Energy Critical Element and Precious Metal Deportment in Cu-(Fe-) Sulphides from the Bingham Canyon Porphyry Cu-Mo-Au Deposit

Author(s):  
Maurice Brodbeck ◽  
Sean McClenaghan ◽  
Balz Samuel Kamber ◽  
Patrick Redmond

<p>Porphyry copper deposits are predominantly mined for the major commodities Cu, Mo and Au. From some of these deposits, minor (trace) elements are also recovered as by-products (e.g. Ag, Pd, Te, Se, Bi, Zn, Pb). This list will potentially expand with the increasing demand for critical raw materials in modern energy-related technologies. Key components for such technologies are energy-critical elements (ECEs), many of which are classified as credit elements (e.g. Co, Ga, Ge and In). However, even if currently recovered as by-products, their deportment in copper ores and their overall distribution at the deposit scale have received little research attention. This gap in knowledge is limiting more effective recovery of ECEs. The same applies to elements that might incur refining penalties (e.g. As, Cd, Sb and Sn). Characterizing the trace element inventory of host mineral phases contributes to an improved understanding of the distribution of trace metals. By informing geometallurgy, element deportment studies can thus potentially promote economic and ecologic benefits in the form of improving recovery, adding value to ore resources and helping to reduce the dispersion of deleterious metals into the environment.</p><p>This study focused on the deportment of ECEs and precious metals in the northwestern high-grade section of the Bingham Canyon Cu-Mo-Au porphyry deposit. Contained Cu-(Fe-) sulphides were characterised with scanning electron microscopy and analysed by laser ablation (LA) ICP-MS for their metal endowment and for their potential use as discriminators of magmatic-hydrothermal processes. The availability of copper (iron) sulfides was found to exert principal control over the chalcophile trace element budget. The abundance of bornite and digenite primarily controls the Bi and Ag- budgets of the overall system and significantly affects variations in Te and Se. Chalcopyrite predominantly controls the Co, Ga and In budgets. By contrast, Ge, As, Cd, Sn, Sb and Au are not significantly controlled by the major sulfides indicating their residence in accessory phases. The presence of electrum and Ag-(Au) tellurides governs the distribution of Au, and most likely also the Te budget.<br>At the small scale relevant to mineral processing, the Bingham ore shows a particularly interesting phenomenon. Digenite (Cu<sub>9</sub>S<sub>5</sub>) is invariably present within bornite likely as the exsolution product of a copper-rich bornite solid solution. LA-ICP-MS analyses revealed that the exsolution process has resulted in a redistribution of trace elements, including some ECEs. Trace element partitioning between bornite and digenite is evident in element maps of the complex intergrowths. Silver, Te and Au strongly partition into digenite, while Se seems to retain its primary homogenous distribution, unaffected by exsolution. Elements that are preferentially retained in bornite (Sn and Bi), or at similar levels between the two sulphide species (In) show more complex zoning patterns in bornite. Zones of lowest concentration in bornite, peripheral around exsolved digenite grains, indicate stress-induced diffusion due to accumulating lattice distortions in bornite during digenite growth. The findings from digenite exsolution in bornite at Bingham show that relatively late, solid-state processes can result in complex deportment of precious metals and ECEs within copper-iron sulphides.</p>

2010 ◽  
Vol 74 (2) ◽  
pp. 227-239 ◽  
Author(s):  
A. V. Kuzyura ◽  
F. Wall ◽  
T. Jeffries ◽  
Yu. A. Litvin

AbstractConcentrations of trace elements in coexisting garnet, clinopyroxene and completely miscible carbonate-silicate melt (formed at 7 GPa from the Chagatai silicocarbonatite rock known to be diamondiferous) were determined using LA-ICP-MS. The partition coefficients for Li, Rb, Cs, Ba, Th, U, Ta, Nb, La, Ce, Pb, Pr, Sr, Nd, Zr, Hf, Sm, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, Lu, Sc and Zn were determined. The new experimental data for trace-element partitioning between garnet, clinopyroxene and carbonate-silicate melt have been compared with published data for partitioning between garnet, clinopyroxene and carbonatite melt, and garnet, clinopyroxene and silicate melt. The results show that the trace-element partitioning is not significantly altered by changes in melt composition, with HREE always concentrated in the garnet. Carbonate-silicate melt, as a diamond-forming medium, and carbonatite or silicate melt equilibrated with mantle silicate minerals, behave similarly in respect of trace-element distribution.


