Sulfide mineralogy and redox conditions in some shergottites

Abstract— Magmatic sulfide mineralogy has been studied in 2 olivine‐phyric shergottites (DaG 476 and SaU 005) and 4 basaltic shergottites (Zagami, Shergotty, Los Angeles, and NWA 480). Modal abundances of magmatic sulfides, as estimated by image analysis on thin section, are high (0.16 to 0.53 area percent) and correlate positively with abundances of Fe‐Ti oxides. Sulfides are mesostasis minerals, being mostly interstitial grains or locally enclosed in post‐cumulus melt inclusions (e.g., SaU 005) in olivine. Sulfides in shergottites are composed of major pyrrhotite containing pentlandite exsolutions associated with minor amounts of Cu sulfides (chalcopyrite and/or cubanite). Hot desert finds (e.g., DaG 476) show abundant fracture‐filling iron (oxy)hydroxides of probable terrestrial origin. Unaltered sulfides show metal‐rich hexagonal pyrrhotite compositions with metal/sulfur (M/S) ratio ranging between 0.936 ± 0.005 and 0.962 ± 0.01. This compositional range corresponds to the two‐phase structural domain 2C + nC of the Fe‐S system; however, the high‐temperature disordered hexagonal 1C pyrrhotite structure would be in better agreement with magnetic properties of shergottites. Ni contents in pyrrhotite increase from Los Angeles (<0.05 at%) to Shergotty, Zagami, and NWA 480 (0.2–0.5 at%), and DaG 476 and SaU 005 (up to 3 at%). The higher Ni values of pyrrhotite in olivine‐phyric shergottites correlate with the abundance of pentlandite exsolutions, both reflecting more primitive Ni‐rich sulfide liquids where abundant olivine crystallized. This result and the strong correlation between sulfide abundances and Fe‐Ti oxides argue for a primary magmatic origin of these sulfides. Although they reproduce the trend of magmatic oxygen fugacity conditions determined from Fe‐Ti oxide pairs, observed pyrrhotite compositions are systematically more metal‐deficient compared to those calculated from the Fe‐S‐O system. This suggests post‐magmatic oxidation during cooling on Mars, followed by terrestrial weathering for hot desert finds.     

Copper and Noble Metal Enrichments Across the Lithosphere--Asthenosphere Boundary of Mantle Diapirs: Evidence from the Lanzo Lherzolite Massif

The Lanzo lherzolite massif shows that the top of asthenosphericdiapirs is a zone of preferential S, Cu, Au, and platinum-groupelement (PGE) enrichment. Residual plagioclase lherzolites whichunderwent a limited extraction of mid-ocean ridge basalt (MORB)melt during diapiric uprise are enriched in Ru, PPGE (Pt andPd), and Au (3–10 times the pristine asthenospheric mantle),whereas they are moderately enriched in Cu (up to 38 ppm), depletedin Ir (Ir–Ni_mn=1–0.1), and have S contents rangingbetween 95 and 215 ppm. The behaviour of chalcophile elementsin the lherzolites cannot be modelled by equilibrium batch melting.The precious metals vary independently of lithophile elementcontent and modal rock composition. It is suggested that theexcess of PPGE, Au, and Cu was introduced either by a plume-typemagma which cross-cut the Lanzo massif before rifting or bydownward percolation of sulphides segregated from the MORB magmasextracted from the asthenospheric diapir. Calculated chalcophile element compositions of the extractedmelts show high Cu/Pd ratios (27–145) typical of meltsthat have experienced early S saturation. This adds straightforwardevidence to theoretical modelling and indirect assumptions basedon extruded MORB, i.e., it is possible to produce high D-elementdepleted magma compositions simply by low degrees of mantlemelting under S-saturated conditions without fractionation inmagma chambers. The MORB magma has circulated via ariegite andgabbro dykes as well as dunitic bands. All of these rocks arestrongly depleted in Ir. Their Ir/Ni_mnratios range between 0192in the gabbros and 0068–0168 in the dunites. The depletionin Ir (and probably Os) is attributed to segregation of Ir-bearingalloys from the MORB melt before it cross-cut the peridotites. The dunitic bands are distinguished from the harzburgites anddunites analysed so far by a large range of total precious metalcontent (17–77 ppb), positive Pd/Ir_mn ratios, and an excessof S (up to 210 ppm) and/or Cu (up to 87 ppm). Chalcophile elementdata support a model whereby the dunitic bands have formed fromreaction with percolating S-saturated melts. The progressiveenrichments in Cu and PPGEs observed in the latest percolationstages (Pd/Ir_mn=16–28; Cu/S=0–4) may be modelledby increasing the degree of melting that produced the percolatingmelt(s). A similar model may account for strong Cu and PPGEenrichments in the dunitic transition zone of some ophioliticcomplexes. ^* Present address; Laurentian University, Ramsey Lake Road, Sudbury, Ontario, P3E 2C6, Canada     

