Pyrite trace-element and sulfur isotope geochemistry of paleo-mesoproterozoic McArthur Basin: Proxy for oxidative weathering

2019 ◽  
Vol 104 (9) ◽  
pp. 1256-1272 ◽  
Author(s):  
Indrani Mukherjee ◽  
Ross R. Large ◽  
Stuart Bull ◽  
Daniel G. Gregory ◽  
Aleksandr S. Stepanov ◽  
...  

Abstract Redox-sensitive trace elements and sulfur isotope compositions obtained via in situ analyses of sedimentary pyrites from marine black shales are used to track atmosphere-ocean redox conditions between ∼1730 and ∼1360 Ma in the McArthur Basin, northern Australia. Three black shale formations within the basin (Wollogorang Formation 1730 ± 3 Ma, Barney Creek Formation 1640 ± 3 Ma, and Upper Velkerri Formation 1361 ± 21 Ma) display systematic stratigraphic variations in pyrite trace-element compositions obtained using LA-ICP-MS. The concentrations of several trace elements and their ratios, such as Se, Zn, Se/Co, Ni/Co, Zn/Co, Mo/Co, Se/Bi, Zn/Bi, Ni/Bi, increase from the stratigraphically lower Wollogorang Formation to the Upper Velkerri Formation. Cobalt, Bi, Mo, Cu, and Tl show a consistent decrease in abundance while Ni, As, and Pb show no obvious trends. We interpret these trace element trends as a response to the gradual increase of oxygen in the atmosphere-ocean system from ∼1730 to 1360 Ma. Elements more mobile during erosion under rising atmospheric oxygen show an increase up stratigraphy (e.g., Zn, Se), whereas elements that are less mobile show a decrease (e.g., Co, Bi). We also propose the increase of elemental ratios (Se/Co, Ni/Co, Zn/Co, Mo/Co, Ni/Bi, and Zn/Bi) up stratigraphy are strong indicators of atmospheric oxygenation. Sulfur isotopic compositions of marine pyrite (δ34Spyrite) from these formations, obtained using SHRIMP-SI, are highly variable, with the Wollogorang Formation exhibiting less variation (δ34S = –29.4 to +9.5‰; mean –5.03‰) in comparison to the Barney Creek (δ34S = –13.8 to +41.8‰; mean +19.88‰) and Velkerri Formations (δ34S = –14.2 to +52.8‰; mean +26.9‰). We propose that the shift in mean δ34S to heavier values up-section corresponds to increasing deep water oxygenation from ∼1730 to 1360 Ma. Incursion of oxygenated waters possibly caused a decrease in the areal extent of anoxic areas, at the same time, creating a possibly efficient reducing system. A stronger reducing system caused the δ34S of the sedimentary pyrites to become progressively heavier. Interestingly, heavy δ34S in pyrites overlaps with the increase in the concentration of certain trace elements (and their ratios) in sedimentary pyrites (Se, Zn, Se/Co, Ni/Co, Zn/Co, Mo/Co, Ni/Bi, and Zn/Bi). This study concludes that there was a gradual increase of atmospheric oxygen accompanied by ocean oxygenation through the first ∼400 million years of the Boring Billion (1800–1400 Ma) in the McArthur Basin.

Author(s):  
Mikael Vasilopoulos ◽  
Ferenc Molnár ◽  
Hugh O’Brien ◽  
Yann Lahaye ◽  
Marie Lefèbvre ◽  
...  

