ISSN 0016 7029, Geochemistry International, 2010, Vol. 48, No. 8, pp. 808–814. © Pleiades Publishing, Ltd., 2010.

Original Russian Text © A.A. Yaroshevsky, A.V. Ivanov, 2010, published in Geokhimiya, 2010, Vol. 48, No. 8, pp. 860–866.

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Geochemical Diversity of Meteorite Minerals: Systematics and Nomenclature of Phosphides and Silicides
A. A. Yaroshevskya, b and A. V. Ivanovb
Geological Faculty, Moscow State University, Moscow, 119899 Russia e mail: aaya@geol.msu.ru b Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul. Kosygina 19, Moscow, 119991 Russia e mail: andrei_ivanov@geokhi.ru
Received June 9, 2009
a

DOI: 10.1134/S0016702910080070

Phosphides, phosphosilicides, and silicides are rare and extremely rare minerals of meteorites, being found also in small amounts in their peculiar types. Among them are minerals established at the beginning of meteoritics development (schreibersite and its morphological variety, rhabdite), but most of these minerals were found in the last decades of 20th century and at the beginning of the cur rent century owing to the use of new highly local methods of analysis. The formation of these minerals requires strongly reducing conditions, which, as was demonstrated by mineralogical data, correspond to the formation con ditions of enstatite meteorites and most iron meteorites. Individual phosphides (barringerite, schreibersite) and silicides (suessite and diverse Fe silicides) were found in terrestrial setting; however, these finds require special interpretation, for instance, their influx to the Earth sur face with cosmic dust or formation under specific settings in the burning (coal) heaps ([1], for instance). Systematization of the minerals of these groups in meteorites was based on the description of their finds, especially those accompanied by chemical analyses. An extensive bibliography available on this problem is not reported here completely, while chemical analyses are shown graphically. In particular cases, however, if definite information is required, references are reported. In total, our collection (available for interested reader in the form of a data base) includes 334 analyses of minerals of these groups, including one analysis of melliniite, 236 analyses of schreibersite group minerals; two analyses of Ni phos phides, 40 analyses of barringerite group minerals, three analyses of suessite, 51 analyses of perryite, and two anal yses of hapkeite group minerals. It should be noted that after recalculation of analyses on the basis of 1 P + Si, 47 of 236 schreibersite analyses fell outside the range of metal content 3.00 ± 0.15 f.u. This is the case both for old anal yses and modern microprobe determinations. Structural studies are presumably required to decide whether these deviations are analytical errors or related to the existence of Fe–P solid solutions; these analyses were excluded in Fig. 1a.

The analysis of links between minerals and their com bination into groups and subgroups were based on not only stoichiometry, chemical composition, and structural characteristics, but also on such geochemical criteria as types of isomorphic links, which provide insight into geochemical environment of the formation of mineral assemblages [2]. Based on these criteria, phosphides are subdivided into five mineral groups: melliniite (Me4P), schreibersite (Me3P), Ni phosphide (Ni5P2), and three mineral groups with stoichiometry Me2P (barringerite, florenskyite, and monipite). Statistics of their chemical compositions are listed in Figs. 1a, 1b, 1c. The most abundant minerals of these groups are schreibersite and its Ni rich variety (nickelphosphide). It is not reasonable to distinguish schreibersite proper and Ni bearing schreibersite as a chemical variety, because analyses with Ni content less than 6.5 wt % (less than approximately 0.3 f.u) are unavailable; in other words, the Ni free schreibersite does not exist in meteorites and all varieties of this mineral with Fe > Ni should be ascribed to schreibersite. Schreibersite is the typomorphic accessory mineral of iron and iron stony meteorites, enstatite chondrites, and aubrites, and extremely rarely occurs in the matrix of CM chondrites. Its Ni rich variety (nickelphosphide) was found in iron meteorites (in association with Ni rich kamacite), as well as in two enstatite meteorites: chondrite inclusions in Cumberland Falls [3] and Norton County aubrite [4] (Fig. 2). Nickelphosphide (“rhabdite”) is noted among refractory inclusions in CV3 chondrite Efre movka [5]. The highest Ni content of 58.5 wt % (Fe/Ni = 0.41) was found in the CM2 chondrite Dhofar 225 [5]. Being disequilibrium in assemblage of ordinary chon drites, schreibersite sometimes occurs as inclusions in chondrite metal, which indicates, in particular, not always equilibrium relations between silicate and metallic phases of chondrites. It was emphasized in the old works (for instance, [7]) that morphological variety of schreibersite, rhabdite,

