Crystallization of sulfide liquids and the interpretation of ore composition

1997 ◽  
Vol 34 (4) ◽  
pp. 352-365 ◽  
Author(s):  
D. S. Ebel ◽  
A. J. Naldrett
Keyword(s):  
Major Elements ◽  
Distribution Coefficients ◽  
Liquid Composition ◽  
Sulfide Liquid ◽  
Free System ◽  
Element Partitioning ◽  
Ore Bodies ◽  
Sulfide Melt ◽  
Magmatic Sulfide ◽  
D Values

We have been exploring ways to quantitatively assess the extent to which fractionation of sulfide melt has effected variations in composition within magmatic sulfide ore bodies. Our approach has been to determine by experiment the crystallization paths of sulfide liquids in temperature and composition dimensions. In this paper, the results of new major-element partitioning experiments below 1050 °C in the nickel-free system are presented and summarized along with new and previous work in the Fe–Ni–Cu–S quaternary. The partition coefficients D for Cu between monosulfid solid solution (mss) and sulfide liquid in the Ni-free system (DCu = (wt.% Cu in mss)/(wt.% Cu in liquid)) cluster near 0.3, but decrease to nearly 0.1 for Cu-rich, S-poor liquids near 1000 °C. DNi also declines with decreasing sulfur content of the liquid, but increases with decreasing temperature. Preliminary data indicate that DNi exceeds 1.0 in low-Ni liquids with greater than 16 wt.% Cu, at 1050 °C. The quality of available data on the Fe–Ni–Cu–S system currently exceeds the sensitivity of crystallization models based on the distribution coefficient approximation for major elements. However, we present equations for variable distribution coefficients for Ni and Cu that can be incorporated into calculations of the ratio of trapped initial liquid to fractionated solid for bulk ore samples, using D values for platinum group elements from the literature. Fractionation can then be modeled quite well using an iterative approach, with D values changing in response to liquid composition with each increment of crystallization along an assumed temperature path.

Quantification of excess 231Pa in late Quaternary igneous baddeleyite

2020 ◽  
Vol 105 (12) ◽  
pp. 1830-1840 ◽  
Author(s):  
Yi Sun ◽  
Axel K. Schmitt ◽  
Lucia Pappalardo ◽  
Massimo Russo
Keyword(s):  
Late Quaternary ◽  
Central Italy ◽  
Direct Analysis ◽  
Weight Percent ◽  
Volcanic Field ◽  
Distribution Coefficients ◽  
Secular Equilibrium ◽  
Melt Distribution ◽  
D Values ◽  
Significant Figures

Abstract Initial excess protactinium (231Pa) is a frequently suspected source of discordance in baddeleyite (ZrO2) geochronology, which limits accurate U/Pb dating, but such excesses have never been directly demonstrated. In this study, Pa incorporation in late Holocene baddeleyite from Somma-Vesuvius (Campanian Volcanic Province, central Italy) and Laacher See (East Eifel Volcanic Field, western Germany) was quantified by U-Th-Pa measurements using a large-geometry ion microprobe. Baddeleyite crystals isolated from subvolcanic syenites have average U concentrations of ~200 ppm and are largely stoichiometric with minor abundances of Nb, Hf, Ti, and Fe up to a few weight percent. Measured (231Pa)/(235U) activity ratios are significantly above the secular equilibrium value of unity and range from 3.4(8) to 14.9(2.6) in Vesuvius baddeleyite and from 3.6(9) to 8.9(1.4) in Laacher See baddeleyite (values within parentheses represent uncertainties in the last significant figures reported as 1σ throughout the text). Crystallization ages of 5.12(56) ka (Vesuvius; MSWD = 0.96, n = 12) and 15.6(2.0) ka (Laacher See; MSWD = 0.91, n = 10) were obtained from (230Th)/(238U) disequilibria for the same crystals, which are close to the respective eruption ages. Applying a corresponding age correction indicates average initial (231Pa)/(235U)0 of 8.8(1.0) (Vesuvius) and 7.9(5) (Laacher See). For reasonable melt activities, model baddeleyite-melt distribution coefficients of DPa/DU = 5.8(2) and 4.1(2) are obtained for Vesuvius and Laacher See, respectively. Speciation-dependent (Pa4+ vs. Pa5+) partitioning coefficients (D values) from crystal lattice strain models for tetra- and pentavalent proxy ions significantly exceed DPa/DU inferred from direct analysis of 231Pa for Pa5+. This is consistent with predominantly reduced Pa4+ in the melt, for which D values similar to U4+ are expected. Contrary to common assumptions, baddeleyite-crystallizing melts from Vesuvius and Laacher See appear to be dominated by Pa4+ rather than Pa5+. An initial disequilibrium correction for baddeleyite geochronology using DPa/DU = 5 ± 1 is recommended for oxidized phonolitic melt compositions.

