⁴⁰Ar/³⁹Ar dating of a hydrothermal pegmatitic buddingtonite–muscovite assemblage from Volyn, Ukraine

We determined 40Ar/39Ar ages of buddingtonite, occurring together with muscovite, with the laser-ablation method. This is the first attempt to date the NH4-feldspar buddingtonite, which is typical for sedimentary–diagenetic environments of sediments, rich in organic matter, or in hydrothermal environments, associated with volcanic geyser systems. The sample is a hydrothermal breccia, coming from the Paleoproterozoic pegmatite field of the Korosten Plutonic Complex, Volyn, Ukraine. A detailed characterization by optical methods, electron microprobe analyses, backscattered electron imaging, and IR analyses showed that the buddingtonite consists of euhedral-appearing platy crystals of tens of micrometers wide, 100 or more micrometers in length, which consist of fine-grained fibers of ≤ 1 µm thickness. The crystals are sector and growth zoned in terms of K–NH4–H3O content. The content of K allows for an age determination with the 40Ar/39Ar method, as well as in the accompanying muscovite, intimately intergrown with the buddingtonite. The determinations on muscovite yielded an age of 1491 ± 9 Ma, interpreted as the hydrothermal event forming the breccia. However, buddingtonite apparent ages yielded a range of 563 ± 14 Ma down to 383 ± 12 Ma, which are interpreted as reset ages due to Ar loss of the fibrous buddingtonite crystals during later heating. We conclude that buddingtonite is suited for 40Ar/39Ar age determinations as a supplementary method, together with other methods and minerals; however, it requires a detailed mineralogical characterization, and the ages will likely represent minimum ages.

Vibrational spectroscopic study of three Mg–Ni mineral series in white and greenish clay infillings of the New Caledonian Ni-silicate ores

This study presents and discusses infrared spectroscopic data of well characterised, naturally occurring trioctahedral layer silicates of the serpentine (Srp), talc (Tlc), and sepiolite (Sep) mineral groups, which are found in reactivated faults and sequences of white and green clay veins (deweylite and garnierite) of the New Caledonian Ni-silicate ores. Bands assigned to the OH stretching vibrations of these 1:1 and 2:1 layer silicates in both the fundamental and first overtone regions of mid- and near-infrared (MIR and NIR) spectra, respectively, are compared to those reported in the literature for synthetic Mg–Ni series of the Srp and Tlc mineral groups. They are also presented according to the sequences of infillings recognised in the white and green veins of the Ni-silicate ores. The study reveals that serpentine-like (SL) minerals of the first sequences of clay infillings are residues of larger crystals of serpentines (lizardite, chrysotile, and antigorite) and that the newly formed talc-like (TL) minerals and Sep are the main Ni-bearing carriers of the Ni-silicate ores. Decreasing crystal size and order in serpentine species have major effects on vibrational bands. They favour the broadening of the OH stretching bands, the degradation of the signals assigned to the interlayer OH, and the enhancement of the signal related to weakly bound water molecules. The replacement of Mg by Ni in octahedral sites of the 2:1 layer silicates (TL, Sep) of the greenish clay infillings can be traced by specific OH stretching bands related to the Mg3OH, Mg2NiOH, MgNi2OH, and Ni3OH configurations in the fundamental (MIR) and first overtone (NIR) regions of the spectra. The dominance of the Mg3OH and Ni3OH configurations with respect to mixed configurations in the Mg–Ni mineral series of the clay infillings (mostly in the dominant TL minerals) suggests that Mg and Ni segregation is related to separate Mg-rich and Ni-rich mineral phases rather than to a cationic clustering within the individual particles. This segregation of Mg and Ni in discrete mineral phases is related to Mg–Ni oscillatory zoning patterns (banded patterns) and is reproduced at the scale of the Ni-silicate ores between the white (deweylite) and greenish (garnierite) veins of the reactivated faults.