AbstractThe Juomasuo Au–Co deposit, currently classified as an orogenic gold deposit with atypical metal association, is located in the Paleoproterozoic Kuusamo belt in northeastern Finland. The volcano-sedimentary sequence that hosts the deposit was intensely altered, deformed, and metamorphosed to greenschist facies during the 1.93–1.76 Ga Svecofennian orogeny. In this study, we investigate the temporal relationship between Co and Au deposition and the relationship of metal enrichment with protolith composition and alteration mineralogy by utilizing lithogeochemical data and petrographic observations. We also investigate the nature of fluids involved in deposit formation based on sulfide trace element and sulfur isotope LA-ICP-MS data together with tourmaline mineral chemistry and boron isotopes. Classification of original protoliths was made on the basis of geochemically immobile elements; recognized lithologies are metasedimentary rocks, mafic, intermediate-composition, and felsic metavolcanic rocks, and an ultramafic sill. The composition of the host rocks does not control the type or intensity of mineralization. Sulfur isotope values (δ34S − 2.6 to + 7.1‰) and trace element data obtained for pyrite, chalcopyrite, and pyrrhotite indicate that the two geochemically distinct Au–Co and Co ore types formed from fluids of different compositions and origins. A reduced, metamorphic fluid was responsible for deposition of the pyrrhotite-dominant, Co-rich ore, whereas a relatively oxidized fluid deposited the pyrite-dominant Au–Co ore. The main alteration and mineralization stages at Juomasuo are as follows: (1) widespread albitization that predates both types of mineralization; (2) stage 1, Co-rich mineralization associated with chlorite (± biotite ± amphibole) alteration; (3) stage 2, Au–Co mineralization related to sericitization. Crystal-chemical compositions for tourmaline suggest the involvement of evaporite-related fluids in formation of the deposit; boron isotope data also allow for this conclusion. Results of our research indicate that the metal association in the Juomasuo Au–Co deposit was formed by spatially coincident and multiple hydrothermal processes.


Author(s):  
John D. Greenough ◽  
Alejandro Velasquez ◽  
Mohamed Shaheen ◽  
Joel Gagnon ◽  
Brian J. Fryer ◽  
...  

Trace elements in native gold provide a “fingerprint” that tends to be unique to individual gold deposits. Fingerprinting can distinguish gold sources and potentially yield insights into geochemical processes operating during gold deposit formation. Native gold grains come from three historical gold ore deposits; Hollinger, McIntyre (quartz-vein ore), and Aunor near Timmins, Ontario, at the western end of the Porcupine gold camp and the south-western part of the Abitibi greenstone belt. Laser-ablation, inductively-coupled plasma mass spectrometry (LA ICP MS) trace element concentrations were determined on 20 to 25 µm wide, 300 µm long rastor trails in ~ 60 native gold grains. Analyses used Ag as an internal standard with Ag and Au determined by a scanning electron microscope with an energy dispersive spectrometer. The London Bullion Market AuRM2 reference material served as the external standard for 21 trace element analytes (Al, As, Bi, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Pd, Pt, Rh, Sb, Se, Si, Sn, Te, Ti, Zn; Se generally below detection in samples). Trace elements in native gold associate according to Goldschmidt’s classification of elements strongly suggesting that element behavior in native Au is not random. Such element behavior suggests that samples from each Timmins deposit formed under similar but slightly variable geochemical conditions. Chalcophile and siderophile elements provide the most compelling fingerprints of the three ore deposits and appear to be mostly in solid solution in Au. Lithophile elements are not very useful for distinguishing these deposits and element ABSTRACT CUT OFF BY SOFTWARE


2021 ◽  
Author(s):  
Jesse Walters ◽  
Alicia Cruz-Uribe ◽  
Won Joon Song ◽  
Joshua Stone ◽  
Hanna Brooks ◽  
...  