Petrology and Thermal History of Highly Deformed Mantle Xenoliths from the Montferrier Basanites, Languedoc, Southern France: A Comparison with Ultramafic Complexes from the North Pyrenean Zone

The Oligocene basanites from Montferrier near Montpellier containvarious ultramafic xenoliths, predominantly spinel-lherzoliteslocally rich in amphibole, and a unique garnet-clinopyroxenite.The sulfide content of spinel-lherzolites is unusually highfor xenoliths and approaches that of MORB mantle sources. Thegarnet-clinopyroxenite, now consisting of recrystallized cpx+ garnet + opx + sp assemblage, results from subsolidus evolutionof a primary subcalcic clinopyroxene (plus minor spinel) compositionallysimilar to those experimentally obtained during high-pressurecrystallization of MORB; such an origin is also attested bythe Ni/Cu ratio of the coexisting sulfide component which isclose to 1. The spinel lherzolites display generally fine-grained porphyroclastictextures with varying proportions of porphyroclasts and neoblasts,and more rarely granuloblastic textures. Within each singlesample, the cores of the pyroxene and spinel porphyroclastshave nearly constant compositions. Significantly inhomogeneouschemical changes appear at the extreme edges of some large crystals,as well as in the fine-grained pyroxenes and spinel, whereasolivine composition is invariable. Such compositional variationsresult from the superimposed effects of two episodes of deformationand recrystallization. Geothermometric determinations show that all the spinel lherzolitesand the garnet-pyroxenite attained an equilibrium state around950?C. From a discussion on the origin of relict opx–cpx–spclusters and relatively high sulfide contents in peridotites,on the reconstructed primary paragenesis of the garnet-pyroxenite,and from a comparison with the North Pyrenean ultramafic associations,it is inferred that this equilibration occurred at the end ofan episode involving partial melting, crystallization, and subsolidusrecrystallization consequent on plastic deformation. Sulfideswere probably retained as sulfide melt early in this episodewhile metasomatism responsible for the crystallization of amphiboleoccurred late. This event is ascribed to a diapiric uplift upto a 45–50 km depth in relation with Oligocene riftingwhich started 35–40 m.y. ago in the Languedoc area. The compositional disequilibrium observed in a number of lherzolitesis related to a second episode of shearing deformation responsiblefor generating porphyroclastic textures, grading locally intomylonites. As a consequence of a concomitant cooling, Al andCr contents decrease in both pyroxenes, and Na content alsodecreases in clinopyroxene. The main chemical change of spinelconsists of a systematic substitution of MgAl₂O₄ by FeCr₂O₄,linked to the development of a porphyroclastic texture, i.e.to the degree of shearing deformations imposed upon the peridotites.The temperature decrease down to 750?C resulted from the ascentof previously equilibrated mantle blocks into colder parts nearthe Moho. This event occurred a few millions years before thecollection of xenoliths by the Montferrier basanites, probablyas the Cevennes fault zone below Oligocene grabens was reactivedat depth.     