Ellinaite, CaCr₂O₄, a new natural post-spinel oxide from Hatrurim Basin, Israel, and Juína kimberlite field, Brazil

Ellinaite, a natural analog of the post-spinel phase β-CaCr2O4, was discovered at the Hatrurim Basin, Hatrurim pyrometamorphic formation (the Mottled Zone), Israel, and in an inclusion within the super-deep diamond collected at the placer of the Sorriso River, Juína kimberlite field, Brazil. Ellinaite at the Hatrurim Basin is confined to a reduced rankinite–gehlenite paralava, where it occurs as subhedral grains up to 30 µm in association with gehlenite, rankinite and pyrrhotite or forms the rims overgrowing zoned chromite–magnesiochromite. The empirical formula of the Hatrurim sample is (Ca0.960Fe0.0162+Na0.012Mg0.003)0.992(Cr1.731V0.1833+Ti0.0683+Al0.023Ti0.0034+)2.008O4. The mineral crystallizes in the orthorhombic system, space group Pnma, unit-cell parameters refined from X-ray single-crystal data: a 8.868(9), b 2.885(3), c 10.355(11) Å, V 264.9(5) Å3 and Z=4. The crystal structure of ellinaite from the Hatrurim Basin has been solved and refined to R1=0.0588 based on 388 independent observed reflections. Ellinaite in the Juína diamond occurs within the micron-sized polyphase inclusion in association with ferropericlase, magnesioferrite, orthorhombic MgCr2O4, unidentified iron carbide and graphite. Its empirical formula is Ca1.07(Cr1.71Fe0.063+V0.06Ti0.03Al0.03Mg0.02Mn0.02)Σ1.93O4. The unit-cell parameters obtained from HRTEM data are as follows: space group Pnma, a 9.017, b 2.874 Å, c 10.170 Å, V 263.55 Å3, Z=4. Ellinaite belongs to a group of natural tunnel-structured oxides of the general formula AB2O4, the so-called post-spinel minerals: marokite CaMn2O4, xieite FeCr2O4, harmunite CaFe2O4, wernerkrauseite CaFe23+Mn4+O6, chenmingite FeCr2O4, maohokite MgFe2O4 and tschaunerite Fe(FeTi)O4. The mineral from both occurrences seems to be crystallized under highly reduced conditions at high temperatures (>1000 ∘C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond).

New data on gersdorffite and associated minerals from the Peloritani Mountains (Sicily, Italy)

Gersdorffite, ideally NiAsS, and associated minerals from Contrada Zillì (Peloritani Mountains, Sicily, Italy) have been characterized through electron microprobe analysis and X-ray diffraction. Primary minerals, hosted in quartz veins, are represented by gersdorffite, tetrahedrite-(Fe), and chalcopyrite with minor pyrite and galena. Rare aikinite inclusions were observed in tetrahedrite-(Fe) and chalcopyrite. Gersdorffite occurs as euhedral to subhedral crystals, up to 1 mm in size, with (Sb,Bi)-enriched cores and (Fe,As)-enriched rims. Its chemical composition is (Ni0.79−0.95Fe0.18−0.04Co0.04−0.01)(As0.90−1.03Sb0.10−0.00Bi0.02−0.00)S0.98−0.92. It crystallizes in the space group P213, with unit-cell parameters a=5.6968(7) Å, V=184.88(7) Å3, and Z=4, and its crystal structure was refined down to R1= 0.035. Associated tetrahedrite-(Fe) has chemical formula (Cu5.79Ag0.07)Σ5.86(Cu3.96Fe1.59Zn0.45)Σ6.00(Sb3.95As0.17Bi0.03)Σ4.15S13.06, with unit-cell parameters a= 10.3815(10) Å, V=1118.9(3) Å3, and space group I-43m. Its crystal structure was refined to R1=0.027. Textural and crystallographic data suggest a polyphasic crystallization of gersdorffite under low-temperature conditions.

Geochronology of granites of the western Korosten AMCG complex (Ukrainian Shield): implications for the emplacement history and origin of miarolitic pegmatites

