The chromian spinels of the Lyavaraka ultrabasic complex, Serpentinite Belt, Kola Peninsula, Russia: Patterns of zoning, hypermagnesian compositions, and early oxidation

ABSTRACT The maximum value of Mg# [= 100Mg/(Mg + Fe2+ + Mn)] in chromium-bearing spinel-group minerals (Chr) in the Ultrabasic Core Zone (UCZ) of the Lyavaraka orthopyroxenite – harzburgite – dunite complex of the Serpentinite Belt in the Kola Peninsula is 54.5–67.5. Such highly magnesian compositions of spinel are associated with notable enrichments of ferric iron (Fe3+# 58–63). There are two generations of accessory Chr in the UCZ unit. The first generation occurs as inclusions in olivine that is not unusually magnesian (Mg# 90.3), and the second is closely associated with serpentine. The compositional series of Chr at Lyavaraka attains more aluminous compositions than was observed in nearby intrusive bodies. The anomalously high level of Mg in Chr, also manifest in ilmenite, is mainly a result of the high intrinsic fugacity of oxygen attained locally in the melt. A progressive buildup in H2O and increase in fO2 likely resulted from efficient vesiculation and selective loss of H2 from the Al-undepleted komatiitic magma crystallizing in a shallow setting. The chromian spinel forming in such a modified magma is virtually unzoned in Mn, and a minor quantity of Mn is also present in olivine and orthopyroxene. In contrast, zinc is strongly partitioned in the core of Chr, as it is relatively incompatible in the coexisting olivine and orthopyroxene at that stage. Zinc efficiently partitioned into the H2O-enriched melt, which crystallized as the pegmatitic orthopyroxenite near the contacts at Lyavaraka. A high potential of oxidation appears to be characteristic of all orthopyroxenite – harzburgite – dunite suites of the Serpentinite Belt formed from a primitive melt of komatiitic composition.

U–Pb and Hf isotope study of detrital zircon and Cr-spinel in the Banavara quartzite and implications for the evolution of the Dharwar Craton, south India

The Sargur Group has been considered to be the oldest group (>3.0 Ga) in the Archaean sequence of the Dharwar Craton in south India, whereas the rocks of the Dharwar Supergroup are younger (between 3.0 and 2.55 Ga). The supracrustal units of the Sargur Group were deposited during the Archaean period. The Banavara quartzite forms part of the supracrustal Sargur Group and contains significant amounts of chromian spinel (Cr-spinel). Here, U–Pb and Hf isotopes of detrital zircons are integrated with compositional data and X-ray refinement parameters for Cr-spinels to decipher the provenance of the metasediments. Zircons show an age spectrum from 3.15 to 2.50 Ga, and juvenile Hf isotopic compositions (ϵHf = +0.8 to +6.4) with model ages between 3.3 and 3.0 Ga. Major- and trace-element contents of the Cr-spinels do not resemble those in the Sargur ultramafic rocks, but resemble well-characterized Archaean anorthosite-hosted chromites. Cr-spinel trace-element signatures indicate that they have undergone secondary alteration or metamorphism. X-ray refinement parameters for the Cr-spinels also resemble the anorthosite-hosted chromites. We conclude that the detrital minerals were probably derived from gneissic and anorthositic rocks of the Western Dharwar Craton, and that the Sargur Group sequences have experienced a younger (2.5 Ga) metamorphic overprint.

Ultramagnesian Olivine in the Monchepluton (Fo96) and Pados-Tundra (Fo93) Layered Intrusions (Kola Peninsula)