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was found in CM2 chondrites Boriskino and ALH83100 [6]. analyses showed that this reg ularity is not fulfilled. However. Florenskyite first described in the carbonaceous– chondrite polymict breccia Kaidun [14] was recognized as individual group on the basis of the absence of isomorphic relations with barringerite group minerals. Cr rich varieties of barrin gerite were established in CH chondrite ALH85085 [10] and in the carbonaceous–chondrite polymict breccia Kaidun [11]. including.3 % Ni)—Fe barringerite—was found in the lunar meteorite Yamato 793274 [9]. 3). there are grounds to believe that these phosphide grains are ascribed to the enstatite–chondrite paragenesis. especially. while its Ni depleted variety (1. Fig. GEOCHEMISTRY INTERNATIONAL Vol.2 wt %. Metal and phosphorus (+silica) proportions in the min erals of different groups of (a) phosphides and (b) barringerite group. which can be criterion for identification of these minerals by chemical composition. but also in trace element chemistry: lowered Ni and relatively high Co contents. Symbols: circles—mellini ite. Phosphides with stoichiometry Me2P (Figs. the rhombic phase FeCrP described as andreyivanovite was later identified in the Kaidun mete orite [12]. In contrast. we dis tinguish three groups: barringerite. Therefore. Hexagonal barringerite was described for the first time in the Ollague pallasite [8]. the appearance of phos phides. Among them. Discovery of phosphides in the palassites and lunar meteorites is quite explainable by their usual formation in reducing conditions. microprobe. magnetite. as well as metal proportions in the minerals of (c) bar ringerite and florenskyite groups. but numer ous. the matrix of ALH 85086 meteorite bearing these phosphides contains mineral grains of admittedly distinct paragenesis—reducing paragenesis of enstatite chondirtes [10]. and diamonds—florenskyite. it is made up of fairly oxidized material (Fe hydrosilicates. and monipite. is usually enriched in Ni with respect to schreibersite. Their position in our systematics is arbitrary. and a variety maxi mally enriched in this element. 1c) are extremely rare phases in meteorites and mainly occur as single grains in unique meteorites. which are regarded to be genetically related to the phos phides of lithophile elements [14]. but their affiliation to hexagonal varieties is not proved. triangles—miner als of barringerite group. boxes—andreyivanovite and Cr bar ringerite.3 and 46. in carbonaceous chondrites requires comment. 1. This mineral was included in the barringerite group as end member (individual mineral species) of pos sible isomorphic series of barringerite–Cr barringerite– andreyivanovite (Fig.GEOCHEMICAL DIVERSITY OF METEORITE MINERALS: SYSTEMATICS 809 which was described in iron meteorites. florenskyite. while the Kaidun meteorite contains numerous fragments of enstatite chondrites [15]. Allabogdanite identified for the first time in the Onello ataxite [13] differs from barringerite proper not only in structure. 1b. of such lithophile elements as Cr and Ti. In spite of the fact that matrix of carbonaceous chondrites contains free carbon as reducing agent. Ni barringerite (49. spots—minerals of schreibersite group. 48 No. particularly. respectively). and others). 8 2010 (a) P + Si 0 Fe 20 40 at % 60 80 100 Co + Ni (b) P + Si 0 20 40 60 Fe + Co + Ni at % (cw) P + Si 80 100 Ti + V + Cr 0 20 40 60 Fe + Co + Ni at % 80 100 Ti + V .