Sulfide petrology of four nakhlites: Northwest Africa 817, Northwest Africa 998, Nakhla,and Governador Valadares

Abstract– The nakhlites contain small proportions of Cu‐Fe‐Ni sulfide minerals; we have studied these sulfides in Northwest Africa (NWA) 998, Nakhla, Governador Valadares, and NWA 817 with optical microscopy, scanning electron microscope, and electron microprobe. Modal abundances of magmatic sulfides, as estimated by image analysis on thin section, are uniformly low (0.02 to 0.05 ± 0.03 vol%), i.e., a factor 5 lower than in shergottites. Sulfides occur within the glassy mesostasis, as composite two‐phase Fe‐Ti oxide‐sulfide grains, intimately associated with interstitial grains or locally enclosed in postcumulus melt inclusions (e.g., Governador Valadares) in olivine. They exhibit a uniform low‐Ni monoclinic pyrrhotite composition ± chalcopyrite. There is a gradation of sulfide grain sizes and textures across the nakhlites flow(s): droplets in NWA 817; resorbed blebs in Governador Valadares; more massive, true intercumulus blebs in Nakhla and NWA 998. These nakhlites also show evidence for sulfide weathering. Hot desert finds (e.g., NWA 998 and NWA 817) show a few percent fracture‐filling iron (oxy) hydroxides of likely terrestrial origin. Original sulfides are 50% altered in our NWA 998 section, with iron (oxy) hydroxides at grain boundaries and as complete pseudomorphs. The compositions of unaltered pyrrhotites are homogeneous, close to that of the monoclinic endmember Fe₇S₈, and are too sulfur‐rich to have been in chemical equilibrium with the late magmatic redox state fixed by the fayalite‐magnetite‐quartz buffer. Therefore, the compositions of the pyrrhotites must have been altered during the later stages of magmatic crystallization, by assimilation of S‐rich regolith and hydrothermal circulation.     

Matching Martian crustal magnetization and magnetic properties of Martian meteorites

Abstract— Magnetic properties of 26 (of 32) unpaired Martian meteorites (SNCs) are synthesized to further constrain the lithology carrying Martian magnetic crustal sources. Magnetic properties of ultramafic cumulates (i.e., Chassigny, Allan Hills [ALH] 84001) and lherzolitic shergottites (ALH 77005, Lewis Cliff [LEW] 88516) are one or two orders of magnitude too weak to account for the crustal magnetizations, assuming magnetization in an Earth‐like field. Nakhlites and some basaltic shergottites, which are the most magnetic SNCs, show the right intensity. Titanomagnetite is the magnetic carrier in the nakhlites (7 meteorites), whereas in most basaltic shergottites (11 meteorites) it is pyrrhotite. Dhofar (Dho) 378, Los Angeles, and NWA 480/1460 and 2046 are anomalous basaltic shergottites, as their magnetism is mainly due to titanomagnetite. Pyrrhotite should be among the candidate minerals for the magnetized Noachian crust.     

Melt inclusions in augite from the nakhlite meteorites: A reassessment of nakhlite parental melt and implications for petrogenesis

Abstract– The nakhlites, a subgroup of eight clinopyroxenites thought to come from a single geological unit at the Martian surface, show melt inclusions in augite and olivine. In contrast to olivine‐hosted melt inclusions, augite‐hosted melt inclusions are not surrounded by fractures, and are thus considered preferential candidates for reconstructing parent liquid compositions. Furthermore, two types of augite‐hosted melt inclusion have been defined and characterized in four different nakhlites (Northwest Africa [NWA] 817, Nakhla, Governador Valadares, and NWA 998): Type‐I isolated inclusions in augite cores that contain euhedral to subhedral augite, Ti‐magnetite, and pigeonite plus silica‐rich glass and a gas bubble; Type‐II microinclusions that form trails crosscutting host augite crystals. Fast‐heating experiments were performed on selected pristine primary augite‐hosted melt inclusions from these four samples. Of these, only data from Nakhla were considered robust for reconstruction of a nakhlite parental magma composition (NPM). Based upon careful petrographic selection and consideration of iron‐magnesium ratios, our data are used to propose an NPM, which is basaltic (49.1 wt% SiO₂), of high Ca/Al (1.95), and K₂O‐poor (0.32 wt%). Thermodynamic modeling at an oxygen fugacity one log unit below the QFM buffer using the MELTS and PETROLOG programs implies that Mg‐rich olivine was not a liquidus phase for this composition. Our analysis is used to suggest that olivine megacrysts found in the nakhlites are unlikely to have coprecipitated with augite, and thus may have been introduced during or subsequent to accumulation in the magma chamber, possibly from more evolved portions of the same chamber.     