—The paper focuses on compositional variations of olivine and chromian spinel in the Monchepluton and Pados-Tundra layered intrusions, which host significant chromitite mineralization. Ore-bearing dunite (with up to 25–30 vol.% Mcr) in the Sopcheozerskoe chromite deposit from the Monchepluton complex, Kola Peninsula, Russia, bears an assemblage of phases with exceptionally high magnesium contents: Fo96 + augite (Mg# = 94) + magnesiochromite, Mcr (Mg# ≈ 65); Mg# = 100·Mg/(Mg + Fe2+ + Mn). However, olivine in the host dunite has normal maximum values of Mg# comparable to those in cumulus olivine from layered intrusions worldwide (Fo≤91–92). The Fo96 phase in the Sopcheozerskoe deposit shows the most primitive composition ever reported from any layered intrusion. Magnesiochromite occurs as unzoned homogeneous euhedral crystals unaffected by subsolidus exchange or metasomatic effects. Olivine in ore-bearing dunite (20–25 vol.% magnesian chromite) from the Pados-Tundra complex attains Fo93, with the Mg# value notably higher than the range (Fo85.5–90.6) in olivine from orthopyroxenite, harzburgite, and dunite within the intrusion. Olivine and chromian spinel in the two complexes behave coherently, with covarying patterns of Mg# and Ni contents in olivine at R = 0.75 (n = 160) and positive correlation between Mg# in coexisting chromian spinel and olivine grains at R = 0.8 (n = 150). This behavior indicates that the two phases attained equilibrium during crystallization. It appears unlikely that the extremely high Mg enrichment in olivine (Fo96), as well as in all associated phases of the Monchepluton complex, would result from a subsolidus reaction between olivine and chromian spinel or low-temperature alteration of olivine. We suggest a more realistic explanation that the olivine (+ high-Mg augite)–chromian spinel assemblage crystallized from komatiitic magma under the conditions of progressively increasing oxygen fugacity (fO2). The high Mg# in the Mcr-chromite-enriched system, above the maximum values common in cumulus olivine from layered intrusions (up to Fo96 against Fo≤91–92), may be caused by shortage of ferrous iron.

Zones of PGE–Chromite Mineralization in Relation to Crystallization of the Pados-Tundra Ultramafic Complex, Serpentinite Belt, Kola Peninsula, Russia

The lopolithic Pados-Tundra layered complex, the largest member of the Serpentinite belt–Tulppio belt (SB–TB) megastructure in the Fennoscandian Shield, is characterized by (1) highly magnesian compositions of comagmatic dunite–harzburgite–orthopyroxenite, with primitive levels of high-field-strength elements; (2) maximum values of Mg# in olivine (Ol, 93.3) and chromian spinel (Chr, 57.0) in the Dunite block (DB), which exceed those in Ol (91.7) and Chr (42.5) in the sills at Chapesvara, and (3) the presence of major contact-style chromite–IPGE-enriched zones hosted by the DB. A single batch of primitive, Al-undepleted komatiitic magma crystallized normally as dunite close to the outer contact, then toward the center. A similar magma gave rise to Chapesvara and other suites of the SB–TB megastructure. Crystallization proceeded from the early Ol + Chr cumulates to the later Ol–Opx and Opx cumulates with accessory Chr in the Orthopyroxenite zone. The accumulation of Chr resulted from efficient cooling along boundaries of the Dunite block. The inferred front of crystallization advanced along a path traced by vectors of Ol and Chr compositions. Grains and aggregates of Chr were mainly deposited early after the massive crystallization of olivine. Chromium, Al, Zn and H2O, all incompatible in Ol, accumulated to produce podiform segregations or veins of chromitites. This occurred episodically along the moving front of crystallization. Crystallization occurred rapidly owing to heat loss at the contact and to a shallow level of emplacement. The Chr layers are not continuous but rather heterogeneously distributed pods or veins of Chr–Ol–clinochlore segregations. Isolated portions of melt enriched in H2O and ore constituents accumulated during crystallization of Ol. Levels of fO2 in the melt and, consequently, the content of ferric iron in Chr, increased progressively, as in other intrusions of the SB–TB megastructure. The komatiitic magma vesiculated intensely, which led to a progressive loss of H2 and buildup in fO2. In turn, this led to the appearance of anomalous Chr–Ilm parageneses. Diffuse rims of Chr grains, abundant in the DB, contain elevated levels of Fe3+ and enrichments in Ni and Mn. In contrast, Zn is preferentially partitioned into the core, leading to a decoupling of Zn from Mn, also known at Chapesvara. The sulfide species display a pronounced Ni-(Co) enrichment in assemblages of cobaltiferous pentlandite, millerite (and heazlewoodite at Khanlauta), deposited at ≤630 °C. The oxidizing conditions have promoted the formation of sulfoselenide phases of Ru in the chromitites. The attainment of high degrees of oxidation during crystallization of a primitive parental komatiitic magma accounts for the key characteristics of Pados-Tundra and related suites of the SB–TB megastructure.