<p>Here we present titanite U-Pb dates from two banded calc silicate gneisses (SSP18-1A and 1B) from western Maine. Mineral textures and compositions display multiple phases of metamorphism. The peak lower granulite facies assemblage is Di + Kfs + Pl + Ttn, with little to no calcite present. Late Czo + Tr replaces Di + Pl, suggesting an influx of X<sub>H2O</sub> > 0.90 fluids. Nearby metapelites show the transition from sillimanite-bearing to muscovite-bearing assemblages, indicating that fluid infiltration may be widespread. Compositional maps of clinopyroxene in SSP18-1B show fracturing and rehealing of early Fe-rich diopside with late Mg-rich diopside. Both samples exhibit overprinting of An-rich plagioclase by increasingly Ab-rich plagioclase. Titanite grains in both samples exhibit BSE textures and compositional variation consistent with multiple phases of growth and dissolution-reprecipitation reactions.</p><p>Titanite trace element and U-Pb data were collected by LA-ICP-MS at the University of Maine using an ESI NWR193<sup>UC</sup> excimer laser ablation system coupled to an Agilent 8900 ICP-MS. Single spot ages range from 280 to 400 Ma with 12-20 Ma propagated 2SE. Four composition-date domains are identified in SSP18-1B: A. 400 ± 8 Ma (dark BSE cores), B. 372 ± 4 Ma (bright BSE cores), C. 342 ± 6 Ma (bright BSE cores, no Eu anomaly), and D. 302 ± 3 Ma (dark BSE rims, low LREE). Titanite Fe and Y concentrations increase with decreasing date, whereas Sr concentrations decrease. In clinopyroxene, Fe and Y decrease between high Fe-diopside and late Mg-diopside, placing the fracturing and rehealing events between 400 and 372 Ma. Strontium concentrations in titanite decrease between subsequent generations of plagioclase, diopside, and titanite, suggesting a continual fractionation of Sr from the reactive bulk composition. Low LREE in ca. 300 Ma titanite domains in both samples are consistent with the formation of texturally late allanite and clinozoisite, thus constraining the timing of the high X<sub>H2O</sub> fluid infiltration event. Zr-in-titanite temperatures for rims in the quartz-bearing SSP18-1B give a weighted mean T of 764 °C at 4.5 GPa, consistent with the muscovite-absent sillimanite-bearing assemblage in garnet cores from metapelite samples. However, the 100-150 °C lower Grt-Bt temperatures for metapelites are not consistent with peak metamorphic phase equilibria. Our data demonstrate the utility of linking titanite textures and trace element concentrations with those of other minerals to reveal past metamorphic and deformational events. Additionally, we show that titanite may reliably preserve U and Pb isotopic ratios, trace elements, and textures over subsequent high-T metamorphic events.</p>


2019 ◽  
Vol 42 (5) ◽  
pp. 1235-1254
Author(s):  
Jemal Ahmed

Abstract This paper reports the results of trace elements geochemistry from Tigray national state, northwestern Ethiopia. The area is part of the Arabian-Nubian Shield, where the dominant exposure is low-grade metamorphic rocks and has a long history of liver-related diseases. The increase in the number of liver-related disease patients of the area has been an environmental health issue of national concern. The aim of the study is to determine the level of trace element concentrations and distributions in water and stream sediments of the area and identify the possible sources in relation to human health. Water, stream sediment and rocks samples (20 water, 20 stream sediments, and 6 rock samples) were collected in March 2011 and analyzed for major and trace element contents using ICP-MS, ICP-OES, ion Chromatography, and XRF methods. Bromine, aluminum, fluorine, arsenic, and nitrate values exceed the WHO maximum acceptable concentration (MAC) for drinking purpose. Bromine ranges from 0.11 to 1.48 mg/l show higher values in all samples, and fluorine ranges from 0.21 to 16.49 mg/l show higher values in 20% of the samples. Other trace elements are aluminum—30%, arsenic—10%, and nitrate (NO3)—10%, and they are examples of elements which have above MAC for drinking water. Selenium deficiency may be the other problematic element in the area for which its deficiency is associated with liver damage and heart muscle disorder. The concentration of cobalt and chromium exceeded world geochemical background value in average shale at most sample stations indicated that these stations were in potential risk.


Minerals ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 588
Author(s):  
Indrani Mukherjee ◽  
Mihir Deb ◽  
Ross R. Large ◽  
Jacqueline Halpin ◽  
Sebastien Meffre ◽  
...  