Metal‐saturated sulfide assemblages in NWA 2737: Evidence for impact‐related sulfur devolatilization in Martian meteorites

NWA 2737, a Martian meteorite from the Chassignite subclass, contains minute amounts (0.010 ± 0.005 vol%) of metal‐saturated Fe‐Ni sulfides. These latter bear evidence of the strong shock effects documented by abundant Fe nanoparticles and planar defects in Northwest Africa (NWA) 2737 olivine. A Ni‐poor troilite (Fe/S = 1.0 ± 0.01), sometimes Cr‐bearing (up to 1 wt%), coexists with micrometer‐sized taenite/tetrataenite‐type native Ni‐Fe alloys (Ni/Fe = 1) and Fe‐Os‐Ir‐(Ru) alloys a few hundreds of nanometers across. The troilite has exsolved flame‐like pentlandite (Fe/Fe + Ni = 0.5–0.6). Chalcopyrite is almost lacking, and no pyrite has been found. As a hot desert find, NWA 2737 shows astonishingly fresh sulfides. The composition of troilite coexisting with Ni‐Fe alloys is completely at odds with Chassigny and Nahkla sulfides (pyrite + metal‐deficient monoclinic‐type pyrrhotite). It indicates strongly reducing crystallization conditions (close to IW), several log units below the fO₂ conditions inferred from chromites compositions and accepted for Chassignites (FMQ‐1 log unit). It is proposed that reduction in sulfides into base and precious metal alloys is operated via sulfur degassing, which is supported by the highly resorbed and denticulated shape of sulfide blebs and their spongy textures. Shock‐related S degassing may be responsible for considerable damages in magmatic sulfide structures and sulfide assemblages, with concomitant loss of magnetic properties as documented in some other Martian meteorites.     

Sulfide Petrology of Spinel and Garnet Pyroxenite Layers from Mantle-derived Spinel Lherzolite Massifs of Arieg`, Northeastern Pyrenees, France

Pyroxenite layers in the orogenic spinel lherzolite massifsof Ari?ge are porphyroclastic textured and range in compositionfrom spinel websterite to garnet clinopyroxenite. Each pyroxenitetype forms individual layers or occurs as part of compositelayers in which the Opx/Cpx and Sp/Gt ratios decrease from marginsto core. They are interpreted as crystalline segregations separatedby flow crystallization from continental tholeiites en routeto the surface. The primary magmatic phases consist of Al-richpyroxenes, together with a minor amount of spinel, which startedto crystallize at 1400?C and 20–22 kb pressure; the pyroxeneshave locally survived plastic strains and subsolidus rccrystallizationsand now occur in the form of clinopyroxene and orthopyroxenemegacrysts displaying unmixing features. Although the differentiated silicate liquid was fully expelledduring the flow crystallization process, the layered pyroxeniteshave concentrated the highly incompatible elements S and Cuand locally display significant chalcophile platinum-group elementenrichment (Pd, Pt). Cu and S behave coherently over the wholerange of pyroxenite composition; their highest concentrationsare found in the thinnest websterite layers or at the marginof composite layers. Microscopic investigation of 214 polishedthin sections shows these elements to be present as accessoryCu-Fe-Ni sulfides interstitial among the silicate phase or formingdiscrete bodies included in the relic pyroxene megacrysts. Allthese features indicate the presence of a sulfide liquid, immisciblewith the silicate magma, during the crystallization of the layeredpyroxenites. Sulfide liquid immiscibility probably occurredin response to thermal contrast between the pyroxenites andthe cooler surrounding peridotites. It is proposed that the megacryst-hosted sulfide inclusionswere trapped as linear arrays arranged on host megacryst growthplanes. Due to the slow cooling and complex unmixing historyof the megacrysts, these arrays have been transformed into coarse,isolated sulfide inclusions by subsolidus migration and spheroidizationprocesses. They started to crystallize at T = 1200?C as monosulfidesolid solution (MSS), probably coexisting with a minor amountof Ni- and Cu-rich sulfide liquid down to r=900?C. The reconstructionof the bulk chemistry of each individual inclusion reveals significantbetween-inclusion variations of Cu/Ni+ Fe and Ni/Fe ratios,which would result from strain-induced immobilization of theseliquids. On cooling, the high-temperature MSS has decomposedbelow 230?C into Ni-rich pyrrhotite, nickeliferous pentlandite,chalcopyrite and minor pyrite. The post-magmatic history ofthe interstitial sulfide grains was not unlike that of the inclusions,except at near-surface temperatures where the primary sulfidesresulting from unmixing of MSS have been partly altered intosecondary sulfides by serpentinizing aqueous fluids. In spite of these post-magmatic alterations, the inclusionsand the interstitial sulfide phases are remarkably homogeneousas regards their bulk Ni/Cu ratio, which is close to 3. Thisvalue is characteristic of sulfide separated from primary ratherthan partially differentiated tholeiitic melts. It is thus concludedthat the continental tholeiite parent to the layered pyroxeniteswas saturated with sulfides when it left its mantle source regioaIn this aspect, it would not be different from MORBs which containsimilar sulfide compositions. In both cases, sulfide fractionationcannot be ignored in models for chalcophile trace element fractionationduring initial evolution of these magmas.     