Minerals ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 495
Author(s):  
Elsa Nyström ◽  
Helen Thomas ◽  
Christina Wanhainen ◽  
Lena Alakangas

Waste rock can contain high concentrations of deleterious trace elements, which upon oxidation can be released, having a significant impact on water quality. Therefore, knowledge about their occurrence and overall mobility is crucial to ensure suitable environmental protection measures. Sulfide-rich waste rock was characterized and quantified using automated mineralogy (QEMSCAN). Selected pyrite grains were analyzed for trace element occurrence using LA-ICP-MS before, during, and after leaching the waste rock in 10 L small-scale test cells for two years to assess trace element occurrence and mobility. Sequential extraction was used to estimate elemental sequestration during the experiment. The high abundance of pyrite (66%) and scarcity of buffering minerals resulted in low pH (<1.3) leachate with high concentrations of trace elements such as As (21 mg/L), Cu (20 mg/L), Hg (13 µg/L, Pb (856 µg/L), Sb (967 µg/L), Tl (317 µg/L ), and Zn (23 mg/L) in solution with limited retention in secondary minerals, primarily due to these elements’ association with pyrite either as inclusions or impurities showing an average abundance of 193 ppm As, 15 ppm Cu, 13 ppm Hg, 20 ppm Pb, 24 ppm Sb, 26 ppm Tl, and 74 ppm Zn in the waste rock. The occurrence of Cu and Zn as inclusions associated with the pyrite led to their extensive mobilization of 79% and 72%, respectively, despite their low abundance in the waste rock. Provided the overall leachability of S (11%) and limited formation of secondary minerals, the average oxidation rate suggests depletion of the pyrite within approximately 18 years. In conclusion, this study shows the importance of detailed mineralogical investigations and early preventive measures of waste rock to ensure sustainable mine waste and water management.


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 ◽  
...  

&lt;p&gt;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&lt;sub&gt;H2O&lt;/sub&gt; &gt; 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.&lt;/p&gt;&lt;p&gt;Titanite trace element and U-Pb data were collected by LA-ICP-MS at the University of Maine using an ESI NWR193&lt;sup&gt;UC&lt;/sup&gt; 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 &amp;#177; 8 Ma (dark BSE cores), B. 372 &amp;#177; 4 Ma (bright BSE cores), C. 342 &amp;#177; 6 Ma (bright BSE cores, no Eu anomaly), and D. 302 &amp;#177; 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&lt;sub&gt;H2O&lt;/sub&gt; fluid infiltration event. Zr-in-titanite temperatures for rims in the quartz-bearing SSP18-1B give a weighted mean T of 764 &amp;#176;C at 4.5 GPa, consistent with the muscovite-absent sillimanite-bearing assemblage in garnet cores from metapelite samples. However, the 100-150 &amp;#176;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.&lt;/p&gt;


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.


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.


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.


2001 ◽  
Vol 65 (2) ◽  
pp. 249-276 ◽  
Author(s):  
G. Tischendorf ◽  
H.-J. Förster ◽  
B. Gottesmann

AbstractMore than 19,000 analytical data mainly from the literature were used to study statistically the distribution patterns of F and the oxides of minor and trace elements (Ti, Sn, Sc, V, Cr, Ga, Mn, Co, Ni, Zn, Sr, Ba, Rb, Cs) in trioctahedral micas of the system phlogopite-annite/siderophyllite-polylithionite (PASP), which is divided here into seven varieties, whose compositional ranges are defined by the parametermgli(= octahedral Mg minus Li). Plots of trace-element contentsvs.mglireveal that the elements form distinct groups according to the configuration of their distribution patterns. Substitution of most of these elements was established as a function ofmgli. Micas incorporate the elements in different abundances of up to four orders of magnitude between the concentration highs and lows in micas of ‘normal’ composition. Only Zn, Sr and Sc are poorly correlated tomgli. In compositional extremes, some elements (Zn, Mn, Ba, Sr, Cs, Rb) may be enriched by up to 2–3 orders of magnitude relative to their mean abundance in the respective mica variety. Mica/melt partition coefficients calculated for Variscan granites of the German Erzgebirge demonstrate that trace-element partitioning is strongly dependent on the position of the mica in the PASP system, which has to be considered in petrogenetic modelling.This review indicates that for a number of trace elements, the concentration ranges are poorly known for some of the mica varieties, as they are for particular host rocks (i.e. igneous rocks of A-type affiliation). The study should help to develop optimal analytical strategies and to provide a tool to distinguish between micas of ‘normal’ and ‘abnormal’ trace-element composition.


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.


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