The Vindhyan Basin in central India preserves a thick (~5 km) sequence of sedimentary and lesser volcanic rocks that provide a valuable archive of a part of the Proterozoic (~1800–900 Ma) in India. Here, we present an analysis of key sedimentary pyrite textures and their trace element and sulfur isotope compositions in the Bijaigarh Shale (1210 ± 52 Ma) in the Vindhyan Supergroup, using reflected light microscopy, LA-ICP-MS and SHRIMP-SI, respectively. A variety of sedimentary pyrite textures (fine-grained disseminated to aggregates, framboids, lags, and possibly microbial pyrite textures) are observed reflecting quiet and strongly anoxic water column conditions punctuated by occasional high-energy events (storm incursions). Key redox sensitive or sensitive to oxidative weathering trace elements (Co, Ni, Zn, Mo, Se) and ratios of (Se/Co, Mo/Co, Zn/Co) measured in sedimentary pyrites from the Bijaigarh Shale are used to infer atmospheric redox conditions during its deposition. Most trace elements are depleted relative to Proterozoic mean values. Sulfur isotope compositions of pyrite, measured using SHRIMP-SI, show an increase in δ34S as we move up stratigraphy with positive δ34S values ranging from 5.9‰ (lower) to 26.08‰ (upper). We propose limited sulphate supply caused the pyrites to incorporate the heavier isotope. Overall, we interpret these low trace element signatures and heavy sulfur isotope compositions to indicate relatively suppressed oxidative weathering on land during the deposition of the Bijaigarh Shale.


2020 ◽  
Vol 105 (6) ◽  
pp. 820-832 ◽  
Author(s):  
Aleksandr S. Stepanov ◽  
Leonid V. Danyushevsky ◽  
Ross R. Large ◽  
Indrani Mukherjee ◽  
Irina A. Zhukova

Abstract Pyrite is a common mineral in sedimentary rocks and is the major host for many chalcophile trace elements utilized as important tracers of the evolution of the ancient hydrosphere. Measurement of trace element composition of pyrite in sedimentary rocks is challenging due to fine-grain size and intergrowth with silicate matrix and other sulfide minerals. In this contribution, we describe a method for calculation of trace element composition of sedimentary pyrite from time-resolved LA-ICP-MS data. The method involves an analysis of both pyrite and pyrite-free sediment matrix, segmentation of LA-ICP-MS spectra, normalization to total, regression analysis of dependencies between the elements, and calculation of normalized composition of the mineral. Sulfur is chosen as an explanatory variable, relative to which all regressions are calculated. The S content value used for calculation of element concentrations from the regressions is calculated from the total, eliminating the need for independent constraints. The algorithm allows efficient measurement of concentrations of multiple chalcophile trace elements in pyrite in a wide range of samples, including quantification of detection limits and uncertainties while excluding operator bias. The data suggest that the main sources of uncertainties in pyrite composition are sample heterogeneity and counting statistics for elements of low abundance. The analysis of regression data of time-resolved LA-ICP-MS measurements could provide new insights into the geochemistry of the sedimentary rocks and minerals. It allows quantification of ratios of elements that do not have reference material available (such as Hg) and provides estimates on the content of non-sulfidic Fe in the silicate matrix. Regression analysis of the mixed LA-ICP-MS signal could be a powerful technique for deconvolution of phase compositions in complex multicomponent samples.