The Haidbach deposit in the Central Tauern Window, Eastern Alps, Austria: a metamorphosed orthomagmatic Ni-Cu-Co-PGE mineralization in the Polymetallic Ore District Venediger Nappe System – Hollersbach Complex

Cu-Ni-Co-PGE mineralization occurs at Haidbachgraben in the Early Palaeozoic, Subpenninic Hollersbach Complex of the Central Tauern Window, Austria. Massive sulfide ore formed from sulfide melt segregated from silicate melt during intrusion of pyroxenite into magmatic rocks formed in an MORB-type environment. Relics of magmatic minerals include chromian spinel and polyphase sulfide droplets composed of pyrrhotite, chalcopyrite and pentlandite preserved in recrystallized pyrite. Both ore and host rocks were multiply deformed and metamorphosed, leading to hornblendite carrying the ore, enveloped by chlorite-epidote schist. Conditions of – likely Variscan – amphibolite facies metamorphism are documented by relict pargasitic cores in hornblende and actinolite-tremolite, and by ternary sulfarsenide compositions in the Co-Ni-Fe solid solution series that are the most common accessory minerals found in the sulfide ore. Pyrrhotite, pentlandite, chalcopyrite and pyrite are the major sulfide minerals. Chalcopyrite is Cd-rich and retains a high-temperature magmatic signature. High Co/Sb and moderate Se/As ratios in pyrite also point to a magmatic environment of mineralization. The accessory mineral assemblage of small grain size (mostly <10 µm) comprises native Au-Ag alloy and petzite as Au-Ag minerals, sperrylite, a variety of Pd tellurides and bismuthotellurides with elevated Sb, irarsite, and Re sulfides such as tarkianite and a Pb-Re sulfide. In addition, minor molybdenite, bournonite, scheelite and selenides have been identified. Two precious metal assemblages are present in individual samples: (1) hessite associated with Pd tellurides, often accompanied by sphalerite and chalcopyrite; (2) tarkianite forming euhedral inclusions in pyrite. Sperrylite and Au-Ag native alloys are present throughout and were also detected in silicate matrix. Most of the precious metal-bearing phases must have formed during recrystallization of base metal sulfides after the magmatic, and probably during later metamorphic events terminating in the Neoalpine Tauern crystallization.

Petrology and geochemistry of high-Al chromitites from the MedellÍn Metaharzburgitic Unit (MMU), Colombia

The Medellin Metaharzburgitic Unit (MMU), emplaced onto the western continental margin of Pangea during Triassic time, is located in the Central Cordillera of Colombia and consists of metaharzburgites, minor metadunites and chromitite bodies (Patio Bonito and San Pedro ore deposits). The ultramafic rocks contain relicts of mantle-derived olivine, chromian spinel and minor orthopyroxene, and a later metamorphic mineral assemblage composed by tremolite, chlorite, talc, fine-grained recrystallized olivine, serpentine-group minerals, magnetite, and secondary chromian spinel, formed during the thermal evolution of the unit. The Cr# [Cr/(Cr+Al) atomic ratio] of the accessory primary chromian spinel in the metaperidotites ranges from 0.58 to 0.62 and overlaps those of supra-subduction peridotites from ophiolites. According to textural and compositional variations, the accessory chromian spinel in the metaperidotites can be classified into three groups: i) partially altered chromian spinel with an Al-rich core, ii) porous, Cr-Fe2+-enriched and Al-Mg-depleted chromian spinel, and iii) homogeneous Fe3+-rich chromian spinel. These variations can be related to superimposed medium-T metamorphism that reached amphibolite facies (ca. 600 ºC). Chromitite bodies associated with the metaperidotites have massive and semi-massive textures, and mainly consist of chromian spinel crystals, which show large unaltered cores surrounded by thin alteration rims of ferrian chromian spinel and chlorite. Chromitites are Al-rich (#Cr <0.6) and strongly depleted in platinum group elements (ΣPGE <41 ppb). The primary petrological and geochemical characteristics preserved in the metaperidotites and chromitites indicate that the MMU formed at shallow levels of a suboceanic lithospheric mantle related to a supra-subduction zone (back-arc basin/incipient arc scenario), and that the chromitites crystallized from a tholeiitic magma (back-arc basin basalt type).