The origin of large miarolitic (also known as “chamber”) pegmatites is not fully understood although they may have great economic value. The formation of cavities in magmatic bodies is related to melt degassing and gas or fluid flow through partially solidified magma. In this paper, the origin of the Volyn pegmatite field, located in the Palaeoproterozoic Korosten anorthosite–mangerite–charnockite–granite (AMCG) complex, North-Western region of the Ukrainian Shield, is discussed. Pegmatites of the field host deposits of piezoelectric quartz that is accompanied by gem-quality beryl and topaz. The Volyn pegmatite field is confined to granites located in the south-western part of the Korosten complex and extends for 22 km along the contact with the anorthosite massif within the Korosten plutonic complex. Geological data indicate hybridization of basic melts and partly crystallized granites, as well as direct impact of fluids derived from basic melts on the chamber pegmatites. The new U–Pb zircon ages obtained for granites and pegmatites of the Korosten complex confirm that the rock assemblage in the northern part of the complex crystallized between 1800 and 1780 Ma, whereas rocks in the southern part intruded mainly between 1768 and 1755 Ma. U–Pb zircon ages for granites from the south-western part of the Korosten complex indicate that granites were emplaced at 1770–1765 Ma, a few million years prior to the intrusion of the gabbro–anorthosite massif (1762–1758 Ma), while chamber pegmatites in these granites crystallized at 1760 ± 3 Ma, coevally with the basic rocks. Ultimately, the formation of the chamber pegmatites was related to the reheating of the semi-crystallized granitic intrusion and to fluids migrating from the underlying gabbro–anorthosite massif.

Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

New insights in the mechanisms of the reaction 3.65 Å phase = clinoenstatite + water down to nanoscales

The reaction of 3.65 Å phase <=> clinoenstatite + water was investigated in five experiments at 10 GPa, 470–600 ∘C, using a rotating multi-anvil press. Under these P/T conditions, clinoenstatite exists in its high-pressure modification, which, however, is not quenchable to ambient conditions but transforms back to low-pressure clinoenstatite. The quenched run products were characterized by electron microprobe analyses (EMPA), powder X-ray diffraction (XRD), Raman spectroscopy and by high-resolution transmission electron microscopy (HRTEM) on focused ion beam (FIB)-cut foils. We bracketed the reaction in the T range 470 to 510 ∘C (at 10 GPa). The hydration of clinoenstatite to the 3.65 Å phase at 470 ∘C was very sluggish and incomplete even after 96 h. Clinoenstatites range in size from less than 1 to up to 50 µm. Usually clinoenstatite has a very small grain size and shows many cracks. In sub-micron-sized broken clinoenstatite, an amorphous phase (0.91Mg:1.04Si, with about 20 wt % H2O) was observed, which further transformed with increasing reaction time into the 3.65 Å phase (1Mg:1Si, with 34 wt % H2O). Thus, the sub-micron-sized fractured clinoenstatite transformed via an amorphous water-bearing precursor phase to the 3.65 Å phase. The dehydration to clinoenstatite was faster but still incomplete after 72 h at 600 ∘C. From the backscattered electron images of the recovered sample of the dehydration experiment, it is obvious that there is a high porosity due to dehydration of the 3.65 Å phase. Again, the grain size of clinoenstatite ranges from less than 1 up to 50 µm. There are still some clinoenstatite crystals from the starting material present, which can clearly be distinguished from newly formed sub-micron-sized clinoenstatite. Additionally, we observe a water-rich crystalline phase, which does not represent the 3.65 Å phase. Its Raman spectra show the double peaks around 700 and 1000 cm−1 characteristic for enstatite and strong water bands at 3700 and 3680 cm−1. The Mg:Si ratio of 0.90:1.04 was determined by EMPA, totalling to 81 wt %, in accordance with its high water content. Diffraction patterns from high-resolution images (fast Fourier transform – FFT) are in agreement with an orthoenstatite crystal structure (Pbca). The surprising observation of this study is that, in both directions of the investigated simple reaction, additional metastable phases occur which are amorphous in the hydration and crystalline in the dehydration reaction. Both additional phases are water rich and slightly deviate in composition from the stable products 3.65 Å phase and clinoenstatite, respectively. Thus, as a general remark, conventional investigations on reaction progress should be complemented by nanoscale investigations of the experimental products because these might reveal unpredicted findings relevant for the understanding of mantle processes. The extreme reduction in grain size observed in the dehydration experiments due to the formation of nanocrystalline clinoenstatite rather than the slowly released fluids might cause mechanical instabilities in the Earth's mantle and, finally, induce earthquakes.