1985 ◽  
Vol 22 (11) ◽  
pp. 1689-1695 ◽  
Author(s):  
Robert O. van Everdingen ◽  
M. Asif Shakur ◽  
Frederick A. Michel

The Paint Pots in Kootenay National Park (British Columbia) appear to derive the Fe, Zn, Pb, and [Formula: see text] contents of their water from sulfide mineralization in Lower and Middle Cambrian carbonates. The Fe, Zn, Ni, and [Formula: see text] contents of groundwater discharging into a tributary of Engineer Creek (Yukon) are likely derived from sulfide mineralization in Devonian or Ordovician black shales exposed in the area. The high Fe and [Formula: see text] contents of a natrojarosite deposit northeast of Fort Norman (Northwest Territories) are probably derived from pyritiferous Cretaceous shales in that area. Isotope analyses of water and of dissolved and precipitated sulfur species from these three sites where acidic, heavy-metal-bearing groundwater is being discharged revealed that between 38 and 74% of the oxygen used in the subsurface oxidation of metal sulfides is supplied by H2O molecules rather than by molecular (dissolved) oxygen. The available data also suggest that lower percentages of water oxygen in the secondary sulfates reflect increasing activity of Thiobacillus ferrooxidans or similar bacteria in the oxidation process.


Minerals ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 725 ◽  
Author(s):  
Constantinos Mavrogonatos ◽  
Panagiotis Voudouris ◽  
Jasper Berndt ◽  
Stephan Klemme ◽  
Federica Zaccarini ◽  
...  

Magnetite is a common accessory phase in various types of ore deposits. Its trace element content has proven to have critical implications regarding petrogenesis and as guides in the exploration for ore deposits in general. In this study we use LA-ICP-MS (laser ablation-inductively coupled plasma-mass spectrometry) analyses of trace elements to chemically characterize magnetite from the Pagoni Rachi Cu–Mo–Re–Au porphyry-style prospect, Thrace, northern Greece. Igneous magnetite mostly occurs as euhedral grains, which are commonly replaced by hematite in fresh to propylitic-altered granodiorite porphyry, whereas, hydrothermal magnetite forms narrow veinlets or is disseminated in sodic/potassic-calcic altered (albite + K-feldspar + actinolite + biotite + chlorite) granodiorite porphyry. Magnetite is commonly associated with chalcopyrite and pyrite and locally exhibits martitization. Laser ablation ICP-MS analyses of hydrothermal magnetite yielded elevated concentrations in several trace elements (e.g., V, Pb, W, Mo, Ta, Zn, Cu, and Nb) whereas Ti, Cr, Ni, and Sn display higher concentration in its magmatic counterpart. A noteworthy enrichment in Mo, Pb, and Zn is an unusual feature of hydrothermal magnetite from Pagoni Rachi. High Si, Al, and Ca values in a few analyses of hydrothermal magnetite imply the presence of submicroscopic or nano-inclusions (e.g., chlorite, and titanite). The trace element patterns of the hydrothermal magnetite and especially the decrease in its Ti content reflect an evolution from the magmatic towards the hydrothermal conditions under decreasing temperatures, which is consistent with findings from analogous porphyry-style deposits elsewhere.


2021 ◽  
Vol 116 (8) ◽  
pp. 1825-1848
Author(s):  
Wei Li ◽  
Nigel J. Cook ◽  
Gui-Qing Xie ◽  
Jing-Wen Mao ◽  
Cristiana L. Ciobanu ◽  
...  