IVANOV 30 25 20 N 15 10 5 0 0 30 25 20 N 15 10 5 0 0 0. Relative Ni content in the minerals of schreibersite group from different types of meteorites. at % 0.1 0.2 0.4 0.4 0. 48 No.1 0.6 N Iron meteorites 0. Symbols: triangles—min erals of barringerite group and boxes–andreyivanovite and Cr barringerite. GEOCHEMISTRY INTERNATIONAL Vol.2 0. 8 2010 .3 0.2 0. 2. Cr 0 Fe 20 40 at % 60 80 100 Ni Fig.5 Ni/(Fe + Ni).4 0. at % 0.3 0.6 N E chondrites 30 25 20 15 10 5 0 0 30 25 20 15 10 5 0 0 0. at % 0.1 0.6 Chondrite inclusion in the Cumberland Falls aubrite Fig. at % 0. 3.2 0. N is the number of analyses.6 Norton Co.810 YAROSHEVSKY.1 0. aubrites 0.3 0. Compositional variations of Fe–Ni and Fe–Cr isomorphic series in the minerals of barringerite group.4 0.5 Ni/(Fe + Ni).5 Ni/(Fe + Ni).3 0.5 Ni/(Fe + Ni).

However. 8 Si + P 0 Fe 20 40 at % 60 80 100 Ni (+ Co + Cr) Fig. as was indicated by Kail and co authors [19]. Ni phos phide. schreibersite.Ni phosphosilicide belong to the hap keite group. and. 18] only supports the reducing nature of this meteor ite group. which is geochemically close to vinonait. is practically pure Fe3Si. florenskyite. hapkeite. This find did not change the accepted viewpoint concerning reducing conditions of the formation of lunar rock. barringerite. This mineral was distinguished in the individual group due to its unusual composition and the absence of isomorphic links with other hexagonal phos phides. and triangle—suessite. ten structural chemical varieties: schreibersite and nickelphosphide belong to the schreibersite group. It should be noted that florenskyite and andreyivano vite are first discovered in nature phosphides of lithophile elements. perryite. it should be noted that in 1989 Kimura and El Goresy [10] found in CH chondrite ALHA 85085 mineral phase. open triangle— melliniite. phosphosilicides. New Fe silicide.4 0. circles—suessite. sues site. 2010 .0 Fig. suessite.6 0. barringerite. perryite.Ni) and (Si. and silicides of meteorites. 5. Proportions of relative Ni and P contents in phos phides.2 0. and silicides in meteorites. 4. Thus. at % 0. monipite. unlike the latter. open boxes—minerals of barringerite group.8 P/(P + Si). corresponds to hapkeite (or barringerite?). schreibersite. Metal and silica (+phosphorus) proportions in the min erals of different groups of silicides and phosphidesilicides. and boxes— hapkeite and Fe.Ni silicide. monipite. monipite. andreyivanovite. but should be considered as individual phase. 48 No. because associated suessite and phosphides are dominated by Fe (Figs. which in terms of proportions of (Fe. Symbols: spots—perryite.2 0 0. andreyivanovite. while hapkeite. 1. represents the end member in the solid solution on the basis of α iron (kamacite). but.7%) admixture of P in addition to the pre dominant Si. 5). The only phosphosilicide. barringerite. 4.8 1. Cr barringerite. analysis of chemical variations of phosphides. Suessite.6 Ni/(Fe + Ni). contains significant (7.4 0. It should be noted that this is the only ferrosilicide representing practically Ni mineral.0 0. boxes—hapkeite and Fe. The discovery of melliniite in NWA 1054 acapulcoite [17. in high temperature condensates (Ca and Al rich inclusions) in the CV3 chondrite Allende seemed to be unexpected [16]. andreyivanovite.3 × 2 μm in size) of Mo and Ni phosphide with barringerite stoichiometry. and distribution over meteorite types allowed us to distinguish 10 mineral species: mel liniite. Ni barringerite. perryite. which include.GEOCHEMICAL DIVERSITY OF METEORITE MINERALS: SYSTEMATICS 811 The discovery of single grain (1. was recently found in the Dhofar 280 lunar meteorite [20]. The appearance of such phosphide of chalcophile element was presumably caused by oxidation and sul fidization of high temperature metal condensate enriched in weakly volatile chalcophile and siderophile elements [16]. circles—perryite. at % 0. Ni phosphide. while monopite represents the first indentified phosphide of chalcophile metal. the rare meteorite mineral. Fe barringerite. in turn. GEOCHEMISTRY INTERNATIONAL Vol. It was initially found in the North Haig polymict ureilite. was established in the aubrites and enstatite chondrites.Ni silicides.P). and all abogdanite are ascribed to the barringerite group. Symbols: spots—minerals of schreibersite group. phosphosilicides. and hapkeite. and hapkeite. florenskyite. and Fe. regularities of their isomorphism. All these minerals are united into nine mineral groups: melliniite.

