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Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite

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Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite minerals Article Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite Xenoliths from East Antarctica Alexandre V. Andronikov * , Irina E. Andronikova and Tamara Sidorinova Department of Geochemistry and Laboratories, Czech Geological Survey, Geologicka 6, 15200 Prague, Czech Republic; [email protected] (I.E.A.); [email protected] (T.S.) * Correspondence: [email protected] Abstract: Sulfides in upper mantle lherzolite xenoliths from Cretaceous alkaline-ultramafic rocks in the Jetty Peninsula (East Antarctica) were studied for their major and trace-element compositions using SEM and LA-ICP-MS applied in situ. Modal abundance of sulfides is the lowest in Cpx-poor lherzolites ≤ Spl-Grt lherzolites << Cpx-rich lherzolites. Most sulfides are either interstitial (i-type) or inclusions in rock-forming minerals (e-type) with minor sulfide phases mostly present in metasomatic veinlets and carbonate-silicate interstitial patches (m-type). The main sulfide assemblage is pent- landite + chalcopyrite ± pyrrhotite; minor sulfides are polydymite, millerite, violarite, siegenite, and monosulfide solution (mss). Sulfide assemblages in the xenolith matrix are a product of the subsolidus re-equilibration of primary mss at temperatures below ≤300 ◦C. Platinum group elements (PGE) Citation: Andronikov, A.V.; abundances suggest that most e-type sulfides are the residues of melting processes and that the i-type Andronikova, I.E.; Sidorinova, T. sulfides are crystallization products of sulfide-bearing fluids/liquids. The m-type sulfides might have Trace-Element Geochemistry of resulted from low-temperature metasomatism by percolating sulfide-carbonate-silicate fluids/melts. Sulfides in Upper Mantle Lherzolite Xenoliths from East Antarctica. The PGE in sulfide record processes are related to partial melting in mantle and intramantle melt Minerals 2021, 11, 773. https:// migration. Most other trace elements initially partitioned into interstitial sulfide liquid and later doi.org/10.3390/min11070773 metasomatically re-enriched residual sulfides overprinting their primary signatures. The extent of element partitioning into sulfide liquids depends on P, T, f O2, and host peridotite composition. Academic Editors: Nigel J. Cook, Paul Sylvester, Hanumantha Keywords: sulfides; trace elements; upper mantle xenoliths; East Antarctica; SEM; LA-ICP-MS Rao Kota, Theodore J. Bornhorst, Anna H. Kaksonen, Huifang Xu, Alexander R Cruden and Sytle M. Antao 1. Introduction Small stock-like Late Jurassic to Early Cretaceous intrusions of alkaline-ultramafic Received: 20 May 2021 rocks (mostly alkaline picrite and ultramafic lamprophyre) in the Jetty Peninsula (Prince Accepted: 13 July 2021 Published: 16 July 2021 Charles Mountains, East Antarctica; Figure1) contain abundant xenoliths representing samples of the subcontinental lithospheric mantle (SCLM) beneath the region [1–6]. The Publisher’s Note: MDPI stays neutral studied area is located on the flank of the small rift system which formed at about 650 Ma with regard to jurisdictional claims in and lies on the western side of the larger Lambert–Amery rift system, which was active from published maps and institutional affil- the Mesozoic period to the Cenozoic period. A detailed description of the geology of the iations. Prince Charles Mountains is given in [4–7]. The upper mantle xenoliths are mostly lherzolite with subordinate harzburgite, dunite and wherlite. Three main groups of lherzolites were identified on the basis of mineral assemblage, textural relationships between the minerals, and mineral composition: (i) clinopyroxene (Cpx)-poor spinel (Spl) lherzolites, (ii) Cpx- rich Spl herzolites, and (iii) Spl-garnet (Grt) lherzolites [3–5]. The East Antarctic SCLM Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. rocks have experienced multiple episodes of infiltration by silicate, carbonate, and minor This article is an open access article sulfide melts; this has resulted in partial melting, recrystallization, and the generation distributed under the terms and of metasomatic minerals such as carbonates and sulfides [5,7–11]. The deepest-sampled ◦ conditions of the Creative Commons upper mantle rocks (Spl-Grt lherzolite) yield ambient temperatures of 1040–1180 C with Attribution (CC BY) license (https:// pressures up to 24 kbar that correspond to P-T conditions at depths of 75–80 km [2,4,12]. creativecommons.org/licenses/by/ Sulfide minerals are a common accessory phase (<0.1%) in mantle rocks and are 4.0/). typically represented by pentlandite, pyrrhotite, and chalcopyrite [13–16]. Despite their Minerals 2021, 11, 773. https://doi.org/10.3390/min11070773 https://www.mdpi.com/journal/minerals Minerals 