasalt Member, and finally the Pickwick Metabasalt Member formed from magma dominated by the parental melt. The Pickwick Metabasalt Member of the Eastern Creek Volcanics has elevated PGE concentrations (including up to 18 ppb Pd and 12 ppb Pt) with palladium behaving incompatibly during magmatic fractionation. This trend is the result of fractionation under sulfide-undersaturated conditions. Conversely, in the basal Cromwell Metabasalt Member the PGE display compatible behaviour during magmatic fractionation, which is interpreted to be the result of fractionation of a sulfide-saturated magma. However, Cu remains incompatible during fractionation, building up to high concentrations in the magma, which is found to be the result of the very small volume of magmatic sulfide formation (0.025%). Geochemical trends in the upper Cromwell Metabasalt Member represent mixing between the contaminated Cromwell Metabasalt magmas and the PGE-undepleted parental melt. Trace-element geochemical trends in both members of the Eastern Creek Volcanics can be explained by the partial melting of a subduction-modified mantle source. The generation of PGE- and copper-rich magmas is attributed to melting of a source in the subcontinental lithospheric mantle below the Mt Isa Inlier which had undergone previous melt extraction during an older subduction event. The previous melt extraction resulted in a sulfur-poor, metal-rich metasomatised mantle source which was subsequently remelted in the Eastern Creek Volcanic continental rift event. The proposed model accounts for the extreme copper enrichment in the Eastern Creek Volcanics, from which the copper has been mobilised by hydrothermal fluids to form the Mt Isa copper deposit. There is also the potential for a small volume of PGE-enriched magmatic sulfide in the plumbing system to the volcanic sequence.     

Constraining input and output fluxes of the southern-central Chile subduction zone: water,chlorine and sulfur

In this paper, we constrain the input and output fluxes of H₂O, Cl and S into the southern-central Chilean subduction zone (31°S–46°S). We determine the input flux by calculating the amounts of water, chlorine and sulfur that are carried into the subduction zone in subducted sediments, igneous crust and hydrated lithospheric mantle. The applied models take into account that latitudinal variations in the subducting Nazca plate impact the crustal porosity and the degree of upper mantle serpentinization and thus water storage in the crust and mantle. In another step, we constrain the output fluxes of the subduction zone both to the subcontinental lithospheric mantle and to the atmosphere–geosphere–ocean by the combined use of gas flux determinations at the volcanic arc, volume calculations of volcanic rocks and the combination of mineralogical and geothermal models of the subduction zone. The calculations indicate that about 68 Tg/m/Ma of water enters the subduction zone, as averaged over its total length of 1,480 km. The volcanic output on the other hand accounts for 2 Tg/m/Ma or 3 % of that input. We presume that a large fraction of the volatiles that are captured within the subducting sediments (which accounts for roughly one-third of the input) are cycled back into the ocean through the forearc. This assumption is however questioned by the present lack of evidence for major venting systems of the submarine forearc. The largest part of the water that is carried into the subduction zone in the crust and hydrated mantle (accounting for two-thirds of the input) appears to be transported beyond the volcanic arc.     

Mapping bedrock lithologies through in situ regolith using retained element ratios: a case study from the Agnew-Lawlers area,Western Australia

Large, high-quality multi-element geochemical datasets are becoming widely available in the exploration industry, and afford excellent opportunities to investigate geochemical processes. A dataset of over 2500 analyses of unweathered and variably weathered mafic and ultramafic rocks for over 50 elements has been collected by Gold Fields Ltd. in the auriferous Agnew-Lawlers area of the eastern Yilgarn Craton of Western Australia. This dataset is used to investigate changes in element abundances and inter-element ratios through varying degrees and styles of weathering in an area of thick regolith characterised by deep in situ weathering. Systematic interrogation of the data, using lithostratigraphic controls derived from regional mapping and geophysics, reveals that a suite of elements, including Ti, Al, Zr, Th, La, Sc and Nb, and to a lesser extent Cr and Ni, behave as essentially immobile components during saprolite formation. In some cases diagnostic element ratios persist into siliceous duricrust. Ratios of these elements are used as reliable discriminants of bedrock type, and delineate features such as cryptic layering within fractionated sills and subtle geochemical variants in a sequence of tholeiitic and komatiitic basalts. Mapping on the basis of discriminant element ratios greatly extends previous trace-element ratio-based schemes for rock type discrimination. The potential to determine several of these elements with adequate precision and accuracy using portable XRF technology opens a potentially useful technique for rapid geochemical bedrock mapping in residual terrains.     