Magmatic haggertyite in olivine lamproites of the West Kimberley region, Western Australia

We report the first occurrence of magmatic haggertyite (BaFe6Ti5MgO19) from the Miocene lamproites of the West Kimberley region of Western Australia. This contrasts with the metasomatic formation reported in an olivine lamproite host at the type locality, Prairie Creek, Arkansas. Haggertyite occurs in the groundmass of a diamondiferous olivine lamproite pipe in the Ellendale field, and within the large zoned Walgidee Hills lamproite where it forms part of an extensive suite of Ba- and K-bearing titanate and Ti-rich silicate minerals. The haggertyite co-exists with chromian spinel, perovskite, and ilmenite in the Ellendale lamproite, and with priderite and perovskite and, in one locality, with priderite, jeppeite, ilmenite, and perovskite, in the Walgidee Hills lamproite. Unlike priderite and perovskite, which are common groundmass phases in the Ellendale olivine lamproites and present throughout the Walgidee Hills lamproite, haggertyite appears restricted in its occurrence and crystallization interval, with sparse ilmenite apparently mostly crystallizing as an alternative phase. In the Walgidee Hills lamproite the haggertyite-bearing assemblage is succeeded by the Ba-titanate assemblage priderite plus jeppeite in the evolved central part of the body. The haggertyite in the main zone of the Walgidee Hills lamproite has an average composition of (Ba0.7K0.3)1.0(Ti5.0Fe2.13+Cr0.1Fe3.82+Mn0.2Mg0.6Na0.1)12O19 and is thus very similar to the original haggertyite described from xenoliths in the Prairie Creek lamproite apart from being poorer in Cr and Ni. Haggertyite in the groundmass of the Ellendale olivine lamproite and the central zone of the Walgidee Hills lamproite, in addition to variations in Mg and Cr, show significant variation in Ti and Fe contents and in calculated Fe3+ and Fe2+. A linear inverse relationship between Ti and Fe, and Ti and Fe3+, indicates that Fe3+ is accommodated by the coupled substitution Ti4+ + Fe2+ ⇆ 2 Fe3+. A marked trend to higher Fe3+ in the haggertyite in Ellendale 9 olivine lamproite is ascribed to increasing oxidation during crystallization, with fO2 estimated from the olivine-spinel thermometer and oxygen barometer at Dlog FMQ = –1 to +3 at temperatures of 790–660 °C. The haggertyite in the central zone of the Walgidee Hills lamproite, in contrast, shows a marked trend to Fe2+ enrichment, which is associated with decreasing Fe in perovskite. This is inferred to indicate formation under more reducing conditions, but sufficiently oxidized to permit Fe3+ in co-existing priderite and jeppeite. Trace-element analysis by LA-ICP-MS shows the Walgidee Hills haggertyite contains minor amounts of Na, Si, Ca, V, Co, Zn, Sr, Zr, Nb, and Pb, and only traces of Al, P, Sc, Rb, REE, Hf, and Ta. Moreover, the haggertyite is preferentially enriched in certain lithophile (Ba, Sr), siderophile (Mn, Fe, Co, Ni), and chalcophile (Zn, Pb) elements relative to co-existing priderite. Haggertyite crystallization appears to be a consequence not only of the very high Ba, Ti, and K contents of the lamproite, but of relatively high-Fe concentrations and low temperatures in evolved olivine lamproite magma with the Fe3+/Fe2+ ratio determined by the prevailing fO2. The new data suggest that haggertyite might also be present but previously unrecognized in the evolved groundmass of other olivine lamproites. Haggertyite is one of an increasing number of new minerals in upper mantle rocks and volcanics derived from the upper mantle hosting large-ion-lithophile and high field strength cations.