Concentrations of Te, As, Bi, Sb (TABS) and Se in the Marginal Zone of the Bushveld Complex: evidence for crustal contamination and the nature of the magma that formed the Merensky Reef

2020 ◽  
Author(s):  
Eduardo Mansur ◽  
Sarah-Jane Barnes
Keyword(s):  
Marginal Zone ◽  
Bushveld Complex ◽  
Crustal Contamination ◽  
Sulfide Minerals ◽  
Sulfide Liquid ◽  
Liquid Component ◽  
Merensky Reef ◽  
Chalcophile Elements ◽  
Magmatic Sulfide ◽  
Primary Magmas

<p>The association of platinum-group elements (PGE) and the chalcophile elements Te, As, Bi, Sb and Sn (TABS) has been documented in several magmatic sulfide deposits. These groups of elements are either hosted within sulfide minerals, or combine to form discrete platinum-group minerals (PGM) associated with sulfide minerals. However, the concentration of TABS in parental magmas from which magmatic sulfide deposits formed was still missing. This study presents the distribution of TABS and Se in B-1, B-2 and B-3 rocks of the Marginal Zone of the Bushveld Complex. These rocks have been proposed as representative of the parental liquids from which the Bushveld Complex crystallized, thus allowing us to assess the concentration of Se and TABS in the liquids from which some of the largest PGE deposits in the world have formed. Concentrations of As and Sb in the initial Bushveld liquid (B-1) are significantly higher than in primary magmas, whereas the Se and TABS of later magmas (B-2 and B-3) are similar to primary magmas. We attribute the difference due upper crustal contamination of the B-1 magma, whereas the B-2 and B-3 magmas were most likely contaminated with a plagioclase-rich residuum formed upon the partial melting of the upper crust. Moreover, we modeled the concentrations of the TABS in the Merensky Reef using a mixture of two of the magma types present in the Marginal Zone (the B-1 and B-2) as the initial silicate liquid. The modeled concentrations closely resemble the measured values obtained for a section across the Merensky Reef at the Impala mine. This supports the B-1 and B-2 mixture as an appropriate initial liquid for the crystallization of the Merensky Reef. The modeling also shows that the distributions of Se, Te and Bi across the Merensky Reef are controlled by the sulfide liquid component. In contrast, As and Sb distributions are influenced both by the amount of silicate melt component in the cumulates and the sulfide liquid component. This is because Se, Te and Bi are moderately to strongly chalcophile elements, but As and Sb are only slightly chalcophile elements. Consequently, the effect of crustal contamination for elements with high partition coefficients between sulfide and silicate liquid (Te, Bi and Se) is obscured by the interaction of sulfides with a large volume of silicate magma. Therefore, the concentrations of these elements are higher in samples with greater proportions of sulfide minerals. In contrast, for elements with lower partition coefficients (As and Sb), the whole-rock concentrations are not upgraded by the presence of sulfide minerals, and thus the effect of crustal contamination can be more readily assessed.</p>

Element partitioning in ferruginous and pyritic phosphorite from the continental margin off Morocco

1978 ◽  
Vol 42 (322) ◽  
pp. 221-228 ◽  
Author(s):  
J. M. McArthur
Keyword(s):  
Organic Matter ◽  
Organic Carbon ◽  
Continental Shelf ◽  
Continental Margin ◽  
Major Elements ◽  
Element Partitioning ◽  
Carbonate Fluorapatite

SummaryPhosphorites from the continental shelf off Morocco have been analysed for major elements and Fe, Mn, V, Cu, Ni, Zn, As, Na, Sr, S, and for carbonate. In pyritic phosphorites Cu, Ni, Zn, and As are present mainly in minor pyrite and organic carbon. In ferruginous phosphorites As, Mn, and V are associated with goethite. In the ferruginous phosphorites Cu, Ni, and Zn may have been introduced in association with organic matter and pyrite during phosphorite formation and been retained during subsequent destruction of these phases by weathering. In all phosphorites Na and Sr are present mainly in carbonate-fluorapatite. Sulphur in the ferru-ginous phosphorites occurs only in carbonate-fluorapatite. In the pyritic samples it is partitioned between pyrite and francolite (carbonate-fluorapatite).

scholarly journals The Distribution Coefficients of Major and Minor Elements in Coral Skeletons Under Variable Calcium Seawater Concentrations

2021 ◽  
Vol 9 ◽  
Author(s):  
Sharon Ram ◽  
Jonathan Erez
Keyword(s):  
Distribution Coefficients ◽  
Natural Seawater ◽  
Acropora Cervicornis ◽  
Pocillopora Damicornis ◽  
Fractionation Process ◽  
Seawater Chemistry ◽  
Minor Elements ◽  
Coral Skeletons ◽  
Fossil Corals ◽  
D Values