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit,Inner Mongolia,China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing'an Range(S(GXR)which forms part of the eastern segment of the Central Asian Orogenic Belt(CAOB)is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo(Cu),skarn Fe(Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn± Cu± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including(i)the early porphyry mineralization stage,(ii)main porphyry mineralization stage,(iii)transition mineralization stage,(iv)vein-type mineralization stage and(v)late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites:Pyl is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium-to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Pyl to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni(0.03-10.79,average 2.13)and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ~(34)S_(cDT) values of Pyl(0.42‰-1.61‰,average1.16‰),Py2(-1.23‰to 0.82‰,average 0.35‰),Py3(—0.36‰to 2.47‰average 0.97‰).Py4(2.51‰--3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit(-5‰to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian(Jurassic-Cretaceous)magmatic-hydrothermal events.Variations of δ~(34) S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type Pb-Zn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.     

Copper mobility in the Eastern Creek Volcanics, Mount Isa, Australia: evidence from laser ablation ICP-MS of iron-titanium oxides

The Palaeoproterozoic Eastern Creek Volcanics are a series of copper-rich tholeiitic basalts which occur adjacent to the giant sediment-hosted Mount Isa copper deposit in Queensland, Australia. The volcanic rocks are often cited as the source of metals for the deposit. New laser ablation ICP-MS analyses of iron–titanium oxides from the basalts provide evidence for the local mobilisation of copper during regional greenschist facies metamorphism. This interpretation is based on the observation that copper-bearing magmatic titanomagnetite was destabilised during greenschist facies metamorphism, and the new magnetite which crystallised was copper poor. Petrological observations, regional geochemical signatures and geochemical modelling suggest that the mobilised copper was concentrated in syn-metamorphic epidote-rich alteration zones, creating a pre-concentration of copper before the main mineralisation event at Mount Isa. Geochemical modelling demonstrates this process is enhanced by the addition of CO₂ from adjacent carbonate-rich sediments during metamorphic devolatilisation. Regional geochemical data illustrate elevated copper concentrations in epidote-rich zones (high CaO), but where these zones are overprinted by potassic alteration (high K₂O), copper is depleted. A two-stage model is proposed whereby after metamorphic copper enrichment in epidote–titanite alteration zones, an oxidised potassium-rich fluid leached copper from the epidote-altered metabasalts and deposited it in the overlying sedimentary rocks to form the Mount Isa copper deposit. This ore-forming fluid is expressed regionally as potassium feldspar-rich veins and locally as biotite-rich alteration, which formed around major fluid conduits between the metabasalt metal source rocks and the overlying deposit host sequence. This model is consistent with the remobilisation of copper from mafic source rocks, as has been found at other world-class copper deposits.Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Deformation and mineralisation in the Scotty Creek Basin,Agnew district,Eastern Goldfields,Western Australia: evidence for D1- and D3-related gold mineralisation

Gold deposits in the Agnew district display markedly different structural styles. The Waroonga and Songvang deposits are hosted in layer-parallel extensional shears formed under highly ductile conditions. In contrast, the New Holland–Genesis deposits are shallow-dipping quartz-filled brittle fractures and breccia zones that cut across the tightly folded bedding and formed during east–west compression. It is difficult to attribute their formation to a single compressive event. The Waroonga and Songvang deposits formed during D₁ extension, uplift and exhumation of the Agnew granitic complex and formation of the Scotty Creek Basin at ca 2670–2660?Ma. The New Holland–Genesis deposits formed during east–west D₃ compression at about ca 2650–2630?Ma. An S₁ foliation wraps around the Agnew granitic complex and L₁ stretching lineations form a radial pattern around the granite, consistent with formation during D₁ uplift of the composite granite body. Uplift and erosion of granite bodies in the surrounding area provide a source for the granite clasts in the upper parts of the Scotty Creek Basin. As clasts in the basin are undeformed, no significant deformation occurred prior to the uplift and erosion of the source granites in this area. Syn-tectonic emplacement of the Lawlers Tonalite during formation of the Scotty Creek Basin at ca 2665?Ma may have provided a good heat/fluid source for the mineralising systems during the first gold event. The distribution of the large deposits along the western edge of the Agnew granitic complex indicates that the extensional shear along the granite contact is a first-order control on gold deposition by providing a conduit for rising hydrothermal fluids. The northerly trend of high-grade shoots in the Waroonga deposit coincides with early north-trending growth faults, which are also likely fluid conduits.