2021, 11, x FOR PEER REVIEW 2 of 32 1040–1180 °C with pressures up to 24 kbar that correspond to P-T conditions at depths of 75–80 km [2,4,12]. Minerals 2021, 11, 773 Sulfide minerals are a common accessory phase (<0.1%) in mantle rocks2 ofand 32 are typ- ically represented by pentlandite, pyrrhotite, and chalcopyrite [13–16]. Despite their in- significant abundances, sulfides are important minerals because they likely control the insignificantplatinum group abundances, element sulfides (PGE), are siderophile, important minerals and chalcophile because they element likely control budget the of mantle platinumrocks and group determine element their (PGE), behavior siderophile, during and melting chalcophile [16–18]. element Although budget sulfides of mantle in mantle rocks and determine their behavior during melting [16–18]. Although sulfides in mantle peridotite xenoliths from different localities have been recently studied to trace their crys- peridotite xenoliths from different localities have been recently studied to trace their crystallizationtallization and and subsolidus subsolidus historieshistories ([ 13([13,17–27],17–27] and and others), others), studies studies of the traceof the element trace element compositioncomposition of of sulfides sulfides in mantle in mantle xenoliths xenoliths are scarce are scarce and are and mostly are limitedmostly tolimited the PGE. to the PGE. FigureFigure 1. 1.Schematic Schematic map map of Antarctica of Antarctica showing showing the position the posi oftion thePrince of the Charles Prince MountainsCharles Mountains and and JettyJetty Peninsula Peninsula (asterix). (asterix). SulfideSulfide minerals minerals in peridotitein peridotite xenoliths xenoliths from from East Antarctica East Antarctica were heretofore were heretofore almost almost completelycompletely unstudied. unstudied. Only Only several several sulfide sulfide grains grains in Spl-Grt in Spl-Grt lherzolite lherzolite xenoliths xenoliths had been had been examined via electron microprobe and Raman spectroscopy by Solovova et al. [11]. In examined via electron microprobe and Raman spectroscopy by Solovova et al. [11]. In order to retrieve information on the origin and evolution of sulfides in mantle xenoliths, weorder conducted to retrieve detailed information in situ scanning on the origin electron and microscopy evolution (SEM) of sulfides and laser in mantle ablation xenoliths, inductivelywe conducted coupled detailed plasma in mass situ spectrometric scanning electron (LA-ICP-MS) microscopy analyses (SEM) of the sulfideand laser phases ablation in- inductively SCLM peridotite coupled xenoliths plasma samplesmass spectrometric from the Jetty (LA-ICP-MS) Peninsula area. analyses The present of the work sulfide is phases basedin SCLM on lherzolite peridotite xenoliths xenoliths that havesamples been from previously the Jetty studied Peninsula in detail area. for bulk The rock present and work is rock-formingbased on lherzolite mineral geochemistryxenoliths that [2 have–4,12 ].been previously studied in detail for bulk rock and rock-forming mineral geochemistry [2–4,12]. 2. Materials and Methods 2.1. Brief Characteristics of Lherzolite Xenoliths 2. Materials and Methods Upper mantle xenoliths in the Jetty Peninsula area are hosted by alkaline ultramafic magmatic2.1. Brief Characteristic rocks (150 ± 5s Ma)of Lherzolite that originated Xenoliths from the melting of the mantle at depths of 120–150Upper km mantle [1,28,29 xenoliths]. The xenoliths in the Jetty were Peninsula trapped by area ascending are hosted magma by alkaline at depths ultramafic frommagmatic75–80 kmrocksup (150 to the ± 5 crustal–mantle Ma) that originated boundary from and the were melting rapidly of deliveredthe mantle to at the depths of surface120–150 [4 ].km The [1,28,29]. studied lherzolite The xenoliths xenolith were samples trapped were by collected ascending by the magma authors at from depths a from single75–80 magmatic km up to body the composedcrustal–mantle of alkaline boundary picrite. and were rapidly delivered to the surface The Cpx-poor Spl lherzolites are medium to coarse-grained inequigranular rocks [4]. The studied lherzolite xenolith samples were collected by the authors from a single composed of 78–82% olivine (Ol), 10–14% orthopyroxene (Opx), 4–7% Cpx, and 1.5–5% Spl. magmatic body composed of alkaline picrite. Low concentrations of CaO and Al2O3 (0.8–1.5 wt% and 0.5–1.6 wt%, respectively) and a high Mg#The (100Mg/(MgCpx-poor Spl + Fe)) lherzolites of 90.2 to are 91.2 medium suggesting to depletion coarse-grained by partial inequigranular melting, are rocks characteristiccomposed of of 78–82% the rock olivine [3,4]. The (Ol), history 10–14% of both orthopyroxene significant depletion (Opx), and4–7% later Cpx, slight and 1.5–5% Spl. Low concentrations of CaO and Al2O3 (0.8–1.5 wt% and 0.5–1.6
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