Found in anomalous Burhal iron meteorites. Andeyivanovite subgroup Andreyivanovite FeCrP rhomb. Onello.Fe)2P First described as rare mineral in the Ollague palassite by Buseck [8]. Cr rich variety of barringerite was first established as extremely scarce in CH chon drite ALH 85085 by Kimura and El Goresy in 1989 [10].Fe)3P tetr. Found also in matrix of CM chondrites.Ni)2P rhomb. Canyon Diablo. (Ni. in 2009 [16]. 48 No. syngony Phosphides Melliniite group Melliniite Schreibersite group Schreibersite (Fe. (Fe. Pratesi et al. . Ivanov et al. and silicides of meteorites Mineral species or variety Chemical compo sition. in 1991 [9]. First described as very rare mineral in the Onello ataxite by Britvin et al. as “Fe. identified as new extremely rare mineral in the carbonaceous–chondrite polymict breccia Kaidun by Zolensky et al. GEOCHEMISTRY INTERNATIONAL Vol. 18].Fe)4P cub. in 2008 [12]. in 1994 [11. Ac cessory mineral in iron and iron–stony meteorites. First described in the Magura IAB iron meteorite by Haidinger in 1847 [21]. in 2002 . (Ni.V. . Described as extremely rare mineral in the NWA 1054 acapulcoite by G.Ni)3P tetr.3% Ni) First described as very rare variety of barringerite in Y 793274 lunar meteorite by . Fe2P (<1. 14] . Morphological variety of schreibersite first described in iron meteorites by Rose in 1865 [22].Ni)2P hex. Brandstätter et al. in 2006 [17. Phosphides.Cr. . Was established for the first time as “Cr barringerite” in CH chondrite ALH 85085 by Kimura and El Goresy in 1989 [10]. Ni rich schreibersite variety (Ni > Fe) was found for the first time in the Canyon Diablo and Lenarto iron meteorites by Reed (1965) [23] and identified as new min eral in Bulter.Cr phosphide. aubrites. . and CM2 matrix of Dhofar 225 chondrite. ureilites.” this mineral was de scribed in the inclusion in carbonaceous–chondrite polymict breccia Kaidun [11]. Described as new very scarce mineral in Ca and Al rich inclusion in CV3 chon drite Allende by Ma et al. Described as new extremely rare mineral in the inclusion in polymict carbon aceous–chondrite breccia Kaidun by A. . 8 2010 FeTiP rhomb. [13]. Ni rich rare variety of barringerite (Ni > Fe) was found in matrix of CM2 chon drites Boriskino and ALH 83100 by Nazarov et al. occasionally occur in other types of meteorites. Bragin and Omolon palassites. earlier. and other iron meteorites. in 2009 [6].Ni)2P (up to 17% Cr) Florenskyite group Florenskyite Monipite group Monipite MoNiP hex. in 1999 [24]. [31].812 YAROSHEVSKY. Ni5P2 Found as very scarce mineral phase in the shell of Zelda Fremdlinge in CAI CV3 chondrite Allende by Armstrong et al. also found as extremely scarce mineral in the inclusion in polymict carbonaceous–chondrite breccia Kai dun and in the thermally metamorphosed CM chondrite Dhofar 225. enstatite chondrites. . composi tionally similar “barringerite” was found in the Santa Catharina ataxite [27]. Occurrence in meteorites Rhabdite Nickelphosphide Group of Ni phosphide Ni phosphide Barringerite group Barringerite subgroup Barringerite Ni barringerite Fe barringerite Allabogdanite (Fe. Cr barringerite (Fe. Occur in iron and iron stony meteorites (Ni. phosphosilicides. . this mineral in Onello was described as “barringerite” [26]. in chondrite inclusion from Cum berland Falls aubrite. and in CV3 chondrite Efremovka by Britvin et al. vinonaits. IVANOV Table 1.

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