Coral skeletons are one of the best archives for past ocean seawater (SW) chemistry and isotopes. However, the distribution coefficients of major and minor elements in coral skeletons are not well determined. In this study, we launched an experiment to determine the distribution coefficients of multiple elements in corals’ skeletons by changing Ca concentrations in SW (CaSW). Two scleractinian corals, Pocillopora damicornis and Acropora cervicornis were cultured in modified Gulf of Eilat water (Red-Sea) with CaSW of approximately 10, 15, 20, and 25 mM. After almost three months, the newly grown skeletons were analyzed for the following elements: Li, Na, Mg, K, Sr, and Ba. Their ratios to Ca in the coral skeleton (El/Cacoral) increased linearly with El/CaSW (with R2 values above 0.98), crossing the origin and thus indicating constant distribution coefficient for each element over the experimental range of El/CaSW. The values of DEl were in good agreement with values reported for corals collected in natural seawater. However, differences were observed between the two species, and both were slightly deviating from inorganic aragonite D values. These deviations are well explained by Rayleigh fractionation process in the calcifying fluid (assuming it is mainly seawater). This was observed both for elements with D > 1 (Ba and Sr) and D < 1 (Li, Mg, Na, and K). P. damicornis showed open system behavior (∼20% of its Ca utilized) while A. cervicornis showed more closed calcifying reservoir (∼50% of its Ca utilized). The finding that the distribution coefficients of the six minor and trace elements are constant for a given species, should help in the reconstruction of past seawater chemistry based on multielement measurements in fossil corals. In particular, Na/Cacoral can be used to reconstruct past ocean Ca concentrations and with El/Cacoral ratios for other elements, their concentrations for the Cenozoic can be reconstructed.

Distribution of microamounts of some M2+ ions during ZnSO4·7H2O crystallization

2000 ◽  
Vol 78 (7) ◽  
pp. 993-1002 ◽  
Author(s):  
Marek Smolik
Keyword(s):  
Solid Solutions ◽  
Ionic Radius ◽  
Electronic Configuration ◽  
Distribution Coefficients ◽  
Octahedral Coordination ◽  
Crystal Chemical ◽  
Trace Impurities ◽  
Ionic Radii ◽  
Sulfate Heptahydrate ◽  
D Values

Distribution coefficients (D) of trace amounts of Ni2+, Co2+, Mg2+, Cd2+, Cu2+, Mn2+, Ca2+, and Fe2+ have been determined during crystallization of ZnSO4·7H2O. Their dependencies on the ionic radii of M2+ ions, solubilities and structures of the corresponding sulfates as well as their abilities to form solid solutions with ZnSO4·7H2O have been analyzed. The D values are in the range <0.006 (DCa) - 1.61 (DNi) and depend mainly on similarity of the structures of the corresponding sulfates and the ability of MSO4·nH2O to form solid solutions with ZnSO4·7H2O. The order of lowering some of the determined distribution coefficients (DNi > DMg > DCo > DFe > Dcu) exactly agrees with increase of the deformation trend of octahedral coordination of corresponding ions resulting from their electronic configuration. The D coefficients do not depend on similarity of size of ionic radii of microcomponent (rM2+) to macrocomponent (rZn2+), however for ions forming monoclinic sulfate hydrates at 20°C (Co2+, Fe2+, Cd2+, Ca2+) this dependence of distribution coefficients on rM2+ is linear in a plot of log D against ionic radius. The effect of solubilities of corresponding sulfates in water on the D coefficients is complex and clouded by crystal-chemical factors.Key words: crystallization, zinc(II) sulfate heptahydrate, cocrystallization, distribution coefficients D (Henderson-Kracek, Khlopin), distribution of trace impurities.

Origin of noble-metal nuggets in sulfide-saturated arc magmas: A case study of olivine-hosted sulfide melt inclusions from the Tolbachik volcano (Kamchatka, Russia)

Geology ◽  
2020 ◽  
Vol 48 (6) ◽  
pp. 620-624
Author(s):  
Vadim S. Kamenetsky ◽  
Michael Zelenski
Keyword(s):  
Noble Metals ◽  
Melt Inclusions ◽  
Basaltic Magma ◽  
Sulfide Liquid ◽  
Direct Crystallization ◽  
Arc Magmas ◽  
Tolbachik Volcano ◽  
Sulfide Melt ◽  
Significant Uptake

Abstract Minerals that contain platinum-group elements (PGEs) and occur in some magmatic Cu-Ni sulfide deposits have been ascribed to crystallization from an originally PGE-rich sulfide liquid. The occurrence of PGE-bearing minerals (PGMs) in some sulfide-undersaturated primitive melts has been envisaged and recently reported, whereas direct crystallization of PGMs in sulfide-saturated silicate magmas is seemingly hindered by strong partitioning of PGE into immiscible sulfide melts. In this study, we discovered abundant nanoparticles containing noble metals in association with sulfide melt inclusions entrapped inside primitive olivine phenocrysts (Fo85–92) from the recent basaltic magma of the Tolbachik volcano (Kamchatka arc, Russia). These nuggets occur in swarms on the surface of the sulfide globules and are represented by native metals, sulfides, and alloys of Pd, Pt, Au, Pb, and Bi. The nuggets on different globules can be either Pd- or Pt-rich nuggets, and the compositions are highly variable, even among adjacent nuggets. We argue that the diffusive supply of Pd from the external nuggets can be responsible for significant uptake of Pd (up to 2 wt%) in the sulfide melt. We consider direct crystallization of PGMs in a primitive basaltic melt undergoing sulfide unmixing, and possibly sulfide breakdown due to oxidation, as another mechanism additional to their “classic” origin from the PGE-rich sulfide melt in response to solidification.

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