Evidence for Modal Metasomatism in the Orogenic Spinel Lherzolite Body from Caussou (Northeastern Pyrenees, France)

Metasomatic mineral-bearing and/or trace element-enriched ultramaficassemblages have been reported from very few Alpine-type massifs.The small ultramafic body from Caussou (Ari?ge, northeasternPyrenees) compared with other north Pyrenean ultramafic complexesshows distinctive features which are similar to those of modallymetasomatized mantle xenoliths found in alkali basalts. It ismainly composed of clinopyroxene-rich spinel lherzolites (cpx/opxratios 1), with subordinate titanian pargasite-rich peridotites,both greatly depleted in orthopyroxene. Moreover the Caussouperidotites differ from other Ari?ge peridotites in the presenceof ilmenite, the abundance of sulfide inclusions in pyroxenesand amphiboles, higher Al, Ca, Na, K, Ti, and lower Mg contents,and enrichment in incompatible trace elements (ITE). Such mineralogicaland geochemical features are interpreted as resulting from modalmetasomatism produced by influxes of silicate melt into theperidotites. At Caussou, the metasomatic assemblage comprisesTi-pargasite+Ti-bearing clinopyr oxene+ilmenite+Ti-phlogopite+sulphide+fluid,suggesting that K, Ti, Na, ITE (including S, H₂O CO₂ and possiblyFe and Ca, were introduced by the metasomatizing agent. Thismetasomatism was probably imposed on an ultramafic associationdominated by LREE-depleted peridotites similar to the northPyrenean spinel lherzolites. These features indicate that, underupper lithospheric mantle conditions, a mafic melt locally infiltratedlherzolites by a grain-boundary percolation process and reactedwith the original mineral assemblage. The infiltration of alkali-basalticliquids into spinel peridotite led to: (1) partial dissolutionof orthopyroxene and, locally, spinel; (2) crystallization ofclinopyroxene directly from introduced melts; and (3) re-crystallization/equilibrationof pre-existing clinopyroxene with these magmatic liquids. Inthe last stage of the metasomatism, segregation of more fractionatedsilicate liquids, coexisting with a (CO₂+H₂O) fluid phase, mayhave been responsible for the crystallization of titanian pargasite,possibly by means of hydro-fracturing mechanism. The pervasive modal metasomatism at Caussou was contemporaneouswith the segregation of amphibole-bearing dykes in the Lherz-Freychin?debodies (northeast Pyrenees) (101–103 Ma). They representtwo manifestations of the same magmatic event in the lithosphericmantle, probably related the Middle Cretaceous alkaline magmatisrnof the Pyrenees.