Abstract Yuhengtang is a representative slate-hosted Au deposit in the Jiangnan orogenic belt, South China, with a reserve of ~55 t Au and an average grade of ~3.9 g/t. Gold mineralization is characterized by veinlet and disseminated ores comprising native gold, auriferous pyrite, and arsenopyrite. Paragenesis of the Yuhengtang deposit can be divided into three stages. Pre-ore stage 1 is composed of bedding-parallel layers of pyrite in slate of the Neoproterozoic Banxi Group. Main ore stage 2 represents the Au mineralization stage, and two distinct types of mineralization can be distinguished: visible Au-arsenopyrite-pyrite in quartz veinlets and auriferous arsenopyrite-pyrite disseminated within altered slate. Post-ore stage 3 consists of quartz-pyrite-calcite-ankerite veins. In this study, we integrate electron microprobe, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and high-resolution ion microprobe (SHRIMP) analyses to document textural, isotopic, and compositional variation among texturally complex pyrite and arsenopyrite assemblages in veinlet and disseminated ores. Additionally, LA-ICP-MS sulfur isotope mapping of pyrite highlights the covariation behavior between trace elements and sulfur isotopes at the grain scale, thus allowing the factors controlling sulfur isotope fractionation in hydrothermal Au deposits to be constrained. Pyrite, of sedimentary origin (stage 1), hosts negligible Au (<1.6 ppm) but is enriched in δ34S (15.6–25.8‰). Pyrite and arsenopyrite from stage 2 veinlet mineralization both display porous and dissolution-reprecipitation textures, have low Au concentrations (<4 and <78 ppm, respectively), and show a large variation in δ34S (–2.7 to 14.7‰ and –10.3 to 12.1‰, respectively). Pyrite and arsenopyrite from disseminated mineralization are, in contrast, characterized by oscillatory zoning textures and homogeneous appearance in backscattered electron (BSE) images, respectively, and are obvious by their relatively high contents of invisible Au (up to 90 and 263 ppm, respectively) and restricted range of δ34S values (0–5.3‰). These data suggest that magmatic-hydrothermal fluids contribute most of the Au and S budget in the Yuhengtang Au deposit. The major differences between veinlet and disseminated mineralization in terms of texture, trace element concentrations, and δ34S signatures of pyrite and arsenopyrite reflect contrasting mechanisms of Au precipitation and an evolution of physicochemical parameters of the ore-forming processes, particularly fO2 and the intensity of fluid-rock interaction. Pyrite from stage 3 appears homogeneous in BSE images yet displays a wide variation in δ34S values (1.2–31.4‰), further highlighting the controlling role played by physicochemical condition (i.e., pressure) on the δ34S signature of sulfides. Results of the coupled LA-ICP-MS sulfur and trace element mapping reveal that some zoned pyrite grains from stage 2 formed via overgrowth of Au-rich, light δ34S (2.4‰) hydrothermal rims onto Au-poor, heavy δ34S (18.1–18.5‰) sedimentary cores. All results support that multiple depositional mechanisms within a dynamic mineral system were responsible for Au concentration and define the specific textural, compositional, and sulfur isotope signatures of sulfides in coexisting vein/veinlet and disseminated mineralization. The new data highlight the ore-forming processes-based interpretation for ore genesis and underpin the importance of performing complementary in situ mineralogical analyses to elucidate the source and evolution of ore-forming fluids and enable correct interpretation of the architecture of the hydrothermal Au system.


Minerals ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 634
Author(s):  
Shitou Wu ◽  
Yadong Wu ◽  
Yueheng Yang ◽  
Hao Wang ◽  
Chao Huang ◽  
...  

Olivine forsterite contents [Fo = 100 × Mg/(Mg + Fe) in mol%] and minor–trace element concentrations can aid our understanding of the Earth’s mantle. Traditionally, these data are obtained by electron probe microanalysis for Fo contents and minor elements, and then by laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) for trace elements. In this study, we demonstrate that LA–ICP–MS, with a simplified 100% quantification approach, allows the calculation of Fo contents simultaneously with minor–trace elements. The approach proceeds as follows: (1) calculation of Fo contents from measured Fe/Mg ratios; (2) according to the olivine stoichiometric formula [(Mg, Fe)2SiO4] and known Fo contents, contents of Mg, Fe and Si can be computed, which are used as internal standards for minor–trace element quantification. The Fo content of the MongOLSh 11-2 olivine reference material is 89.55 ± 0.15 (2 s; N = 120), which agrees with the recommended values of 89.53 ± 0.05 (2 s). For minor–trace elements, the results matched well with the recommended values, apart from P and Zn data. This technique was applied to olivine phenocrysts in the Lijiang picrites from the Emeishan large igneous province. The olivine compositions suggest that the Lijiang picrites have a peridotitic mantle source.


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