Zinkgruvanite, Ba₄Mn²⁺₄Fe³⁺₂(Si₂O₇)₂(SO₄)₂O₂(OH)₂, a new ericssonite-group mineral from the Zinkgruvan Zn-Pb-Ag-Cu deposit, Askersund, Örebro County, Sweden

Zinkgruvanite, ideally Ba4Mn42+Fe23+(Si2O7)2(SO4)2O2(OH)2, is a new member of the ericssonite group, found in Ba-rich drill core samples from a sphalerite- and galena- and diopside-rich metatuffite succession from the Zinkgruvan mine, Örebro County, Sweden. Zinkgruvanite is associated with massive baryte, barytocalcite, diopside and minor witherite, cerchiaraite-Al, and sulfide minerals. It occurs as subhedral to euhedral flattened and elongated crystals up to 4 mm. It is almost black and semi-opaque with a dark-brown streak. The lustre is vitreous to sub-adamantine on crystal faces and resinous on fractures. The mineral is brittle with an uneven fracture. VHN100=539, and HMohs ≈ 4.5. In thin fragments, it is reddish-black, translucent and optically biaxial (+), 2Vz > 70∘. Pleochroism is strong and deep brown-red (E ⊥ {001} cleavage) to olive-pale-brown. Chemical point analyses by WDS-EPMA (wavelength-dispersive X-ray spectroscopy electron probe microanalyser) together with iron valencies determined from Mössbauer spectroscopy yielded the empirical formula (based on 26 O+OH+F+Cl anions): (Ba4.02Na0.03)Σ4.05(Mn1.79Fe1.562+Fe0.423+Mg0.14Ca0.10Ni0.01Zn0.01)Σ4.03(Fe1.743+Ti0.20Al0.06)Σ2.00Si4(S1.61Si0.32P0.07)Σ1.99O24(OH1.63Cl0.29F0.08)Σ2.00. The mineral is triclinic, in space group P1¯, with unit-cell parameters a=5.3982(1) Å, b=7.0237(1) Å, c=14.8108(4) Å, α= 98.256(2)∘, β= 93.379(2)∘, γ= 89.985(2)∘ and V= 554.75(2) Å3 for Z=1. The eight strongest X-ray powder diffraction lines are the following (d Å (I %; hkl)): 3.508 (70; 103), 2.980(70; 114‾), 2.814 (68; 12‾2), 2.777 (70; 121), 2.699 (714; 200), 2.680 (68; 201‾), 2.125 (100; 124, 204) and 2.107 (96; 2‾21). The crystal structure (R1=0.0379 for 3204 reflections) is an array of TS (titanium silicate) blocks alternating with intermediate blocks. The TS blocks consist of HOH sheets (H for heteropolyhedral and O for octahedral) parallel to (001). In the O sheet, the Mn2+-dominant MO(1,2,3) sites give ideally Mn42+ pfu (per formula unit). In the H sheet, the Fe3+-dominant MH sites and AP(1) sites give ideally Fe23+Ba2 pfu. In the intermediate block, SO4 oxyanions and 11 coordinated Ba atoms give ideally 2× SO4Ba pfu. Zinkgruvanite is related to ericssonite and ferroericssonite in having the same topology and type of linkage of layers in the TS block. Zinkgruvanite is also closely compositionally related to yoshimuraite, Ba4Mn4Ti2(Si2O7)2(PO4)2O2(OH)2, via the coupled heterovalent substitution 2 Ti4++ 2 (PO4)3-→2 Fe3++ 2 (SO4)2− but presents a different type of linkage. The new mineral probably formed during a late stage of regional metamorphism of a Ba-enriched, syngenetic protolith, involving locally generated oxidized fluids of high salinity.

First-principles modeling of the infrared spectrum of Fe- and Al-bearing lizardite

The theoretical vibrational properties of a series of Fe- and Al-bearing lizardite models have been determined at the density functional theory level. Each periodic model displays a single cationic impurity substituted at an octahedral or tetrahedral site of a supercell of lizardite (Mg3Si2O5(OH)4) containing 162 atoms. The isovalent Fe2+ for Mg2+ substitution has been considered, as well as the heterovalent substitution of Fe3+ or Al3+ for Mg2+ or Si4+. Comparison of the theoretical absorption spectra with previously reported experimental spectra of natural and laboratory-grown lizardite samples allows us to propose an interpretation for most of the observed bands. Although the identification of specific bands related to octahedral Fe2+ in FTIR spectra is challenging, broad bands at 3584 and 3566 cm−1 reflect the occurrence of octahedral Al3+ and Fe3+, respectively, in the natural samples. These broad bands likely overlap with potential contribution related to tetrahedral Al3+. It is suggested that the modification of the H-bonding pattern related to the incorporation of trivalent ions at tetrahedral sites has an overall broadening effect on the interlayer-OH stretching bands of lizardite.